JP2009217037A - Photosensitive film, method for producing the same, and permanent pattern forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide: a photosensitive film which includes a photosensitive layer of stable plane shape free of foreign matter defects, and is suitably used in the manufacture of a printed wiring board, a high density multilayer board, a semiconductor package, and the like; and a method for producing the photosensitive film. <P>SOLUTION: The method for producing the photosensitive film includes: a dispersion preparation step of preparing a dispersion containing a binder, a heat curing accelerator, and a silica compound as a filler; a filtration step of filtering the prepared dispersion through a filter having an average hole diameter of 10-30 μm; a photosensitive composition preparation step of preparing a photosensitive composition by adding a polymerizable compound and a heat crosslinking agent to the filtered dispersion; and a photosensitive layer formation step of forming the photosensitive layer by applying the prepared photosensitive composition on a support. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a photosensitive film, a method for producing the same, and a method for forming a permanent pattern (a protective film, an interlayer insulating film, a solder resist, etc.), and in particular, for producing printed wiring boards, high-density multilayer boards, semiconductor packages, and the like. The present invention relates to a photosensitive film suitably used, a method for producing the same, a wiring board and an electronic component module, and is excellent in heat fatigue resistance, moisture resistance, insulation, and the like, and relates to an efficient method for forming a high-definition permanent pattern.

In general, in a printed wiring board having a conductor circuit, a permanent pattern such as a solder resist is formed on the surface of the printed wiring board having the conductor circuit in order to protect the conductor circuit from oxidation and peeling.
In recent printed wiring boards, as electronic devices have become smaller and lighter and have higher performance, there is an increasing need to increase the density of conductive circuits, etc. A high-definition permanent pattern is required for forming a solder resist or forming an interlayer resin insulation layer of a multilayer printed wiring board. As a method of forming such a permanent pattern, a photosensitive pattern (polymerizable composition) solution is applied to the printed wiring board and the photosensitive layer is laminated, and a permanent pattern forming method using a liquid photo solder resist or a photosensitive layer is laminated. A permanent pattern forming method is often used in which the photosensitive film formed is transferred to the printed wiring board.

As a method for producing the photosensitive film, a method is generally used in which a photosensitive composition coating solution obtained by preparing a photosensitive composition with a solvent is applied onto the support to form the photosensitive layer. ing. In the photosensitive composition, a polymerization inhibitor, a binder, a polymerizable compound, a thermal cross-linking agent, a filler (for example, a silica compound) are used in order to improve the resolution by increasing the photosensitivity and further improve the storage stability. Etc. are included (patent documents 1 to 5).
As the silica compound, for example, when a sol-gel synthesized method is used, the sol-gel synthesized method contains a large amount of Na ⁺ ions, so the photosensitive film is used as an electronic material. I can't do that. Therefore, as the silica compound, one produced by a combustion method that does not contain a lot of Na ⁺ ions is usually used.

However, the silica produced by the combustion method usually shows a particle size distribution of 0.1 μm to 5 μm, but the silica produced by the combustion method is outside the particle size distribution range of 0.1 μm to 5 μm. When coarse particles of 20 μm or more are contained in several ppm to several hundred ppm, and a photosensitive composition containing these coarse particles is applied on a support, there is a problem that foreign matter failure occurs.
Although a method for efficiently filtering and removing fine particles in a resist solution has already been disclosed (for example, Patent Documents 6 and 7), a photosensitive composition using a silica compound as a filler is provided on a support. There has been no disclosure of efficiently suppressing foreign matter failure that occurs during coating, and a method for efficiently suppressing foreign matter failure has long been desired.

JP 2002-268211 A JP 2003-29399 A JP 2004-4527 A Japanese Patent Laid-Open No. 2004-4528 JP 2007-156404 A JP 2007-253126 A JP 2002-99098 A

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention provides a photosensitive film suitable for the production of printed wiring boards, high-density multilayer boards, semiconductor packages, and the like, and a method for producing the same, in which a stable planar photosensitive layer free from foreign matter failure can be obtained. The purpose is to do. The present invention is also used for wiring boards and electronic component modules by a photosensitive layer formed by the method for producing a photosensitive film, and has excellent heat fatigue resistance, moisture resistance, insulation, etc., and has a high-definition permanent pattern. It is to provide an efficient forming method.

Means for solving the problems are as follows. That is,
<1> A dispersion preparing step of preparing a dispersion containing a binder, a thermosetting accelerator, and a silica compound as a filler, and a filtration step of filtering the prepared dispersion with a filter having an average pore size of 10 to 30 μm. A photosensitive composition preparation step of preparing a photosensitive composition by adding a polymerizable compound and a thermal crosslinking agent to the filtered dispersion, and applying the prepared photosensitive composition on a support And a photosensitive layer forming step of forming a photosensitive layer.
According to the method for producing a photosensitive film described in <1>, after preparing a dispersion containing a binder, a thermosetting accelerator, and a silica compound as a filler, the dispersion has an average pore size of 10 to 30 μm. Therefore, even if coarse particles of 20 μm or more are contained in the silica compound in a few ppm to several hundred ppm, a stable planar photosensitive layer free from foreign matter failure can be obtained.
<2> The method for producing a photosensitive film according to <1>, wherein the silica compound is silica produced by a combustion method.
<3> The method for producing a photosensitive film according to any one of <1> to <2>, wherein the average particle diameter of the dispersed particles in the dispersion is 0.1 to 5 μm.
According to the method for producing a photosensitive film described in <3>, since the average particle diameter of the dispersed particles in the dispersion is 0.1 to 5 μm, the viscosity of the dispersion can be maintained in a more suitable state for a long time. it can.
<4> The method for producing a photosensitive film according to any one of <1> to <3>, wherein the photosensitive composition contains a photopolymerization initiator.
According to the method for producing a photosensitive film described in <4>, since the photosensitive composition contains a photopolymerization initiator, photosensitivity is imparted to the photosensitive composition, and a photosensitive composition can be obtained. . Accordingly, the photosensitive composition can be suitably used as a solder resist or the like.
<5> The method for producing a photosensitive film according to any one of <1> to <4>, wherein the thermosetting accelerator is a solid.
<6> The thermosetting accelerator is selected from amine compounds, imidazole derivatives, quaternary ammonium salt compounds, phosphorus compounds, guanamine compounds, S-triazine derivatives, aromatic acid anhydrides, aliphatic acid anhydrides, and polyphenols. It is a manufacturing method of the photosensitive film in any one of said <1> to <5> which is at least 1 sort.
<7> The method for producing a photosensitive film according to any one of <1> to <6>, wherein the content of the silica compound is 5 to 50% by mass.
<8> The method for producing a photosensitive film according to any one of <1> to <7>, wherein the binder includes a polymer compound having an acidic group and an ethylenically unsaturated bond in a side chain.
<9> A binder in which a polymerizable compound containing a cyclic ether group is added to a part of an acidic group of a polymer compound in the presence of a catalyst, and a part or all of a cyclic ether group of a polymer compound is carboxylated <1> to <1> wherein the polymer compound is selected from any of those obtained by adding a polymerizable compound containing a group in the presence of a catalyst, and the catalyst is selected from either an acidic compound or a neutral compound. 8>. The method for producing a photosensitive film according to any one of 8>.
<10> The binder according to any one of <1> to <8>, wherein the binder includes a polymer compound having an acidic group, an aromatic group that may include a heterocyclic ring, and an ethylenically unsaturated bond in a side chain. It is a manufacturing method of the photosensitive film of.
<11> The method for producing a photosensitive film according to any one of <1> to <7>, wherein the binder comprises a compound in which an ethylenically unsaturated double bond and an acidic group are introduced into an epoxy compound.
<12> The method for producing a photosensitive film according to any one of <1> to <7>, wherein the binder includes a vinyl copolymer having a (meth) acryloyl group and an acidic group in a side chain.
<13> From the above <1> to <7, wherein the binder is a copolymer obtained by reacting 0.1 to 1.2 equivalents of a primary amine compound with respect to the anhydride group of the maleic anhydride copolymer. > A method for producing a photosensitive film according to any one of the above.
<14> The method for producing a photosensitive film according to any one of <1> to <13>, wherein the polymerizable compound includes at least one selected from monomers having a (meth) acrylate group. .
<15> From the above <1>, wherein the thermal crosslinking agent is at least one selected from an epoxy resin compound, an oxetane compound, a polyisocyanate compound, a compound obtained by reacting a polyisocyanate compound with a blocking agent, and a melamine derivative. <14> A method for producing a photosensitive film according to any one of the above.

  <16> A photosensitive film produced by the method for producing a photosensitive film according to any one of <1> to <15>.

<17> A method for forming a permanent pattern, wherein the photosensitive layer in the photosensitive film according to <16> is transferred to a surface of a substrate, and then exposed and developed.
<18> The method for forming a permanent pattern according to <17>, wherein the exposure is performed using a laser beam having a wavelength of 395 to 415 nm.
<19> The method for forming a permanent pattern according to any one of <17> to <18>, wherein after the development, the photosensitive layer is subjected to a curing treatment.
In the method for forming a permanent pattern described in <19>, after the development, the curing process is performed on the photosensitive layer. As a result, the film strength of the cured region of the photosensitive layer is increased.
<20> The method for forming a permanent pattern according to <19>, wherein the curing treatment is at least one of a whole surface exposure treatment and a whole surface heat treatment performed at 120 to 200 ° C.
In the permanent pattern forming method according to <20>, curing of the resin in the photosensitive composition is promoted in the entire surface exposure process. Moreover, the film | membrane intensity | strength of a cured film is raised in the whole surface heat processing performed on the said temperature conditions.
<21> The method for forming a permanent pattern according to any one of <17> to <20>, wherein at least one of a protective film, an interlayer insulating film, and a solder resist pattern is formed.
In the permanent pattern forming method according to <21>, since at least one of a protective film, an interlayer insulating film, and a solder resist pattern is formed, the wiring is externally provided due to the insulation, heat resistance, etc. of the film. Protected from impact and bending.

<22> A permanent pattern formed by the method for forming a permanent pattern according to any one of <17> to <21>.
Since the permanent pattern according to <22> is formed by the permanent pattern forming method, it has excellent chemical resistance, surface hardness, heat resistance, and the like, and has high definition and multilayer wiring of semiconductors and components. This is useful for high-density mounting on boards and build-up wiring boards.
<23> The permanent pattern according to <22>, which is at least one of a protective film, an interlayer insulating film, and a solder resist pattern.
Since the permanent pattern according to <23> is at least one of a protective film, an interlayer insulating film, and a solder resist pattern, the wiring may be subjected to external impact or bending due to the insulating property, heat resistance, etc. Protected from.

  According to the present invention, there is provided a photosensitive film which can obtain a stable planar photosensitive layer free from foreign matter failure, and can be suitably used for manufacturing printed wiring boards, high-density multilayer boards, semiconductor packages, and the like, and a method for manufacturing the same. can do. The present invention is also used for wiring boards and electronic component modules by a photosensitive layer formed by the method for producing a photosensitive film, and has excellent heat fatigue resistance, moisture resistance, insulation, etc., and has a high-definition permanent pattern. An efficient forming method can be provided.

(Method for producing photosensitive film)
The method for producing a photosensitive film of the present invention includes a dispersion preparing step, a filtration step, a photosensitive composition preparing step, a photosensitive layer forming step, and other steps appropriately selected as necessary. From the viewpoint of imparting photosensitivity to the photosensitive composition obtained in the photosensitive composition preparation step, the photosensitive composition preferably contains a photopolymerization initiator.

<Dispersion preparation process>
The dispersion preparation step is a step of preparing a dispersion containing a binder, a thermosetting accelerator, and a silica compound as a filler.
The dispersion preparation process includes a dispenser system, a static mixer, a micro mixer, and the like that automatically perform the preparation of the dispersion, the preparation of the photosensitive composition by mixing the thermal crosslinking agent, and the application of the photosensitive composition. You may carry out using a mixer, an in-line mixing apparatus, etc.
The average dispersed particle size of the dispersed particles in the dispersion is preferably from 0.1 to 5 μm, and more preferably from 0.5 to 3 μm. When the average dispersed particle size is less than 0.1 μm, the viscosity of the dispersion may increase due to coalescence or agglomeration of the dispersed particles. When the average dispersed particle size exceeds 5 μm, sedimentation of the dispersed particles occurs, resulting in a stable liquid viscosity. May not be obtained.
The average particle diameter of the dispersed particles in the dispersion is a volume average particle diameter, and can be measured by, for example, a particle diameter measuring device (LB-500: manufactured by Horiba, Ltd.).

<Filtration process>
The filtration step is a step of filtering the prepared dispersion with a filter having an average pore size of 10 to 30 μm. Here, the average pore size of the filter is the manufacturer's nominal pore size value and the nominal filtration accuracy or absolute filtration accuracy. In particular, the absolute filtration accuracy is a display method that can remove all foreign substances beyond the display, and has high reliability. Examples of manufacturers include Nippon Pole Co., Ltd. and Nihon Millipore Co., Ltd.
The filtration method of the dispersion is not particularly limited as long as it is filtration using a filter having an average pore size of 10 to 30 μm, and can be appropriately selected according to the purpose. For example, suction filtration using a pump, And pressure filtration with air etc. are mentioned.
There is no restriction | limiting in particular as a material of the said filter, According to the objective, it can select suitably, For example, polyamide resins, such as polyolefin resin, such as a polypropylene and polyethylene, nylon 6 and nylon 66, and stainless steel are mentioned.
There is no restriction | limiting in particular as a shape of the said filter, According to the objective, it can select suitably, For example, a disk type, a cartridge type, and a filter cloth shape are mentioned.

<Photosensitive composition preparation process>
The photosensitive composition preparation step is a step of preparing a photosensitive composition by adding a polymerizable compound and a thermal crosslinking agent to the filtered dispersion.
The method for adding (mixing) the polymerizable compound and the thermal cross-linking agent is not particularly limited and may be appropriately selected depending on the purpose. For example, the polymerizable compound and the thermal cross-linking agent are included. It is prepared by dissolving, emulsifying and dispersing other components appropriately selected in a solvent.
Specifically, there is a method in which a polysynthetic compound and a solution obtained by dissolving a thermal crosslinking agent in a solvent are mixed with the dispersion. Further, there is a method in which a liquid obtained by dissolving a polysynthetic compound in a solvent and a liquid obtained by dissolving a thermal crosslinking agent in a solvent are mixed with the dispersion. Furthermore, there is a method of mixing the polysynthetic compound and the thermal crosslinking agent in the dispersion without dissolving them in a solvent.
The preparation may be performed using the dispenser system, a static mixer, a micromixer, an in-line mixing device, or the like.
When the polymerizable compound, the thermal crosslinking agent, and the dispersion component are mixed before the coating step and the coating solution is prepared, after a long time has elapsed, a crosslinking reaction is initiated by the thermal crosslinking agent, and the viscosity of the coating solution increases. Sometimes.
Specifically, the coating liquid containing the photosensitive composition obtained by mixing the thermal crosslinking agent is preferably applied within 72 hours after preparation, and more preferably within 24 hours after preparation of the coating liquid. If the coating solution is applied after 72 hours have elapsed after the preparation of the coating solution, the viscosity of the solution increases and a suitable coating may not be performed, and a stable surface state of the photosensitive layer may not be obtained.
The viscosity of the photosensitive composition obtained by mixing the polymerizable compound and the thermal crosslinking agent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the viscosity is 10 to 200 cp (mPa · s). 30 to 100 cp (mPa · s) is more preferable. When the viscosity is less than 10 cp (mPa · s), it becomes more fluid, and when the photosensitive layer is formed, the target thickness may not be obtained efficiently, and when it exceeds 200 cp (mPa · s). In some cases, the fluidity of the photosensitive layer decreases, and ripples, pitch streaks such as white streaks and streaks such as black unevenness occur on the surface of the photosensitive layer, and a stable coated surface may not be obtained.

  The viscosity is measured using a viscometer. The viscometer is not particularly limited and may be appropriately selected depending on the purpose. For example, (1) in accordance with Hagen-Poiseuille's law, a time required for a certain amount of sample to flow out through the capillary tube Obtain: Capillary viscometer, (2) Obtain from object fall speed or bubble rise speed in sample according to Stokes' law: Bubble viscometer, fallen body viscometer, Hepra viscometer, viscolator, (3) Received by object in fluid Obtained from viscosity resistance: rotational viscometer, vibration viscometer, flat plate viscometer and the like can be mentioned.

-binder-
The binder is preferably a compound that is insoluble in water and swells or dissolves in an alkaline aqueous solution.
The binder is preferably a polymer compound containing an acidic group and an ethylenically unsaturated bond in the side chain. Examples of the acidic group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group, and a carboxyl group is preferable from the viewpoint of obtaining raw materials.
In addition, as the binder, at least one polymerizable double bond in the molecule, for example, an acrylic group such as a (meth) acrylate group or a (meth) acrylamide group, a vinyl ester of carboxylic acid, a vinyl ether, an allyl ether, etc. Various polymerizable double bonds can be used. More specifically, an acrylic resin containing a carboxyl group as an acidic group, a cyclic ether group-containing polymerizable compound such as a glycidyl ester of an unsaturated fatty acid such as glycidyl acrylate, glycidyl methacrylate, cinnamic acid, or an alicyclic epoxy group. Examples thereof include compounds obtained by adding an epoxy group-containing polymerizable compound such as a compound having a (meth) acryloyl group (for example, an epoxy group such as cyclohexene oxide in the same molecule). In addition, a compound obtained by adding an isocyanate group-containing polymerizable compound such as isocyanate ethyl (meth) acrylate to an acrylic resin containing an acidic group and a hydroxyl group, an acrylic resin containing an anhydride group, a hydroxyalkyl ( Examples thereof include compounds obtained by adding a polymerizable compound containing a hydroxyl group such as (meth) acrylate. Also included are compounds obtained by copolymerizing cyclic ether group-containing polymerizable compounds such as glycidyl methacrylate and vinyl monomers such as (meth) acryloyl alkyl esters and adding (meth) acrylic acid to the side chain epoxy groups. It is done.
Examples of these include Japanese Patent No. 2763775, Japanese Patent Laid-Open No. 3-172301, Japanese Patent Laid-Open No. 2000-232264, and the like.

Among these, the binder is obtained by adding a cyclic ether group (for example, a group having an epoxy group or an oxetane group in a partial structure) -containing polymerizable compound to a part of the acidic group of the polymer compound, and the polymer compound More preferably, the polymer is selected from any of those obtained by adding a carboxyl group-containing polymerizable compound to a part or all of the cyclic ether group. In this case, the addition reaction between the acidic group and the compound having a cyclic ether group is preferably carried out in the presence of a catalyst. In particular, the catalyst is preferably selected from an acidic compound and a neutral compound.
Among them, from the viewpoint of development stability of the photosensitive composition over time, the binder is a polymer compound containing an aromatic group which may contain a carboxyl group and a heterocycle in the side chain, and an ethylenically unsaturated bond in the side chain. Is preferred.

-Aromatic group which may contain a heterocycle-
Examples of the aromatic group that may include the heterocycle (hereinafter, also simply referred to as “aromatic group”) include, for example, a benzene ring, a group in which 2 to 3 benzene rings form a condensed ring, A benzene ring and a 5-membered unsaturated ring formed a condensed ring.
Specific examples of the aromatic group include phenyl group, naphthyl group, anthryl group, phenanthryl group, indenyl group, acenaphthenyl group, fluorenyl group, benzopyrrole ring group, benzofuran ring group, benzothiophene ring group, pyrazole ring group, isoxazole. Ring group, isothiazole ring group, indazole ring group, benzisoxazole ring group, benzisothiazole ring group, imidazole ring group, oxazole ring group, thiazole ring group, benzimidazole ring group, benzoxazole ring group, benzothiazole ring Group, pyridine ring group, quinoline ring group, isoquinoline ring group, pyridazine ring group, pyrimidine ring group, pyrazine ring group, phthalazine ring group, quinazoline ring group, quinoxaline ring group, acylidine ring group, phenanthridine ring group, carbazole ring Group, purine ring group, pyran ring group, Lysine ring group, a piperazine ring group, an indole ring group, an indolizine ring group, a chromene ring group, a cinnoline ring group, an acridine ring group, a phenothiazine ring group, a tetrazole ring group, such as a triazine ring group. In these, a hydrocarbon aromatic group is preferable and a phenyl group and a naphthyl group are more preferable.

  The aromatic group may have a substituent. Examples of the substituent include a halogen atom, an amino group which may have a substituent, an alkoxycarbonyl group, a hydroxyl group, an ether group, a thiol group, A thioether group, a silyl group, a nitro group, a cyano group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, and the like, each of which may have a substituent, may be mentioned.

Examples of the alkyl group include linear alkyl groups having 1 to 20 carbon atoms, branched alkyl groups, and cyclic alkyl groups.
Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group. , Octadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group , Cyclopentyl group, 2-norbornyl group and the like. Among these, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, and a cyclic alkyl group having 5 to 10 carbon atoms are preferable.

Examples of the substituent that the alkyl group may have include a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom. Examples of such substituents include halogen atoms (—F, —Br, —Cl, —I), hydroxyl groups, alkoxy groups, aryloxy groups, mercapto groups, alkylthio groups, arylthio groups, alkyldithio groups, aryldithio groups. Group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfo Xyl group, acylthio group, acylamino group, N-a Killacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N′-arylureido group, N ′, N′-diarylureido group, N '-Alkyl-N'-arylureido group, N-alkylureido group, N-arylureido group, N'-alkyl-N-alkylureido group, N'-alkyl-N-arylureido group, N', N ' -Dialkyl-N-alkylureido group, N ', N'-dialkyl-N-arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N-arylureido group, N', N ' -Diaryl-N-alkylureido group, N ', N'-diaryl-N-arylureido group, N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl-N '-Aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N- Alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl Group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group ( Referred to as -SO 3 _H) and its conjugated base group (a sulfonato group), alkoxy sulfonyl group, aryloxy sulfonyl group, sulfinamoyl group, N- alkylsulfinamoyl group, N, N- dialkyl sulfide Inamo yl group, N- Arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N - arylsulfamoyl group, (referred to as phosphonato group) N, N- diaryl sulfamoyl group, N- alkyl -N- arylsulfamoyl group, a phosphono group _(-PO 3 _{H 2)} and its conjugated base group, Dialkylphosphono group (—PO ₃ (alkyl) ₂ ) (hereinafter “alkyl” means an alkyl group) Taste. ), Diaryl phosphono group _{(-PO 3 (aryl) 2)} ( hereinafter, "aryl" means an aryl group.), Alkyl aryl phosphono group _{(-PO 3 (alkyl) (aryl} )), monoalkyl phosphonates Group (—PO ₃ (alkyl)) and its conjugate base group (referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group (referred to as arylphosphonate group) ), A phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (referred to as a phosphonatoxy group), a dialkylphosphonooxy group (—OPO ₃ H (alkyl) ₂ ), a diarylphosphonooxy group (—OPO ₃ (aryl)) ) _2), alkylaryl phosphono group _{(-OPO 3 (alkyl) (aryl} )), monoalkyl phosphonates Oxy group _(-OPO 3 H (alkyl)) and its conjugated base group (referred to as alkylphosphonato group), monoarylphosphono group _(-OPO 3 H (aryl)) and its conjugate base (aryl phosphite Hona preparative oxy Group), cyano group, nitro group, aryl group, alkenyl group, alkynyl group, heterocyclic group, silyl group and the like.

Specific examples of the alkyl group in these substituents include the aforementioned alkyl groups.
Specific examples of the aryl group in the substituent include phenyl, biphenyl, naphthyl, tolyl, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxy Phenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxy Carbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, cyanophenyl group, sulfophenyl group, sulphonatophenyl group, phosphonopheny Groups, such as phosphate Hona preparative phenyl group.

Specific examples of the alkenyl group in the substituent include a vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group and the like.
Specific examples of the alkynyl group in the substituent include ethynyl group, 1-propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like.
Examples of ^{R 01} of the acyl group in the substituents ^(R 01 CO-), a hydrogen atom, an alkyl group described above, and aryl groups.
Among these substituents, halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N-dialkylamino groups, acyloxy groups Group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N- Dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-aryl Sulfamoyl group, N-alkyl N-arylsulfamoyl group, phosphono group, phosphonato group, dialkylphosphono group, diarylphosphono group, monoalkylphosphono group, alkylphosphonato group, monoarylphosphono group, arylphosphonato group, phosphonooxy group, phosphonatoxy Group, aryl group, alkenyl group and the like are preferable.
Moreover, examples of the heterocyclic group in the substituent include a pyridyl group and a piperidinyl group, and examples of the silyl group in the substituent include a trimethylsilyl group.

On the other hand, examples of the alkylene group in the alkyl group include those obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms to obtain a divalent organic residue. For example, a linear alkylene group having 1 to 12 carbon atoms, a branched alkylene group having 3 to 12 carbon atoms, and a cyclic alkylene group having 5 to 10 carbon atoms are preferable.
Preferable specific examples of the substituted alkyl group obtained by combining such a substituent and an alkylene group include a chloromethyl group, a bromomethyl group, a 2-chloroethyl group, a trifluoromethyl group, a methoxymethyl group, and an isopropoxymethyl group. , Butoxymethyl group, s-butoxybutyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, pyridylmethyl group, tetramethylpiperidinylmethyl group, N-acetyltetra Methylpiperidinylmethyl group, trimethylsilylmethyl group, methoxyethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl Group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxycarbonylbutyl group, chloro Phenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group, Sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphonov Nyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl Group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1- Examples include propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group and the like.

Examples of the aryl group include a benzene ring, a group in which 2 to 3 benzene rings form a condensed ring, and a group in which a benzene ring and a 5-membered unsaturated ring form a condensed ring.
Specific examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. In these, a phenyl group and a naphthyl group are preferable.
The alkyl group may have a substituent, and examples of the aryl group having such a substituent (hereinafter sometimes referred to as “substituted aryl group”) include the ring-forming carbon of the above-described aryl group. The thing which has group which consists of monovalent nonmetallic atomic groups other than a hydrogen atom as a substituent on an atom is mentioned.
As the substituent that the aryl group may have, for example, those described above as the substituent that the alkyl group, the substituted alkyl group, and the alkyl group may have are preferable.

  Preferred examples of the substituted aryl group include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group, hydroxyphenyl. Group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, benzoyloxyphenyl Group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, Nyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl group, methyl Phosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allylphenyl group, 1-propenylmethylphenyl group, 2-butenylphenyl group, 2-methylallylphenyl group, 2- Examples thereof include a methylpropenylphenyl group, a 2-propynylphenyl group, a 2-butynylphenyl group, and a 3-butynylphenyl group.

Examples of the alkenyl group (—C (R ⁰² ) ═C (R ⁰³ ) (R ⁰⁴ )) and the alkynyl group (—C≡C (R ⁰⁵ )) include, for example, R ⁰² , R ⁰³ , R ⁰⁴ , and R ^A group in which ⁰⁵ is a group composed of a monovalent non-metallic atomic group is exemplified.
Examples of R ⁰² , R ⁰³ , R ⁰⁴ , and R ⁰⁵ include a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group. Specific examples thereof include those shown as the above-mentioned examples. Among these, a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group, and a cyclic alkyl group are preferable.

Preferable specific examples of the alkenyl group and alkynyl group include a vinyl group, 1-propenyl group, 1-butenyl group, 1-pentenyl group, 1-hexenyl group, 1-octenyl group, 1-methyl-1-propenyl group, 2-methyl-1-propenyl group, 2-methyl-1-butenyl group, 2-phenyl-1-ethenyl group, 2-chloro-1-ethenyl group, ethynyl group, 1-propynyl group, 1-butynyl group, phenyl Examples include an ethynyl group.
As said heterocyclic group, the pyridyl group illustrated as a substituent of a substituted alkyl group etc. are mentioned, for example.

Examples of the oxy group (R ⁰⁶ O—) include those in which R ⁰⁶ is a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom.
Examples of such oxy groups include alkoxy groups, aryloxy groups, acyloxy groups, carbamoyloxy groups, N-alkylcarbamoyloxy groups, N-arylcarbamoyloxy groups, N, N-dialkylcarbamoyloxy groups, N, N- A diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, phosphonooxy group, phosphonatoxy group and the like are preferable.
Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Examples of the acyl group (R ⁰⁷ CO—) in the acyloxy group include those in which R ⁰⁷ is an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group mentioned above. Among these substituents, an alkoxy group, an aryloxy group, an acyloxy group, and an arylsulfoxy group are more preferable.
Specific examples of preferred oxy groups include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, pentyloxy, hexyloxy, dodecyloxy, benzyloxy, allyloxy, phenethyloxy, carboxy Ethyloxy group, methoxycarbonylethyloxy group, ethoxycarbonylethyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, morpholinoethoxy group, morpholinopropyloxy group, allyloxyethoxyethoxy group, phenoxy Group, tolyloxy group, xylyloxy group, mesityloxy group, mesityloxy group, cumenyloxy group, methoxyphenyloxy group, ethoxyphenyloxy group, chlorophenyloxy group Group, bromophenyl group, acetyloxy group, benzoyloxy group, naphthyloxy group, a phenylsulfonyloxy group, a phosphonooxy group, a phosphonatooxy group.

As the amino group (R ⁰⁸ NH—, (R ⁰⁹ ) (R ⁰¹⁰ ) N—) which may contain an amide group, for example, R ⁰⁸ , R ⁰⁹ , and R ⁰¹⁰ are monovalent nonmetallic atoms excluding a hydrogen atom A group consisting of a group is mentioned. R ⁰⁹ and R ⁰¹⁰ may be bonded to form a ring.
Examples of the amino group include N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acylamino group, N -Alkylacylamino group, N-arylacylamino group, ureido group, N'-alkylureido group, N ', N'-dialkylureido group, N'-arylureido group, N', N'-diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N′-alkyl-N-arylureido group, N ′, N '-Dialkyl-N-alkylureido group, N'-alkyl-N'-arylureido group, N', N'-dialkyl-N-alkylureido group, N ', N'- Alkyl-N′-arylureido group, N′-aryl-N-alkylureido group, N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N ′ -Diaryl-N-arylureido group, N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino Group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group and the like. It is done. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Also, ^{R 07} acylamino group, N- alkylacylamino group, N- arylacylamino group definitive acyl group ^(R 07 CO-) are as defined above. Of these, an N-alkylamino group, an N, N-dialkylamino group, an N-arylamino group, and an acylamino group are more preferable.
Specific examples of preferred amino groups include methylamino group, ethylamino group, diethylamino group, morpholino group, piperidino group, pyrrolidino group, phenylamino group, benzoylamino group, acetylamino group and the like.

Examples of the sulfonyl group (R ⁰¹¹ —SO ₂ —) include those in which R ⁰¹¹ is a group composed of a monovalent nonmetallic atomic group.
As such a sulfonyl group, for example, an alkylsulfonyl group, an arylsulfonyl group, and the like are preferable. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group.
Specific examples of the sulfonyl group include a butylsulfonyl group, a phenylsulfonyl group, and a chlorophenylsulfonyl group.

As described above, the sulfonate group (—SO ₃ —) means a conjugated base anion group of a sulfo group (—SO ₃ H), and is usually preferably used together with a counter cation.
As such counter cations, generally known ones can be appropriately selected and used. For example, oniums (for example, ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.), metal ions (For example, Na ⁺ , K ⁺ , Ca ²⁺ , Zn ^{2+ and the} like).

Examples of the carbonyl group (R ⁰¹³ —CO—) include those in which R ⁰¹³ is a group composed of a monovalent nonmetallic atomic group.
Examples of such carbonyl group include formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, and N-arylcarbamoyl group. N, N-diarylcarbamoyl group, N-alkyl-N′-arylcarbamoyl group and the like. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group.
As the carbonyl group, a formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, and N-arylcarbamoyl group are preferable. A group, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group are more preferable.
Specific examples of the carbonyl group include formyl group, acetyl group, benzoyl group, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, allyloxycarbonyl group, dimethylaminophenylethenylcarbonyl group, methoxycarbonylmethoxycarbonyl group, N- A methylcarbamoyl group, an N-phenylcarbamoyl group, an N, N-diethylcarbamoyl group, a morpholinocarbonyl group and the like are preferable.

Examples of the sulfinyl group (R ⁰¹⁴ —SO—) include those in which R ⁰¹⁴ is a monovalent nonmetallic atomic group.
Examples of such sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, sulfinamoyl groups, N-alkylsulfinamoyl groups, N, N-dialkylsulfinamoyl groups, N-arylsulfinamoyl groups, N, N -Diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, etc. are mentioned. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Among these, an alkylsulfinyl group and an arylsulfinyl group are preferable.
Specific examples of the substituted sulfinyl group include a hexylsulfinyl group, a benzylsulfinyl group, a tolylsulfinyl group and the like.

The phosphono group means one in which one or two hydroxyl groups on the phosphono group are substituted with another organic oxo group, for example, the above-mentioned dialkylphosphono group, diarylphosphono group, alkylarylphosphono group. , Monoalkylphosphono group, monoarylphosphono group and the like are preferable. Of these, dialkylphosphono groups and diarylphosphono groups are more preferred.
More preferred specific examples of the phosphono group include a diethylphosphono group, a dibutylphosphono group, a diphenylphosphono group, and the like.

The phosphonato group _{(-PO 3 H 2 -, -} PO 3 H-) and, as mentioned above, the phosphono group _(-PO 3 _{H 2),} coupled from the first dissociation acid, or the second dissociated acid bases An anionic group is meant. Usually, it is preferable to use it with a counter cation. As such counter cations, generally known ones can be appropriately selected. For example, various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.), metal ions (Na ⁺ , K ⁺ , Ca ²⁺ , Zn ^2+, etc.).

The phosphonato group may be a conjugated base anion group obtained by substituting one organic oxo group in the phosphono group. Specific examples thereof include the monoalkylphosphono group (—PO ₃ H (alkyl)) and a conjugate base of a monoarylphosphono group (—PO ₃ H (aryl)).

The aromatic group can be produced by an ordinary radical polymerization method by using one or more radically polymerizable compounds containing an aromatic group and, if necessary, one or more other radically polymerizable compounds as a copolymerization component. .
Examples of the radical polymerization method generally include a suspension polymerization method and a solution polymerization method.

As the radically polymerizable compound containing an aromatic group, for example, a compound represented by the structural formula (A) and a compound represented by the structural formula (B) are preferable.
However, in said structural formula (A), R < ₁ >, R < ₂ > and R < ₃ > represent a hydrogen atom or monovalent organic group. L represents an organic group and may not be present. Ar represents an aromatic group that may contain a heterocycle.
However, in said structural formula (B), R < ₁ >, R < ₂ >, R < ₃ >, and Ar represent the same meaning as the said structural formula (A).

The organic group of L is, for example, a polyvalent organic group composed of non-metallic atoms, and includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, and 0 to 50 oxygen atoms. Those consisting of atoms, 1 to 100 hydrogen atoms, and 0 to 20 sulfur atoms.
More specifically, examples of the organic group of L include those formed by combining the following structural units, polyvalent naphthalene, and polyvalent anthracene.

  The L linking group may have a substituent, and examples of the substituent include the aforementioned halogen atom, hydroxyl group, carboxyl group, sulfonate group, nitro group, cyano group, amide group, amino group, alkyl group, Examples include alkenyl groups, alkynyl groups, aryl groups, substituted oxy groups, substituted sulfonyl groups, substituted carbonyl groups, substituted sulfinyl groups, sulfo groups, phosphono groups, phosphonato groups, silyl groups, and heterocyclic groups.

In the compound represented by the structural formula (A) and the compound represented by the structural formula (B), the structural formula (A) is preferable in terms of sensitivity. Among the structural formulas (A), those having a linking group are preferable from the viewpoint of stability, and the organic group of L is an alkylene group having 1 to 4 carbon atoms that can remove non-image areas. It is preferable in terms of (developability).
The compound represented by the structural formula (A) is a compound containing a structural unit of the following structural formula (I). The compound represented by the structural formula (B) is a compound containing a structural unit of the following structural formula (II). Among these, the structural unit of the structural formula (I) is preferable from the viewpoint of storage stability.

However, in said structural formula (I) and (II), R < ₁ >, R < ₂ >, R < ₃ > and Ar represent the same meaning as said structural formula (A) and (B).
In the structural formulas (I) and (II), R ₁ and R ₂ are preferably a hydrogen atom, and R ₃ is preferably a methyl group from the viewpoint of removability (developability) of a non-image area.
In addition, L in the structural formula (I) is preferably an alkylene group having 1 to 4 carbon atoms from the viewpoint of removability (developability) of non-image areas.

  Although there is no restriction | limiting in particular as a compound represented by the said structural formula (A) or a structural formula (B), For example, the following exemplary compounds (1)-(30) are mentioned.

  Among the exemplary compounds (1) to (30), (5), (6), (11), (14), and (28) are preferable, and among these, (5) and (6) are storage stable. Is more preferable from the viewpoints of colorability and developability.

  The content of the aromatic group that may contain a heterocycle in the binder is not particularly limited, but the structure represented by the structural formula (I) when the total structural unit of the polymer compound is 100 mol%. It is preferable to contain 20 mol% or more of a unit, and it is more preferable to contain 30-45 mol%. When the content is less than 20 mol%, storage stability may be lowered, and when it exceeds 45 mol%, developability may be deteriorated.

-Ethylenically unsaturated bond-
There is no restriction | limiting in particular as said ethylenically unsaturated bond, Although it can select suitably according to the objective, For example, what is represented by following Structural formula (III)-(V) is preferable.

However, in the structural formulas (III) to (V), R _{1 to} R ₁₁ each independently represents a monovalent organic group. X and Y each independently represent an oxygen atom, a sulfur atom, or —N—R ₄ . Z represents an oxygen atom, a sulfur atom, —N—R ₄ , or a phenylene group. R ₄ represents a hydrogen atom or a monovalent organic group.

In the structural formula (III), as R ₁ , for example, a hydrogen atom and an alkyl group which may have a substituent are each preferable, and the hydrogen atom and the methyl group have high radical reactivity. More preferred.
R ₂ and R ₃ are each independently, for example, a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, or an alkyl which may have a substituent. Group, aryl group which may have a substituent, alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylamino group which may have a substituent, substituent An arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and the like, such as a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, a substituent An alkyl group that may have a substituent and an aryl group that may have a substituent are more preferable because of high radical reactivity.
As R ₄ , for example, an alkyl group which may have a substituent is preferable, and a hydrogen atom, a methyl group, an ethyl group, and an isopropyl group are more preferable because of high radical reactivity.
Here, examples of the substituent that can be introduced include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, an amino group, an alkylamino group, an arylamino group, a carboxyl group, and an alkoxy group. Examples include carbonyl group, sulfo group, nitro group, cyano group, amide group, alkylsulfonyl group, arylsulfonyl group and the like.

In the structural formula (4), examples of R _{4 to} R ₈ include a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, and a substituent. An optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxy group, an optionally substituted aryloxy group, and optionally having a substituent An alkylamino group, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent are preferable, and a hydrogen atom, a carboxyl group, alkoxy A carbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are more preferable.
Examples of the substituent that can be introduced include those listed in the structural formula (III).

In the structural formula (5), as R ₉ , for example, a hydrogen atom or an alkyl group which may have a substituent is preferable, and a hydrogen atom or a methyl group is more preferable because of high radical reactivity.
R ₁₀ and R ₁₁ each independently have, for example, a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, or a substituent. An alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino which may have a substituent Group, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and the like, preferably a hydrogen 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 because of high radical reactivity.
Here, as the substituent which can be introduced, those exemplified in the structural formula (III) are exemplified.
Z represents an oxygen atom, a sulfur atom, —NR ₁₃ —, or a phenylene group which may have a substituent. R ₁₃ represents an alkyl group which may have a substituent, and a hydrogen atom, a methyl group, an ethyl group, and an isopropyl group are preferable because of high radical reactivity.

Among the side chain ethylenically unsaturated bonds represented by the structural formulas (III) to (V), those having the structural formula (III) are more preferable because of high polymerization reactivity and high sensitivity.
The content of the ethylenically unsaturated bond in the polymer compound is not particularly limited, but is preferably 0.5 to 3.0 meq / g, more preferably 1.0 to 3.0 meq / g, 1.5 ˜2.8 meq / g is particularly preferred. When the content is less than 0.5 meq / g, the curing reaction amount is small, so the sensitivity may be low. When the content is more than 3.0 meq / g, the storage stability may be deteriorated.
Here, the content (meq / g) can be measured by, for example, iodine value titration.

A method for introducing an ethylenically unsaturated bond represented by the structural formula (III) into the side chain is not particularly limited. It can be obtained by addition reaction of a compound having an epoxy group.
The polymer compound containing a carboxyl group in the side chain is usually composed of, for example, one or more radical polymerizable compounds containing a carboxyl group and, if necessary, one or more other radical polymerizable compounds as a copolymerization component. The radical polymerization method includes, for example, suspension polymerization method, solution polymerization method and the like.

The compound having an ethylenically unsaturated bond and an epoxy group is not particularly limited as long as it has these, but for example, a compound represented by the following structural formula (VI) and a compound represented by (VII) are preferable. . In particular, the use of the compound represented by the structural formula (VI) is preferable from the viewpoint of increasing sensitivity.
However, in said structural formula (VI), R1 represents a hydrogen atom or a methyl group. L1 represents an organic group.
However, in the structural formula (VII), R ₂ represents a hydrogen atom or a methyl group. L ₂ represents an organic group. W represents a 4- to 7-membered aliphatic hydrocarbon group.
Of the compound represented by the structural formula (VI) and the compound represented by the structural formula (VII), the compound represented by the structural formula (VI) is preferable. In the structural formula (VI), L ₁ is Those having 1 to 4 carbon atoms are more preferred.

Although there is no restriction | limiting in particular as a compound represented by the said structural formula (VI) or a structural formula (VII), For example, the following exemplary compounds (31)-(40) are mentioned.

  Examples of the radical polymerizable compound containing a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, incrotonic acid, maleic acid, p-carboxyl styrene, and particularly preferred is acrylic acid. And methacrylic acid.

  Examples of the introduction reaction to the side chain include tertiary amines such as triethylamine and benzylmethylamine, quaternary ammonium salts such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, and tetraethylammonium chloride, pyridine, triphenylphosphine, and the like. Can be carried out by reacting in an organic solvent at a reaction temperature of 50 to 150 ° C. for several hours to several tens of hours.

The structural unit having an ethylenically unsaturated bond in the side chain is not particularly limited. For example, the structure represented by the following structural formula (i), the structure represented by the structural formula (ii), and these Those represented by mixing are preferred.
However, in said structural formula (i) and (ii), Ra-Rc represents a hydrogen atom or monovalent organic group. R ₁ represents a hydrogen atom or a methyl group. L ₁ represents an organic group that may have a linking group.

  The content in the polymer compound having the structure represented by the structural formula (i) or the structural formula (ii) is preferably 20 mol% or more, more preferably 20 to 50 mol%, and more preferably 25 to 45 mol%. Particularly preferred. When the content is less than 20 mol%, the curing reaction amount is small, so that the sensitivity may be low. When the content is more than 50 mol%, the storage stability may be deteriorated.

--Carboxyl group--
The polymer compound of the present invention may have a carboxyl group in order to improve various performances such as non-image area removability.
The carboxyl group can be imparted to the polymer compound by copolymerizing a radical polymerizable compound having an acid group.
Examples of the acid group having such radical polymerizability include carboxylic acid, sulfonic acid, and phosphoric acid group, and carboxylic acid is particularly preferable.
The radical polymerizable compound having a carboxyl group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, incrotonic acid, maleic acid, p -Carboxylstyrene etc. are mentioned, Among these, acrylic acid, methacrylic acid, and p-carboxylstyrene are preferable. These may be used alone or in combination of two or more.

  Content in the binder of the said carboxyl group is 1.0-4.0 meq / g, and 1.5-3.0 meq / g is preferable. If the content is less than 1.0 meq / g, the developability may be insufficient, and if it exceeds 4.0 meq / g, the image strength may be easily damaged by alkaline water development.

The polymer compound of the present invention is preferably further copolymerized with another radical polymerizable compound in addition to the above-mentioned radical polymerizable compound for the purpose of improving various properties such as image strength.
Examples of the other radical polymerizable compounds include radical polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes, and the like.

Specific examples include acrylic acid esters such as alkyl acrylate, methacrylic acid esters such as aryl acrylate and alkyl methacrylate, styrenes such as aryl methacrylate, styrene and alkyl styrene, alkoxy styrene, and halogen styrene.
As the acrylate esters, alkyl groups having 1 to 20 carbon atoms are preferable. For example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, ethyl hexyl acrylate Octyl acrylate, tert-octyl acrylate, chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl Examples thereof include acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate and the like.
Examples of the aryl acrylate include phenyl acrylate.

As the methacrylic acid esters, those having 1 to 20 carbon atoms in the alkyl group are preferable. For example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl. Methacrylate, octyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate, furfuryl methacrylate, tetrahydro And furfuryl methacrylate.
Examples of the aryl methacrylate include phenyl methacrylate, cresyl methacrylate, and naphthyl methacrylate.

Examples of the styrenes include methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, and trifluoromethyl. Examples thereof include styrene, ethoxymethyl styrene, acetoxymethyl styrene and the like.
Examples of the alkoxystyrene include methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, and the like.
Examples of the halogen styrene include chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, and 2-bromo-4-trifluoro. Examples include rumethylstyrene and 4-fluoro-3-trifluoromethylstyrene.
These radically polymerizable compounds may be used individually by 1 type, and may use 2 or more types together.

  The solvent used in synthesizing the polymer compound of the present invention is not particularly limited and can be appropriately selected depending on the purpose. For example, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, Butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, Examples include dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, and ethyl lactate. These may be used alone or in combination of two or more.

The molecular weight of the polymer compound of the present invention is preferably 10,000 or more, more preferably 10,000 to 50,000 in terms of mass average molecular weight. When the mass average molecular weight is less than 10,000, the cured film strength may be insufficient, and when it exceeds 50,000, the developability tends to decrease.
Further, the polymer compound of the present invention may contain an unreacted monomer. In this case, the content of the monomer in the polymer compound is preferably 15% by mass or less.

  The polymer compound according to the present invention may be used alone or in combination of two or more. Moreover, you may mix and use another high molecular compound. In this case, the content of the other polymer compound in the polymer compound of the present invention is preferably 50% by mass or less, and more preferably 30% by mass or less.

  5-80 mass% is preferable and, as for solid content content in the said photosensitive composition of the said binder, 10-70 mass% is more preferable.

  Furthermore, a compound in which an ethylenically unsaturated double bond and an acidic group are introduced into an epoxy resin is also suitable. Moreover, the vinyl copolymer which has a (meth) acryloyl group and an acidic group in a side chain is also preferable.

--Compound in which an ethylenically unsaturated double bond and an acidic group are introduced into an epoxy resin--
The compound in which an ethylenically unsaturated double bond and an acidic group are introduced into the epoxy resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an epoxy group-containing polymerizable compound and an unsaturated carboxyl Examples thereof include a reaction product obtained by reacting an acid and a reaction product obtained by reacting an epoxy group-containing polymerizable compound with an unsaturated carboxylic acid and further adding a polybasic acid anhydride.

  Examples of the epoxy group-containing polymerizable compound include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin; phenol novolac type epoxy resin, cresol novolac type epoxy resin, novolak type Novolac epoxy resins such as biphenyl type epoxy resins; cycloaliphatic epoxy resins; polyfunctional glycidyl amine resins such as tetraglycidyl diaminodiphenylmethane; polyfunctional glycidyl ether resins such as tetraphenyl glycidyl ether ethane; phenol, o-cresol, naphthol A reaction product of a polyphenol compound and epichlorohydrin obtained by a condensation reaction of a phenol compound such as an aromatic aldehyde having a phenolic hydroxyl group; A reaction product of a polyphenol compound obtained by addition reaction of a diol compound with a diolefin compound such as divinylbenzene or dicyclopentadiene and epichlorohydrin; a ring-opening polymer of 4-vinylcyclohexene-1-oxide with peracetic acid or the like. Epoxidized ones; epoxy resins having a heterocyclic ring such as triglycidyl isocyanurate; These may be used individually by 1 type and may use 2 or more types together.

  Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, α-cyanocinnamic acid, β-stilacrylic acid, β-acryloxypropionic acid, and one hydroxyl group. Examples include a reaction product of a compound having one or more (meth) acryloyl groups and a dibasic acid anhydride. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the polybasic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, citraconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexa Hydrophthalic anhydride, methyl endomethylenetetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecenyl succinic anhydride, chlorendic anhydride, trimellitic anhydride, pyromellitic anhydride, 5- (2,5-dioxotetrahydrofuryl) ) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, benzophenone tetracarboxylic acid anhydride, and the like. These may be used individually by 1 type and may use 2 or more types together.

Among the compounds obtained by introducing an ethylenically unsaturated double bond and an acidic group into the epoxy compound, epoxy acrylate compounds represented by the following structural formulas (1) and (2) are preferable.
However, in the structural formula (1), X represents a hydrogen atom or a substituent containing at least an acidic group. Y represents a methylene group, an isopropylidene group, or a sulfonyl group. n represents an integer of 1 to 20.

However, in said structural formula (2), n represents the integer of 1-20.

The epoxy acrylate compound represented by the structural formula (1) is specifically represented by the bisphenol F type epoxy acrylate compound represented by the following structural formula (3) and the following structural formula (4). Bisphenol A type epoxy acrylate compounds are more preferred.

  The molecular weight of the compound in which an ethylenically unsaturated double bond and an acidic group are introduced into the epoxy resin is preferably 200 to 1,500, and more preferably 300 to 1,000. When the molecular weight is less than 200, the tackiness of the surface of the photosensitive layer may become strong, and after curing of the photosensitive layer described later, the film quality may become brittle, or the surface hardness may deteriorate. If it exceeds 1, developability may deteriorate.

Examples of the binder include an unsaturated resin obtained by a reaction between an unsaturated-basic acid copolymer resin and an epoxy group-containing unsaturated compound, and a reaction between the epoxy group-containing copolymer resin and an acid group-containing unsaturated compound. The unsaturated resin obtained by (1) is mentioned.
As these unsaturated resins, those appropriately synthesized may be used, or commercially available products may be used.
Examples of the commercially available products include cyclomer P series (manufactured by Daicel).

--Vinyl copolymer having (meth) acryloyl group and acidic group in side chain--
Examples of the vinyl copolymer having a (meth) acryloyl group and an acidic group in the side chain include, for example, (1) a vinyl monomer having an acidic group, and (2) a function that can be used for a polymer reaction described later, if necessary. A (co) polymer obtained by vinyl (co) polymerization of a vinyl monomer having a group and (3) other copolymerizable vinyl monomer if necessary, and (4) the (co) polymer It is obtained by polymer-reacting a compound having a (meth) acryloyl group with a functional group having reactivity with at least one of an acidic group in the coalescence or a functional group available for polymer reaction.
There is no restriction | limiting in particular as an acidic group of the vinyl monomer which has said (1) acidic group, According to the objective, it can select suitably, For example, a carboxyl group, a sulfonic acid group, a phosphoric acid group etc. are mentioned, These Among these, a carboxyl group is preferable. Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, and a monomer having a hydroxyl group. Addition reaction product of a monomer (for example, 2-hydroxyethyl (meth) acrylate) and a cyclic anhydride (for example, maleic anhydride, phthalic anhydride, cyclohexanedicarboxylic anhydride), ω-carboxy-polycaprolactone mono ( And (meth) acrylate. Among these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like. Moreover, these monomers may be used individually by 1 type, and may use 2 or more types together.
Moreover, you may use the monomer which has anhydrides, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group.
In the vinyl monomer having a functional group usable for the polymer reaction of (2), the functional group usable for the polymer reaction is a hydroxyl group, an amino group, an isocyanate group, an epoxy group, an acid halide group, an active halide group, Etc. Moreover, the carboxyl group and acid anhydride group of the above-mentioned (1) are also mentioned as usable functional groups.

  Examples of the vinyl monomer having a hydroxyl group include compounds represented by the following structural formulas (5) to (13).

However, in the structural formulas (5) to (13), R ₁ represents a hydrogen atom or a methyl group, and n, n1, and n2 represent an integer of 1 or more.

  Examples of the vinyl monomer having an amino group include vinyl benzylamine and aminoethyl methacrylate.

  Examples of the monomer having an isocyanate group include compounds represented by the following structural formulas (14) to (16).

However, in the structural formulas (14) to (16), R ¹ represents a hydrogen atom or a methyl group.

  Examples of the vinyl monomer having an epoxy group include glycidyl (meth) acrylate and a compound represented by the following structural formula (17).

However, in said structural formula (17), R represents either H or Me.

Examples of the vinyl monomer having an acid halide group include (meth) acrylic acid chloride.
Examples of the vinyl monomer having an active halide group include chloromethylstyrene.
As these commercially available products, for example, “Kaneka Resin AX; manufactured by Kaneka Chemical Industry Co., Ltd.”, “Cyclomer (CYCLOMER) A-200; manufactured by Daicel Chemical Industries, Ltd.”, “Cyclomer (CYCLOMER) M-” 200; manufactured by Daicel Chemical Industries, Ltd. "," SPCP1X, SPCP2X, SPCP3X; manufactured by Showa High Polymer Co., Ltd. "can be used.
Moreover, each said monomer may be used individually by 1 type, and may use 2 or more types together.

  The other copolymerizable monomer used as necessary in (3) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include (meth) acrylic acid esters and crotonic acid. Esters, vinyl esters, maleic diesters, fumaric diesters, itaconic diesters, (meth) acrylamides, vinyl ethers, vinyl alcohol esters, styrenes (eg, styrene, styrene derivatives, etc.), (Meth) acrylonitrile, heterocyclic groups substituted with vinyl groups (for example, vinylpyridine, vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinylcaprolactone, 2-acrylamide-2 -Methylpropanesulfonic acid, Vinyl monomers having mono (2-acryloyloxyethyl ester) acid, mono (1-methyl-2-acryloyloxyethyl ester) phosphate, and functional groups (eg, urethane group, urea group, sulfonamide group, imide group) Etc.

  Examples of the (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) ) Acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, t-octyl (meth) acrylate, Dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate 2- (2-methoxyethoxy) ethyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monophenyl ether (meth) acrylate, triethylene Glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monoethyl ether (meth) acrylate, β-phenoxyethoxyethyl acrylate, nonylphenoxy polyethylene glycol ( (Meth) acrylate, dicyclopentanyl (meth) acrylate, dis Clopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, tribromophenyl (meth) acrylate, And tribromophenyloxyethyl (meth) acrylate.

  Examples of the crotonic acid esters include butyl crotonate and hexyl crotonate.

  Examples of the vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.

  Examples of the maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

  Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, dibutyl fumarate and the like.

  Examples of the itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  Examples of the (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- n-butylacryl (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, Examples thereof include N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide and the like.

  Examples of the styrenes include the styrene, the styrene derivatives (for example, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, Bromostyrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, α-methylstyrene, and the like).

  Examples of the vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

  Examples of the method for synthesizing a vinyl monomer having a urethane group or a urea group as the functional group include an addition reaction of an isocyanate group and a hydroxyl group or an amino group. Specifically, a monomer having an isocyanate group, and a hydroxyl group An addition reaction with a compound containing 1 or a compound having one primary or secondary amino group, an addition reaction between a monomer having a hydroxyl group or a monomer having a primary or secondary amino group, and a monoisocyanate. .

Examples of the monomer having an isocyanate group include compounds represented by the structural formulas (10) to (12), as in the above-described (2).
Examples of the monoisocyanate include cyclohexyl isocyanate, n-butyl isocyanate, toluyl isocyanate, benzyl isocyanate, and phenyl isocyanate.
Examples of the monomer having a hydroxyl group include the compounds represented by the structural formulas (1) to (9) in the same manner as in the above (2).

  Examples of the compound containing one hydroxyl group include alcohols (for example, methanol, ethanol, n-propanol, i-propanol, n-butanol, sec-butanol, t-butanol, n-hexanol, 2-ethylhexanol). , N-decanol, n-dodecanol, n-octadecanol, cyclopentanol, cyclohexanol, benzyl alcohol, phenylethyl alcohol, etc.), phenols (eg, phenol, cresol, naphthol, etc.), and further containing substituents Examples thereof include fluoroethanol, trifluoroethanol, methoxyethanol, phenoxyethanol, chlorophenol, dichlorophenol, methoxyphenol, acetoxyphenol, and the like.

  Examples of the monomer having a primary or secondary amino group include vinylbenzylamine.

  Examples of the compound containing one primary or secondary amino group include alkylamines (methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, sec-butylamine, t-butylamine, hexyl). Amine, 2-ethylhexylamine, decylamine, dodecylamine, octadecylamine, dimethylamine, diethylamine, dibutylamine, dioctylamine), cyclic alkylamine (cyclopentylamine, cyclohexylamine, etc.), aralkylamine (benzylamine, phenethylamine, etc.), Arylamines (aniline, toluylamine, xylylamine, naphthylamine, etc.), combinations thereof (N-methyl-N-benzylamine, etc.), and amines containing further substituents (trifluoroethylamino) , Hexafluoro isopropyl amine, methoxyaniline, methoxypropylamine and the like) and the like.

Moreover, these monomers may be used individually by 1 type, and may use 2 or more types together.
By vinyl (co) polymerizing these, an (co) polymer containing an acid group, an acid anhydride group and, if necessary, a hydroxyl group, an amino group, an isocyanate group, an epoxy group, an acid halide group, an active halide group, etc. can get. The vinyl (co) polymer can be prepared by copolymerizing corresponding monomers according to a conventional method according to a conventional method. For example, it can be prepared by using a method (solution polymerization method) in which the monomer is dissolved in a suitable solvent and a radical polymerization initiator is added thereto to polymerize in a solution. Moreover, it can prepare by utilizing superposition | polymerization by what is called emulsion polymerization etc. in the state which disperse | distributed the said monomer in the aqueous medium.
With respect to the (co) polymer thus obtained, as the above (4), an acidic group in these copolymers and, if necessary, a hydroxyl group, an amino group, an isocyanate group, a glycidyl group, an acid halide It is obtained by polymer-reacting a functional group having reactivity with at least one of the groups and a compound having a (meth) acryloyl group.

As the compound having a (meth) acryloyl group and a functional group reactive to at least one of the acidic group in the (co) polymer of the above (4) or a functional group available for polymer reaction The compounds shown in (2) above can be used.
Examples of combinations of functional groups in performing these polymer reactions include, for example, a copolymer having an acidic group (such as a carboxyl group) and a vinyl monomer having an epoxy group, and a copolymer having an amino group Combination of vinyl monomer having epoxy group, combination of copolymer having amino group and vinyl monomer having isocyanate group, combination of copolymer having hydroxyl group and vinyl monomer having isocyanate group, copolymer having hydroxyl group and acid Combination of vinyl monomer having halide group, combination of copolymer having amino group and vinyl monomer having active halide group, combination of copolymer having acid anhydride group and vinyl monomer having hydroxyl group, having isocyanate group Combination of copolymer and vinyl monomer having amino group, isocyanate Combinations of vinyl monomer having a copolymer and a hydroxyl group with the combination of the vinyl monomer having a copolymer and an amino group having an active halide groups, and the like. Two or more of these combinations may be used in combination.

-Other binders-
Other binders may be used as the binder.
There is no restriction | limiting in particular as said other binder, Although it can select suitably according to the objective, For example, a maleamic acid type copolymer etc. are mentioned.
The maleamic acid-based copolymer is a copolymer obtained by reacting one or more primary amine compounds with an anhydride group of a maleic anhydride copolymer. The copolymer is a maleamic acid-based copolymer having at least a maleamic acid unit B having a maleic acid half amide structure and a unit A not having the maleic acid half amide structure, represented by the following structural formula (VII): It is preferably a coalescence.
The unit A may be one type or two or more types. For example, assuming that the unit B is one type, when the unit A is one type, the maleamic acid-based copolymer means a binary copolymer, and the unit A is 2 When it is a seed, the maleamic acid-based copolymer means a terpolymer.
The unit A is an aryl group which may have a substituent and a vinyl monomer described later, and the glass transition temperature (Tg) of the homopolymer of the vinyl monomer is less than 80 ° C. A combination with the vinyl monomer (c) is preferred.

In the Structural Formula (18), R ³ and R ⁴ represents a hydrogen atom or a lower alkyl group. x and y represent the mole fraction of the repeating unit. For example, when the unit A is one, x is 85 to 50 mol%, and y is 15 to 50 mol%.

In the structural formula (18), as R ¹ , for example, (—COOR ¹⁰ ), (—CONR ¹¹ R ¹² ), an aryl group which may have a substituent, (—OCOR ¹³ ), (—OR ¹⁴ ), substituents such as (—COR ¹⁵ ). Here, said R < ¹⁰ > -R < ¹⁵ > represents either a hydrogen atom (-H), the alkyl group which may have a substituent, an aryl group, and an aralkyl group. The alkyl group, aryl group and aralkyl group may have a cyclic structure or a branched structure.
Examples of R ^{10 to} R ¹⁵ include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, pentyl, allyl, n-hexyl, and cyclohexyl. 2-ethylhexyl, dodecyl, methoxyethyl, phenyl, methylphenyl, methoxyphenyl, benzyl, phenethyl, naphthyl, chlorophenyl and the like.
Specific examples of R ¹ include, for example, benzene derivatives such as phenyl, α-methylphenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl; n-propyloxycarbonyl, Examples include n-butyloxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, n-butyloxycarbonyl, n-hexyloxycarbonyl, 2-ethylhexyloxycarbonyl, methyloxycarbonyl and the like.

Examples of R ² include an alkyl group, an aryl group, and an aralkyl group that may have a substituent. These may have a cyclic structure or a branched structure. Specific examples of R ² include, for example, benzyl, phenethyl, 3-phenyl-1-propyl, 4-phenyl-1-butyl, 5-phenyl-1-pentyl, 6-phenyl-1-hexyl, and α-methyl. Benzyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2- (p-tolyl) ethyl, β-methylphenethyl, 1-methyl-3-phenylpropyl, 2-chlorobenzyl, 3-chlorobenzyl, 4-chlorobenzyl, 2-fluorobenzyl, 3-fluorobenzyl, 4-fluorobenzyl, 4-bromophenethyl, 2- (2-chlorophenyl) ethyl, 2- (3-chlorophenyl) ethyl, 2- (4-chlorophenyl) Ethyl, 2- (2-fluorophenyl) ethyl, 2- (3-fluorophenyl) ethyl, 2- (4-fluorophenyl) Til, 4-fluoro-α, α-dimethylphenethyl, 2-methoxybenzyl, 3-methoxybenzyl, 4-methoxybenzyl, 2-ethoxybenzyl, 2-methoxyphenethyl, 3-methoxyphenethyl, 4-methoxyphenethyl, methyl, Ethyl, propyl, 1-propyl, butyl, t-butyl, sec-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, lauryl, phenyl, 1-naphthyl, methoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 3 -Methoxypropyl, 2-butoxyethyl, 2-cyclohexyloxyethyl, 3-ethoxypropyl, 3-propoxypropyl, 3-isopropoxypropylamine and the like.

  The binder is, in particular, (a) maleic anhydride, (b) an aromatic vinyl monomer, and (c) a vinyl monomer, the glass transition temperature (Tg) of the homopolymer of the vinyl monomer. ) Is preferably a copolymer obtained by reacting a primary amine compound with an anhydride group of a copolymer comprising a vinyl monomer having a temperature of less than 80 ° C. A copolymer comprising the component (a) and the component (b) can obtain a high surface hardness of the photosensitive layer described later, but it may be difficult to ensure laminating properties. Moreover, in the copolymer which consists of this (a) component and this (c) component, although lamination property can be ensured, it may become difficult to ensure the said surface hardness.

<< (b) Aromatic vinyl monomer >>
There is no restriction | limiting in particular as said aromatic vinyl monomer, Although it can select suitably according to the objective, The surface of the photosensitive layer formed using the photosensitive composition (polymerizable composition) of this invention A compound having a glass transition temperature (Tg) of the homopolymer of 80 ° C. or higher is preferable and a compound of 100 ° C. or higher is more preferable in that the hardness can be increased.
Specific examples of the aromatic vinyl monomer include, for example, styrene (homopolymer Tg = 100 ° C.), α-methylstyrene (homopolymer Tg = 168 ° C.), 2-methylstyrene (homopolymer Tg = 136 ° C.), 3-methylstyrene (homopolymer Tg = 97 ° C.), 4-methylstyrene (homopolymer Tg = 93 ° C.), 2,4-dimethylstyrene (homopolymer Tg = 112 ° C.) Preferred examples include derivatives. These may be used individually by 1 type and may use 2 or more types together.

<< (c) Vinyl monomer >>
The vinyl monomer is required to have a glass transition temperature (Tg) of a homopolymer of the vinyl monomer of less than 80 ° C., preferably 40 ° C. or less, and more preferably 0 ° C. or less.
Examples of the vinyl monomer include n-propyl acrylate (homopolymer Tg = −37 ° C.), n-butyl acrylate (homopolymer Tg = −54 ° C.), pentyl acrylate, or hexyl acrylate (homopolymer acrylate). Tg = −57 ° C.), n-butyl methacrylate (Tg of homopolymer = −24 ° C.), n-hexyl methacrylate (Tg of homopolymer = −5 ° C.), and the like. These may be used individually by 1 type and may use 2 or more types together.

<< Primary amine compound >>
Examples of the primary amine compound include benzylamine, phenethylamine, 3-phenyl-1-propylamine, 4-phenyl-1-butylamine, 5-phenyl-1-pentylamine, 6-phenyl-1-hexylamine, α-methylbenzylamine, 2-methylbenzylamine, 3-methylbenzylamine, 4-methylbenzylamine, 2- (p-tolyl) ethylamine, β-methylphenethylamine, 1-methyl-3-phenylpropylamine, 2-chloro Benzylamine, 3-chlorobenzylamine, 4-chlorobenzylamine, 2-fluorobenzylamine, 3-fluorobenzylamine, 4-fluorobenzylamine, 4-bromophenethylamine, 2- (2-chlorophenyl) ethylamine, 2- ( 3-chlorophenyl) ethyla Min, 2- (4-chlorophenyl) ethylamine, 2- (2-fluorophenyl) ethylamine, 2- (3-fluorophenyl) ethylamine, 2- (4-fluorophenyl) ethylamine, 4-fluoro-α, α-dimethyl Phenethylamine, 2-methoxybenzylamine, 3-methoxybenzylamine, 4-methoxybenzylamine, 2-ethoxybenzylamine, 2-methoxyphenethylamine, 3-methoxyphenethylamine, 4-methoxyphenethylamine, methylamine, ethylamine, propylamine, 1 -Propylamine, butylamine, t-butylamine, sec-butylamine, pentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, laurylamine, aniline, octylaniline, anisi Gin, 4-chloroaniline, 1-naphthylamine, methoxymethylamine, 2-methoxyethylamine, 2-ethoxyethylamine, 3-methoxypropylamine, 2-butoxyethylamine, 2-cyclohexyloxyethylamine, 3-ethoxypropylamine, 3- Examples thereof include propoxypropylamine and 3-isopropoxypropylamine. Among these, benzylamine and phenethylamine are particularly preferable.
The said primary amine compound may be used individually by 1 type, and may use 2 or more types together.

  The reaction amount of the primary amine compound needs to be 0.1 to 1.2 equivalents relative to the anhydride group, and preferably 0.1 to 1.0 equivalents. When the reaction amount exceeds 1.2 equivalents, the solubility may be significantly deteriorated when one or more primary amine compounds are reacted.

  The content of the (a) maleic anhydride in the binder is preferably 15 to 50 mol%, more preferably 20 to 45 mol%, particularly preferably 20 to 40 mol%. When the content is less than 15 mol%, alkali developability cannot be imparted, and when it exceeds 50 mol%, alkali resistance deteriorates and synthesis of the copolymer becomes difficult, resulting in a normal permanent pattern. Formation may not be possible. In this case, the content of (b) the aromatic vinyl monomer and (c) the vinyl monomer having a glass transition temperature (Tg) of the homopolymer of less than 80 ° C. in the binder is 20 respectively. -60 mol% and 15-40 mol% are preferable. When the content satisfies the numerical range, both surface hardness and laminating properties can be achieved.

  The molecular weight of the maleamic acid copolymer is preferably 3,000 to 500,000, more preferably 8,000 to 150,000. When the molecular weight is less than 3,000, the film quality becomes brittle and the surface hardness may deteriorate after curing of the photosensitive layer described later. When the molecular weight exceeds 500,000, the photosensitive composition is heated and laminated. The fluidity of the resin tends to be low, and it may be difficult to ensure proper laminating properties, and the developability may deteriorate.

  Further, a compound obtained by adding an acid anhydride to an epoxy acrylate having a fluorene skeleton described in JP-A-5-70528, a polyamide (imide) resin described in JP-A-11-288087, and JP-A-2-097502 Styrene or a styrene derivative and an acid anhydride copolymer containing an amide group described in JP-A No. 2003-20310 and a polyimide precursor described in JP-A No. 11-282155 can be used. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  The molecular weight of a binder such as a compound obtained by adding an acid anhydride to the epoxy acrylate having the fluorene skeleton, polyamide (imide), amide group-containing styrene / acid anhydride copolymer, or polyimide precursor is 3, 000 to 500,000 are preferable, and 5,000 to 100,000 are more preferable. When the molecular weight is less than 3,000, the tackiness of the surface of the photosensitive layer may become strong, and after curing of the photosensitive layer described later, the film quality may become brittle or the surface hardness may be deteriorated. If it exceeds 1,000, developability may deteriorate.

  The solid content in the solid content of the photosensitive composition of the binder is preferably 5 to 70% by mass, and more preferably 10 to 50% by mass. When the solid content is less than 5% by mass, the film strength of the photosensitive layer described later tends to be weak, and the tackiness of the surface of the photosensitive layer may be deteriorated. Sensitivity may decrease.

-Thermosetting accelerator-
The thermosetting accelerator has a function of accelerating the thermosetting of the epoxy resin compound or the polyfunctional oxetane compound, and is preferably added to the photosensitive resin.
The thermosetting accelerator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy. Amine compounds such as -N, N-dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; quaternary ammonium salt compounds such as triethylbenzylammonium chloride; blocked isocyanate compounds such as dimethylamine; imidazole and 2-methyl Imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methyl Imidazole Any imidazole derivatives bicyclic amidine compounds and salts thereof; phosphorus compounds such as triphenylphosphine; guanamine compounds such as melamine, guanamine, acetoguanamine, benzoguanamine; 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2 -Vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid S-triazine derivatives such as adducts, boron trifluoride-amine complex, organic hydrazides, phthalic anhydride, trimellitic anhydride, ethylene glycol bis (anhydro trimellitate), glycerol tris (anhydro trimellitate) , Benzo Aromatic acid anhydrides such as phenonetetracarboxylic anhydride, aliphatic acid anhydrides such as maleic anhydride and tetrahydrophthalic anhydride, polyphenols such as polyvinylphenol, polyvinylphenol bromide, phenol novolac and alkylphenol novolac Can be used. Among these, dicyandiamide, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct and the like are preferable. These may be used alone or in combination of two or more. The epoxy resin compound or the polyfunctional oxetane compound is a curing catalyst, or any compound capable of promoting the reaction of the carboxyl group with these, and any compound capable of promoting thermal curing other than the above. May be used.
The solid content in the solid content of the photosensitive composition solution of the thermosetting accelerator is not particularly limited, but is preferably 0.1 to 3% by mass, and 0.5 to 2% by mass. More preferred. If the solid content is less than 0.1% by mass, curing by heat may not be accelerated. If the solid content exceeds 3% by mass, the viscosity of the coating solution increases, and a suitable coating is not performed. A stable surface shape of the layer may not be obtained.

-Silica compound-
The silica compound is used as a filler, has the function of improving the surface hardness of the permanent pattern, suppressing the coefficient of linear expansion low, and suppressing the dielectric constant and dielectric loss tangent of the cured layer itself.
There is no restriction | limiting in particular as said silica compound, According to the objective, it can select suitably, For example, a silicon oxide powder, a fine powder silicon oxide, a gaseous-phase method silica, an amorphous silica, a crystalline silica, a fused silica, spherical Although silica etc. are mentioned, the silica manufactured with the combustion method is preferable at the point which has little Na ^<+> content and is suitable for an electronic material use. Here, specific examples of silica produced by the combustion method include Aerosil (manufactured by DEGUSSA) and Admafine (manufactured by Admatechs). Aerosil is a fine particle obtained by burning a mixture of silicon tetrachloride and hydrogen in air at 1000 to 1200 ° C. Admafine, on the other hand, melts metallic silica, disperses it in an oxygen stream from a nozzle, ignites it to oxidize (combust), converts the metal and oxide into vapor or liquid with its reaction heat, and cools it. Fine oxide particles.

The average particle size of the silica compound is preferably less than 3 μm, more preferably 0.1 to 2 μm. When the average particle diameter is 3 μm or more, resolution may be deteriorated due to light scattering. The silica compound has a particle size distribution of about 0.1 to 5 μm.
5-50 mass% is preferable, as for the addition amount of the said silica compound, 10-40 mass% is more preferable, and 15-30 mass% is especially preferable. When the addition amount is less than 5% by mass, the linear expansion coefficient may not be sufficiently reduced. When the addition amount exceeds 50% by mass, when the cured film is formed on the surface of the photosensitive layer, The film quality becomes fragile, and when a wiring is formed using a permanent pattern, the function of the wiring as a protective film may be impaired.

  It is also possible to add organic fine particles to the silica compound as necessary. The organic fine particle is not particularly limited and may be appropriately selected depending on the intended purpose. For example, melamine resin, benzoguanamine resin, cross-linked polystyrene resin and the like are preferable. Further, silica having an average particle size of 0.1 to 2 μm and an oil absorption of about 100 to 200 ml / g, spherical porous fine particles made of a crosslinked resin, and the like can be used.

  Since the silica compound contains particles having an average particle size of 0.1 to 2 μm, even if the permanent pattern is thinned to a thickness of 5 to 20 μm in accordance with the thinning of the printed wiring board, it is inorganic. The filler particles do not cross-link both surfaces of the permanent pattern, and as a result, no ion migration occurs even in the high acceleration test (HAST), and a permanent pattern excellent in heat resistance and moisture resistance can be obtained.

-Polymerizable compound-
The polymerizable compound is not particularly limited and may be appropriately selected depending on the intended purpose. The compound has at least one addition-polymerizable group in the molecule and has a boiling point of 100 ° C. or higher at normal pressure. For example, at least one selected from monomers having a (meth) acryl group is preferable.

  There is no restriction | limiting in particular as a monomer which has the said (meth) acryl group, According to the objective, it can select suitably, For example, 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 hex (Meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, Polyfunctional alcohols such as glycerin tri (meth) acrylate, trimethylolpropane, glycerin, bisphenol, and the like, and (meth) acrylated after addition reaction of ethylene oxide or propylene oxide, Japanese Patent Publication No. 48-41708, Japanese Patent Publication Urethane acrylates described in publications such as JP 50-6034 and JP 51-37193; JP 48-64183, JP 49-4319 Polyester acrylates described in various publications such as JP, JP 30-30490, and polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid. It is done. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are particularly preferable.

  5-75 mass% is preferable and, as for solid content in the said photosensitive composition solid content of the said polymeric compound, 10-40 mass% is more preferable. If the solid content is less than 5% by mass, problems such as deterioration in developability and reduction in exposure sensitivity may occur, and if it exceeds 75% by mass, the adhesiveness of the photosensitive layer may become too strong. Yes, not preferred.

-Thermal crosslinking agent-
There is no restriction | limiting in particular as said heat-crosslinking agent, According to the objective, it can select suitably, For example, an epoxy resin, a polyfunctional oxetane compound, etc. are mentioned suitably.
There is no restriction | limiting in particular as said epoxy resin and a polyfunctional oxetane compound, According to the objective, it can select suitably, For example, the photosensitive layer formed using the photosensitive composition (polymerizable composition) of this invention. In order to improve the film strength after curing, an epoxy resin compound having at least two oxirane groups in one molecule and an oxetane having at least two oxetanyl groups in one molecule within a range that does not adversely affect developability and the like Compounds, compounds represented by the following structural formulas I to III, and the like can be used.

  There is no restriction | limiting in particular as said epoxy resin, According to the objective, it can select suitably, For example, a bixylenol type or a biphenol type epoxy resin ("YX4000; Japan Epoxy Resin Co., Ltd." etc.) or mixtures thereof, isocyania Heterocyclic epoxy resins having a nurate skeleton ("TEPIC; manufactured by Nissan Chemical Industries", "Araldite PT810; manufactured by Ciba Specialty Chemicals"), bisphenol A type epoxy resin, novolak type epoxy resin, bisphenol F type Epoxy resin, hydrogenated bisphenol A type epoxy resin, glycidylamine type epoxy resin, hydantoin type epoxy resin, alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol S type epoxy resin, bisphenol A Borac type epoxy resin, tetraphenylolethane type epoxy resin, glycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group-containing epoxy resin (“ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.”, “HP-4032” , EXA-4750, EXA-4700; manufactured by Dainippon Ink & Chemicals, Inc.), epoxy resins having a dicyclopentadiene skeleton (“HP-7200, HP-7200H; manufactured by Dainippon Ink & Chemicals, Inc.”), glycidyl Examples thereof include a methacrylate copolymer epoxy resin (“CP-50S, CP-50M; manufactured by NOF Corporation”), a copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, and the like. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.

  The polyfunctional oxetane compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether and bis [(3-ethyl-3 -Oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3 -Methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate or oligomers thereof or In addition to polyfunctional oxetanes such as copolymers, oxetane groups and Novo And ether compounds with hydroxyl groups such as poly (p-hydroxystyrene), cardo-type bisphenols, calixarenes, calixresorcinarenes, silsesquioxanes, etc., and oxetane A copolymer of an unsaturated monomer having a ring and an alkyl (meth) acrylate is also included.

  The solid content in the solid content of the photosensitive composition solution of the epoxy resin or the polyfunctional oxetane compound is not particularly limited and can be appropriately selected depending on the purpose, for example, 2 to 50% by mass. Preferably, 3-30 mass% is more preferable. If the solid content is less than 2% by mass, the hygroscopicity of the cured film is increased, resulting in deterioration of insulation, or solder heat resistance and electroless plating resistance may be reduced. If it exceeds mass%, the developability may deteriorate and the exposure sensitivity may decrease, which is not preferable.

-Other thermal crosslinking agents-
The other thermal crosslinking agent can be added separately from the epoxy resin and the polyfunctional oxetane compound. The thermal crosslinking agent is not particularly limited and can be appropriately selected depending on the purpose. For example, a polyisocyanate compound described in JP-A-5-9407 can be used. As the polyisocyanate compound, It may be derived from an aliphatic, cycloaliphatic or aromatic group-substituted aliphatic compound containing at least two isocyanate groups.
Specifically, a mixture of 1,3-phenylene diisocyanate and 1,4-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate, 1,3- and 1,4-xylylene diisocyanate, bis (4 -Isocyanate-phenyl) methane, bis (4-isocyanatocyclohexyl) methane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, etc .; bifunctional isocyanate; A polyfunctional alcohol; an alkylene oxide adduct of the polyfunctional alcohol and an adduct of the bifunctional isocyanate; hexamethylene diisocyanate, hexamethylene-1,6-diisocyanate Over preparative and cyclic trimer of such derivatives, and the like.

Furthermore, for the purpose of improving the preservability of the photosensitive composition, a compound obtained by reacting a blocking agent with the isocyanate group of the polyisocyanate and its derivative may be used.
The isocyanate group blocking agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alcohols such as isopropanol and tert-butanol; lactams such as ε-caprolactam; phenol, cresol, p- phenols such as tert-butylphenol, p-sec-butylphenol, p-sec-amylphenol, p-octylphenol and p-nonylphenol; heterocyclic hydroxyl compounds such as 3-hydroxypyridine and 8-hydroxyquinoline; dialkylmalonate; Active methylene compounds such as methyl ethyl ketoxime, acetylacetone, alkyl acetoacetate oxime, acetoxime, and cyclohexanone oxime; In addition to these, compounds having at least one polymerizable double bond and at least one blocked isocyanate group in the molecule described in JP-A-6-295060 can be used.

  Moreover, an aldehyde condensation product, a resin precursor, etc. can be used. Specifically, N, N′-dimethylolurea, N, N′-dimethylolmalonamide, N, N′-dimethylolsuccinimide, trimethylolmelamine, tetramethylolmelamine, hexamethylolmelamine, 1,3-N, N'-dimethylol terephthalamide, 2,4,6-trimethylolphenol, 2,6-dimethylol-4-methyliloanisole, 1,3-dimethylol-4,6-diisopropylbenzene and the like can be mentioned. Instead of these methylol compounds, the corresponding ethyl or butyl ether, or acetic acid or propionic acid ester may be used. Moreover, you may use the hexamethylated methylol melamine which consists of a formaldehyde condensation product of a melamine and urea, the butyl ether of a melamine and a formaldehyde condensation product, etc.

-Photopolymerization initiator-
The photopolymerization initiator is preferably contained because it imparts photosensitivity to the photosensitive composition, can be used as a photosensitive composition, and can be suitably used for a solder resist or the like.
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators, for example, visible from the ultraviolet region. Those having photosensitivity to light are preferable, and may be an activator that generates an active radical by causing some action with a photoexcited sensitizer, and initiates cationic polymerization depending on the type of monomer. It may be an initiator.
The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a range of about 300 to 800 nm (more preferably 330 to 500 nm).

  Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, those having an oxadiazole skeleton), phosphine oxide, hexaarylbiimidazole, Examples include oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, and ketoxime ethers.

  Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent 1388492, a compound described in JP-A-53-133428, a compound described in German Patent 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US Pat. No. 4,221,976 And the compounds described in the book.

  Wakabayashi et al., Bull. Chem. Soc. As a compound described in Japan, 42, 2924 (1969), for example, 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-chlorophenyl) -4,6 -Bis (trichloromethyl) -1,3,5-triazine, 2- (4-tolyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxyphenyl)- 4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,4-dichlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2, 4,6-tris (trichloromethyl) -1,3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2-n-nonyl-4,6- Bis (trichloromethyl) 1,3,5-triazine, and 2-(alpha, alpha, beta-trichloroethyl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

Examples of the compound described in the British Patent 1388492 include 2-styryl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methylstyryl) -4,6- Bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl)- 4-amino-6-trichloromethyl-1,3,5-triazine and the like can be mentioned.
Examples of the compounds described in JP-A-53-133428 include 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2 -(4-Ethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl]- 4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5- Examples include triazine and 2- (acenaphtho-5-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

  Examples of the compound described in the specification of German Patent 3333724 include 2- (4-styrylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4 -Methoxystyryl) phenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (1-naphthylvinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5 -Triazine, 2-chlorostyrylphenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-thiophen-2-vinylenephenyl) -4,6-bis (trichloromethyl)- 1,3,5-triazine, 2- (4-thiophene-3-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-furan-2 Vinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, and 2- (4-benzofuran-2-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3 5-triazine etc. are mentioned.

  F. above. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964) include, for example, 2-methyl-4,6-bis (tribromomethyl) -1,3,5-triazine, 2,4,6-tris (tribromomethyl); -1,3,5-triazine, 2,4,6-tris (dibromomethyl) -1,3,5-triazine, 2-amino-4-methyl-6-tri (bromomethyl) -1,3,5- Examples include triazine and 2-methoxy-4-methyl-6-trichloromethyl-1,3,5-triazine.

  Examples of the compounds described in JP-A-62-258241 include 2- (4-phenylethynylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- Naphthyl-1-ethynylphenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-tolylethynyl) phenyl) -4,6-bis (trichloromethyl) -1 , 3,5-triazine, 2- (4- (4-methoxyphenyl) ethynylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-isopropylphenyl) Ethynyl) phenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-ethylphenylethynyl) phenyl) -4,6-bis (trichloromethyl) Le) -1,3,5-triazine.

  Examples of the compound described in JP-A-5-281728 include 2- (4-trifluoromethylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2, 6-difluorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,6-dichlorophenyl) -4,6-bis (trichloromethyl) -1,3,5- Examples include triazine, 2- (2,6-dibromophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

  Examples of the compound described in JP-A-5-34920 include 2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethylamino) -3-bromophenyl] -1, 3,5-triazine, trihalomethyl-s-triazine compounds described in US Pat. No. 4,239,850, 2,4,6-tris (trichloromethyl) -s-triazine, 2- (4-chlorophenyl) Examples include -4,6-bis (tribromomethyl) -s-triazine.

  Examples of the compound described in US Pat. No. 4,221,976 include compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2- Trichloromethyl-5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5 -(2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl) -1,3,4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1, 3,4-oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl) -1,3,4-oxadiazole, 2-tripromomethyl-5-styryl-1,3,4 Oxadiazole, etc.).

  Examples of the oxime derivative suitably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, and 2-acetoxy. Iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2- ON, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.

Further, as photopolymerization initiators other than those described above, polyhalogen compounds (for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N-phenylglycine (for example, Carbon tetrabromide, phenyl tribromomethyl sulfone, phenyl trichloromethyl ketone, etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) ) Coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis (5 , 7-di-n-propoxycoumarin), 3,3′-carbonyl (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3 -(3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, JP-A-5-19475, JP-A-7-271028, JP JP-A 2002-363206, JP-A 2002-363207, JP-A 2002-363208, JP-A 2002-363209, and the like, and amines (for example, ethyl 4-dimethylaminobenzoate). , 4-dimethylaminobenzoic acid n-butyl, 4-dimethyl Phenethyl aminobenzoate, 2-dimethylimidoethyl 4-dimethylaminobenzoate, 2-methacryloyloxyethyl 4-dimethylaminobenzoate, pentamethylenebis (4-dimethylaminobenzoate), phenethyl 3-dimethylaminobenzoate, pentamethylene Ester, 4-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylaminobenzyl alcohol, ethyl (4-dimethylaminobenzoyl) acetate, 4-piperidinoacetophenone, 4-dimethylaminobenzoin, N, N-dimethyl-4-toluidine, N, N-diethyl-3-phenidine, tribenzylamine, dibenzylphenylamine, N-methyl-N-phenylbenzylamine, 4-bromo-N, N-dimethyl Ruaniline, tridodecylamine, aminofluoranes (ODB, ODBII, etc.), crystal violet lactone, leuco crystal violet, etc., acylphosphine oxides (for example, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, etc.), metallocenes (for example, bis (η ₅ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, η ₅ -cyclopentadienyl-η ₆ -cumenyl-iron (1 +)-hexafluorophosphate (1-), etc.) JP, 53-133428, A JP, Sho 57-1819, JP-the 57-6096 and JP, US Patent compounds described in the 3,615,455 Patent specification mentioned.

  Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzolphenone, benzophenonetetracarboxylic acid or tetramethyl ester thereof, 4,4′-bis (dialkylamino) benzophenone (for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′- Bis (dicyclohexylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4′-dimethylamino Benzophenone, 4,4′-dimethoxybenzophenone, 4-dimethylaminobenzophenone), 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2- Chlor-thioxanthone, 2,4-diethylthioxanthone, fluorenone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2- Morpholino-1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether, Emission zone in propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloro acridone, N- methyl acridone, N- butyl acridone, N- butyl - such as chloro acrylic pyrrolidone.

In addition to the photopolymerization initiator, a sensitizer can be added for the purpose of adjusting the exposure sensitivity and the photosensitive wavelength in exposure to the photosensitive layer described later.
The sensitizer can be appropriately selected by a visible light, an ultraviolet laser, a visible light laser or the like as a light irradiation means described later.
The sensitizer is excited by active energy rays and interacts with other substances (eg, radical generator, acid generator, etc.) (eg, energy transfer, electron transfer, etc.) to thereby generate radicals, acids, etc. It is possible to generate a useful group of

  The sensitizer is not particularly limited and may be appropriately selected from known sensitizers. For example, known polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, Fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, indocarbocyanine, thiacarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue) , Toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squariums (eg, squalium), acridones (eg, acridone, chloroacrid) N-methylacridone, N-butylacridone, N-butyl-chloroacridone, etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7 -(1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3 ′ -Carbonylbis (5,7-di-n-propoxycoumarin), 3,3'-carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylamino Coumarin, 3- (4-Diethylaminocinnamoyl) -7-diethylaminocoumarin Examples thereof include 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, and others, such as JP-A-5-19475, JP-A-7-271028, No. 2002-363206, JP-A 2002-363207, JP-A 2002-363208, JP-A 2002-363209, and the like.

  Examples of the combination of the photopolymerization initiator and the sensitizer include, for example, an electron transfer start system described in JP-A-2001-305734 [(1) an electron donating initiator and a sensitizing dye, (2) A combination of an electron-accepting initiator and a sensitizing dye, (3) an electron-donating initiator, a sensitizing dye and an electron-accepting initiator (ternary initiation system)], and the like.

  The content of the sensitizer is preferably 0.05 to 30% by mass, more preferably 0.1 to 20% by mass, and 0.2 to 10% by mass with respect to all the components in the photosensitive composition. Particularly preferred. When the content is less than 0.05% by mass, the sensitivity to active energy rays is reduced, the exposure process takes time, and productivity may be reduced. The sensitizer may be precipitated from the photosensitive layer.

The said photoinitiator may be used individually by 1 type, and may use 2 or more types together.
Particularly preferred examples of the photopolymerization initiator include halogenated carbonization having the phosphine oxides, the α-aminoalkyl ketones, and the triazine skeleton capable of supporting laser light having a wavelength of 405 nm in the exposure described later. Examples include a composite photoinitiator, a hexaarylbiimidazole compound, or titanocene, which is a combination of a hydrogen compound and an amine compound as a sensitizer described later.

  0.5-20 mass% is preferable, as for content in the said photosensitive composition of the said photoinitiator, 1-15 mass% is more preferable, and 2-10 mass% is especially preferable.

-Other ingredients-
The other components are not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include solvents, adhesion promoters, thermal polymerization inhibitors, colorants, and other additives. Adhesion promoters and other auxiliaries to the material surface (for example, conductive particles, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, etc.) May be used in combination. By appropriately containing these components, it is possible to adjust properties such as the stability, photographic properties, and film properties of the intended photosensitive composition or photosensitive film.

--Solvent--
There is no restriction | limiting in particular as said solvent, According to the objective, it can select suitably, For example, alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, n-hexanol; acetone , Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone; esters such as ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxypropyl acetate Aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene; halogenated carbonization such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, monochlorobenzene Motorui; tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethers such as 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and sulfolane. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.

-Adhesion promoter-
The adhesion promoter has a function of improving adhesion between layers, adhesion between the photosensitive layer and the substrate, and electrolytic corrosion.
The adhesion promoter is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include melamine, acetoguanamine, benzoguatemine, melamine-phenol formalin resin, ethyldiamino-S-triazine, 2,4-diamino. And triazine compounds such as -S-triazine and 2,4-diamino-6-xylyl-S-triazine. Commercially available triazine compounds include Shikoku Kasei Kogyo Co., Ltd. shown in the following structural formulas (B) to (D); 2MZ-AZINE (structural formula (B)), 2E4MZ-AZINE (structural formula (C)), CllZ -AZINE (structural formula (D)) and the like.

  These compounds increase the adhesion to the copper circuit, improve the PCT resistance, and have an effect on electrolytic corrosion. These can be used alone or in combination of two or more. 0.1-40 mass% is preferable with respect to the photosensitive composition solid content, and, as for the compounding quantity of an adhesion promoter, 0.1-20 mass% is more preferable.

--- Thermal polymerization inhibitor ---
The thermal polymerization inhibitor is preferably added to prevent thermal polymerization or temporal polymerization of the polymerizable compound and improve storage stability.
The thermal polymerization inhibitor is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 4-methoxyphenol, hydroquinone, hydroquinone monomethyl ether, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, chloranil, naphthylamine, β-naphthol, 2,6-di-t-butyl-4-cresol, 2,2′-methylenebis ( 4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, and phenothiazine, nitroso compound, nitroso compound Such as chelates with Al and the like.

  The content of the thermal polymerization inhibitor is preferably 0.001 to 5% by mass, more preferably 0.005 to 2% by mass, and particularly preferably 0.01 to 1% by mass with respect to the polymerizable compound. When the content is less than 0.001% by mass, stability during storage may be lowered, and when it exceeds 5% by mass, sensitivity to active energy rays may be lowered.

--Colorant--
There is no restriction | limiting in particular as said coloring agent, According to the objective, it can select suitably, For example, dyes, such as a coloring pigment suitably selected from well-known dyes, can be used.

  There is no restriction | limiting in particular as said coloring pigment, According to the objective, it can select suitably, For example, phthalocyanine green, Victoria pure blue BO (CI. 42595), auramine (CI. 41000), fat Black HB (C.I. 26150), Monolite Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (C.I) Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Hoster Balm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11) ) Fastel Pink B Spula (CI Pigment Red 1) Monasutoraru Fast Blue (C.I. Pigment Blue 15), mono Light Fast Black B (C.I. Pigment Black 1), carbon, C. I. Pigment red 97, C.I. I. Pigment red 122, C.I. I. Pigment red 149, C.I. I. Pigment red 168, C.I. I. Pigment red 177, C.I. I. Pigment red 180, C.I. I. Pigment red 192, C.I. I. Pigment red 215, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 22, C.I. I. Pigment blue 60, C.I. I. Pigment blue 64 and the like. These may be used alone or in combination of two or more.

  The solid content in the solid content of the photosensitive composition solution of the color pigment can be determined in consideration of the exposure sensitivity, resolution, etc. of the photosensitive layer during permanent pattern formation. Although depending on the type, generally 0.1 to 10% by mass is preferable, and 0.5 to 8% by mass is more preferable.

-Other additives-
The other additive is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include thixotropic agents such as benton, montmorillonite, aerosol, amide wax, silicone-based, fluorine-based, and polymer-based. Additives such as antifoaming agents and leveling agents can be used.
The method for producing a photosensitive composition of the present invention is preferably used in the method for producing a photosensitive film of the present invention, which will be described later, because the viscosity of the resulting photosensitive composition is maintained in a suitable state and is excellent in stability over time. be able to.

<Photosensitive layer forming step>
The photosensitive layer forming step is performed by applying the photosensitive composition solution on a support using a coating apparatus. The application time is not particularly limited, but preferably starts within 72 hours from completion of the photosensitive composition, and more preferably starts within 24 hours. When 72 hours have passed since the mixing, the viscosity of the photosensitive composition may change, and a stable coated surface may not be obtained. Therefore, the shorter the time from completion of the photosensitive composition to application, the smaller the change in viscosity of the photosensitive composition and the better the application surface. By this photosensitive layer forming step, a photosensitive layer made of the photosensitive composition is formed on the support.

There is no restriction | limiting in particular as a coating method of the said photosensitive composition, According to the objective, it can select suitably, For example, a coating operation may be performed continuously and you may carry out discontinuously. The discontinuous application operation is not particularly limited and can be appropriately selected according to the purpose. For example, the discontinuous application operation may be intermittent, in which the application is continued for 30 minutes and then applied for 60 minutes. Alternatively, the continuous interruption may be repeated, or a coating method may be used in which after a photosensitive layer having a certain thickness is formed, an interruption for drying is provided and further overcoating is performed.
Specific coating methods include spraying, roll coating, spin coating, slit coating, extrusion coating, curtain coating, die coating, gravure coating, wire bar coating, and knife coating. The coating method is mentioned.

  The coating device is not particularly limited and can be appropriately selected depending on the purpose. For example, a dispenser system that automatically performs coating from mixing of a coating solution, a static mixer or a micromixer, an in-line mixing device, a feeding device. Examples thereof include a coating apparatus combined with a liquid apparatus.

-Support-
The support is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferable that the photosensitive layer can be peeled off and has good light transmittance, and further has a smooth surface. It is more preferable that it is good.

The support is preferably made of a synthetic resin and transparent, for example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester, poly ( (Meth) acrylic acid ester copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoro Various plastic films such as ethylene, cellulosic film, nylon film and the like can be mentioned, and among these, polyethylene terephthalate is particularly preferable. These may be used alone or in combination of two or more.
As the support, for example, the support described in JP-A-4-208940, JP-A-5-80503, JP-A-5-173320, JP-A-5-72724, or the like is used. You can also.

There is no restriction | limiting in particular in the thickness of the said support body, According to the objective, it can select suitably, For example, 4-300 micrometers is preferable and 5-175 micrometers is more preferable.
There is no restriction | limiting in particular as a shape of the said support body, According to the objective, it can select suitably, A long shape is preferable. There is no restriction | limiting in particular in the length of the said elongate support body, For example, the thing of the length of 10m-20,000m is mentioned.

-Photosensitive layer-
The portion of the photosensitive layer provided in the photosensitive film is not particularly limited and may be appropriately selected depending on the purpose. May be.

  There is no restriction | limiting in particular in the thickness of the said photosensitive layer, According to the objective, it can select suitably, For example, 3-100 micrometers is preferable and 5-70 micrometers is more preferable.

  In the exposure process described later, the photosensitive layer modulates the light from the light irradiating means by means of a light modulating means having n picture element portions that receive and emit light from the light irradiating means, and then It is preferable that exposure is performed with light passing through a microlens array in which microlenses having aspherical surfaces capable of correcting aberration due to distortion of the exit surface at the portion are arranged.

<Other processes>
There is no restriction | limiting in particular as said other process, According to the objective, it can select suitably, For example, a drying process, a protective film formation process, another layer formation process, etc. are mentioned.

-Drying process-
The drying step varies depending on each component, the type of solvent, the ratio of use, etc., but can be appropriately selected according to the purpose. And the like.

-Protective film formation process-
The protective film forming step is a step of forming a protective film having a function of preventing and protecting the photosensitive layer from being stained and damaged.
There is no restriction | limiting in particular as a location provided in the said photosensitive film of the said protective film, Although it can select suitably according to the objective, Usually, it is provided on the said photosensitive layer.
Examples of the protective film include those used for the support, silicone paper, polyethylene, paper laminated with polypropylene, polyolefin or polytetrafluoroethylene sheet, etc. Among these, polyethylene film, Polypropylene film is preferred.
There is no restriction | limiting in particular in the thickness of the said protective film, Although it can select suitably according to the objective, For example, 5-100 micrometers is preferable and 8-30 micrometers is more preferable.

When the protective film is used, it is preferable that the adhesive force A between the photosensitive layer and the support and the adhesive force B between the photosensitive layer and the protective film satisfy the relationship of adhesive force A> adhesive force B.
Examples of the combination of the support and the protective film (support / protective film) include polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate, and the like. . Moreover, the above-mentioned relationship of adhesive force can be satisfy | filled by surface-treating at least any one of a support body and a protective film. The surface treatment of the support may be performed in order to increase the adhesive force with the photosensitive layer. For example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow treatment Examples thereof include discharge irradiation treatment, active plasma irradiation treatment, and laser beam irradiation treatment.

Moreover, as a static friction coefficient of the said support body and the said protective film, 0.3-1.4 are preferable and 0.5-1.2 are more preferable.
When the coefficient of static friction is less than 0.3, slipping is excessive, so that winding deviation may occur when the roll is formed, and when it exceeds 1.4, it is difficult to wind into a good roll. Sometimes.

  The photosensitive film is preferably stored, for example, wound around a cylindrical core, wound in a long roll shape. There is no restriction | limiting in particular in the length of the said elongate photosensitive film, For example, it can select suitably from the range of 10-20,000m. Further, slitting may be performed so that the user can easily use, and a long body in the range of 100 to 1,000 m may be formed into a roll. In this case, it is preferable that the support is wound up so as to be the outermost side. Moreover, you may slit the said roll-shaped photosensitive film in a sheet form. When storing, from the viewpoint of protecting the end face and preventing edge fusion, it is preferable to install a separator (particularly moisture-proof and containing a desiccant) on the end face, and use a low moisture-permeable material for packaging. Is preferred.

  The protective film may be surface-treated in order to adjust the adhesion between the protective film and the photosensitive layer. In the surface treatment, for example, 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 to the surface of the protective film and then drying at 30 to 150 ° C. (especially 50 to 120 ° C.) for 1 to 30 minutes.

-Other layer formation process-
There is no restriction | limiting in particular as said other layer formation process, According to the objective, it can select suitably, For example, a cushion layer, an oxygen barrier layer (PC layer), a peeling layer, an adhesive layer, a light absorption layer, surface protection Examples include a step of forming a layer such as a layer.
The cushion layer is a layer that has no tackiness at room temperature and melts and flows when laminated under vacuum and heating conditions. The PC layer is usually a film having a thickness of about 1.5 μm formed mainly of polyvinyl alcohol.
The photosensitive film of the present invention has a photosensitive layer on which a photosensitive composition that exhibits excellent storage stability and exhibits excellent chemical resistance, surface hardness, heat resistance and the like after development is laminated. For this reason, it can be widely used for the formation of permanent patterns such as printed wiring boards, color filters, pillar materials, rib materials, spacers, partition members, etc., holograms, micromachines, proofs, etc. It can use suitably for a method.
In particular, since the photosensitive film of the present invention has a uniform thickness, even when the permanent pattern (protective film, interlayer insulating film, solder resist, etc.) is thinned during the formation of the permanent pattern, the heat resistance, Since a high-definition permanent pattern excellent in moisture resistance can be obtained, lamination to the substrate is performed more finely.

(Permanent pattern forming method)
A permanent pattern is obtained by the permanent pattern forming method of the present invention.
In the method for forming a permanent pattern of the present invention, as a first embodiment, the photosensitive composition of the present invention is applied to the surface of a substrate, dried to form a photosensitive layer, and then exposed and developed.
In addition, in the method for forming a permanent pattern of the present invention, as a second aspect, the photosensitive film of the present invention is laminated on the surface of the substrate under at least one of heating and pressing, and then exposed and developed. .
Hereinafter, the details of the permanent pattern will be clarified through the description of the method for forming a permanent pattern of the present invention.

-Base material-
The base material is not particularly limited, and can be appropriately selected from known materials having high surface smoothness to those having an uneven surface. A plate-shaped base material (substrate) is preferable, Specifically, a known printed wiring board forming substrate (for example, a copper-clad laminate), a glass plate (for example, a soda glass plate), a synthetic resin film, paper, a metal plate, etc. may be mentioned. Among them, a printed wiring board forming substrate is preferable, and the printed wiring board forming substrate has already been formed with a wiring in that it enables high-density mounting of a semiconductor or the like on a multilayer wiring board or a build-up wiring board. Is particularly preferred.

  The substrate is a laminate in which a photosensitive layer made of the photosensitive composition (polymerizable composition) of the present invention is formed on the substrate as the first embodiment, or the second embodiment, It can be used by forming a laminate in which the photosensitive layers in the photosensitive film are laminated so as to overlap. That is, by exposing the photosensitive layer in the laminated body to be described later, the exposed region can be cured, and a permanent pattern can be formed by development to be described later.

-Laminate-
There is no restriction | limiting in particular as a formation method of the laminated body of a said 1st aspect, According to the objective, it can select suitably, The photosensitive composition (polymerizable composition) of this invention is put on the said base material. It is preferable to laminate a photosensitive layer formed by coating and drying.
There is no restriction | limiting in particular as the method of the said application | coating and drying, According to the objective, it can select suitably, For example, application | coating of the said photosensitive composition solution performed when forming the photosensitive layer in the said photosensitive film. For example, a method of applying the photosensitive composition solution using a spin coater, a slit spin coater, a roll coater, a die coater, a curtain coater, or the like can be given.

There is no restriction | limiting in particular as a formation method of the laminated body of the said 2nd aspect, According to the objective, it can select suitably, At least any one of heating and pressurizing the said photosensitive film on the said base material is performed. However, it is preferable to laminate them. In addition, when the said photosensitive film has the said protective film, it is preferable to peel this protective film and to laminate | stack so that the said photosensitive layer may overlap with the said base material.
There is no restriction | limiting in particular in the said heating temperature, According to the objective, it can select suitably, For example, 70-130 degreeC is preferable and 80-110 degreeC is more preferable.
There is no restriction | limiting in particular in the pressure of the said pressurization, According to the objective, it can select suitably, For example, 0.01-1.0 MPa is preferable and 0.05-1.0 MPa is more preferable.

  There is no restriction | limiting in particular as an apparatus which performs at least any one of the said heating and pressurization, According to the objective, it can select suitably, For example, heat press, a heat roll laminator (For example, Taisei Laminator company make, VP-II). ), A vacuum laminator (for example, MVLP500, manufactured by Meiki Seisakusho) and the like are preferable.

<Exposure process>
The exposure step is a step of exposing the photosensitive layer.

  The object of the exposure is not particularly limited as long as it is a material having a photosensitive layer, and can be appropriately selected according to the purpose. For example, the photosensitive composition (polymerizable composition) of the present invention on a substrate. ) Or the laminate formed with the photosensitive film.

  There is no restriction | limiting in particular as said exposure, According to the objective, it can select suitably, Digital exposure, analog exposure, etc. are mentioned, Among these, digital exposure is preferable.

  The digital exposure is not particularly limited and can be appropriately selected depending on the purpose. For example, a control signal is generated based on pattern formation information to be formed, and light modulated in accordance with the control signal is used. Preferably.

  The digital exposure means is not particularly limited and may be appropriately selected depending on the purpose. For example, light irradiation means for irradiating light, light emitted from the light irradiation means based on pattern information to be formed And a light modulation means for modulating the light intensity.

<Light modulation means>
The light modulation means is not particularly limited as long as it can modulate light, and can be appropriately selected according to the purpose. For example, it preferably has n pixel portions.
There is no restriction | limiting in particular as a light modulation means which has the said n image drawing part, According to the objective, it can select suitably, For example, a spatial light modulation element is preferable.

  Examples of the spatial light modulator include a digital micromirror device (DMD), a MEMS (Micro Electro Mechanical Systems) type spatial light modulator (SLM), and modulates transmitted light by an electro-optic effect. An optical element (PLZT element), a liquid crystal optical shutter (FLC), etc. are mentioned, Among these, DMD is mentioned suitably.

  As an example of the light modulation means, for example, the means described in the specification [0016] to [0047] of JP-A-2005-258431 can be cited.

<Light irradiation means>
The light irradiation means is not particularly limited and may be appropriately selected depending on the purpose. For example, (ultra) high pressure mercury lamp, xenon lamp, carbon arc lamp, halogen lamp, copier, fluorescent tube, LED, etc. , A known light source such as a semiconductor laser, or a means capable of synthesizing and irradiating two or more lights. Among these, a means capable of synthesizing and irradiating two or more lights is preferable.
The light emitted from the light irradiation means is, for example, an electromagnetic wave that passes through the support and activates the photopolymerization initiator and sensitizer used when the light is irradiated through the support. In particular, ultraviolet to visible light, electron beam, X-ray, laser beam, and the like can be mentioned. Of these, laser beam is preferable, and laser beam obtained by combining two or more beams (hereinafter, referred to as “combined laser beam”). ) Is more preferable. Even when light irradiation is performed after the support is peeled off, the same light can be used.

For example, the wavelength of ultraviolet to visible light is preferably 300 to 1,500 nm, more preferably 320 to 800 nm, and particularly preferably 330 to 650 nm.
For example, the wavelength of the laser beam is preferably 200 to 1,500 nm, more preferably 300 to 800 nm, still more preferably 330 to 500 nm, and particularly preferably 395 to 415 nm.

  Examples of means capable of irradiating the combined laser beam include a plurality of lasers, a multimode optical fiber, and a set for condensing and coupling the laser beams respectively emitted from the plurality of lasers to the multimode optical fiber. Means having an optical system are preferred.

  Hereinafter, examples of the means (fiber array light source) capable of irradiating the combined laser light include means described in the specifications [0110] to [0157] of JP-A-2005-258431.

<Microlens array>
Further, the exposure is preferably performed through the microlens array with the modulated light, and may be performed through an aperture array, an imaging optical system, or the like.

  The microlens array is not particularly limited and may be appropriately selected depending on the purpose. For example, a microlens array having an aspherical surface capable of correcting aberration due to distortion of the exit surface in the pixel portion Are preferable.

  There is no restriction | limiting in particular as said aspherical surface, According to the objective, it can select suitably, For example, a toric surface is preferable.

  Hereinafter, the microlens array, the aperture array, the imaging optical system, and the like are described in, for example, specifications [0050] to [0073] and [0083] to [0088] of JP-A-2005-258431. The means currently used are mentioned.

<Other optical systems>
In the permanent pattern forming method of the present invention, it may be used in combination with other optical systems appropriately selected from known optical systems, for example, a light quantity distribution correcting optical system composed of a pair of combination lenses.
The light amount distribution correcting optical system changes the light flux width at each exit position so that the ratio of the light flux width at the peripheral portion to the light flux width at the central portion close to the optical axis is smaller on the exit side than on the incident side. When the DMD is irradiated with the parallel light flux from the light irradiation means, the light amount distribution on the irradiated surface is corrected so as to be substantially uniform. Hereinafter, examples of the light amount distribution correcting optical system include means described in the specification [0090] to [0105] of JP-A-2005-258431.

-Development process-
The developing step is a step of forming a permanent pattern by exposing the photosensitive layer by the exposing step, curing the exposed region of the photosensitive layer, and then developing by removing the uncured region.

  There is no restriction | limiting in particular as the removal method of the said unhardened area | region, According to the objective, it can select suitably, For example, the method etc. which remove using a developing solution are mentioned.

  The developer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, alkali metal or alkaline earth metal hydroxide or carbonate, hydrogen carbonate, aqueous ammonia, quaternary ammonium salt An aqueous solution of Among these, an aqueous sodium carbonate solution is particularly preferable.

  The developer includes a surfactant, an antifoaming agent, an organic base (for example, benzylamine, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.) May be used in combination with an organic solvent (for example, alcohols, ketones, esters, ethers, amides, lactones, etc.). The developer may be an aqueous developer obtained by mixing water or an alkaline aqueous solution and an organic solvent, or may be an organic solvent alone.

-Curing process-
The permanent pattern forming method of the present invention preferably further includes a curing treatment step.
The curing treatment step is a step of performing a curing treatment on the photosensitive layer in the formed permanent pattern after the development step is performed.

  There is no restriction | limiting in particular as said hardening process, According to the objective, it can select suitably, For example, a whole surface exposure process, a whole surface heat processing, etc. are mentioned suitably.

Examples of the entire surface exposure processing method include a method of exposing the entire surface of the laminate on which the permanent pattern is formed after the developing step. The entire surface exposure accelerates the curing of the resin in the photosensitive composition forming the photosensitive layer, and the surface of the permanent pattern is cured.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface exposure, According to the objective, it can select suitably, For example, UV exposure machines, such as an ultrahigh pressure mercury lamp, are mentioned suitably.

Examples of the entire surface heat treatment method include a method of heating the entire surface of the laminate on which the permanent pattern is formed after the developing step. By heating the entire surface, the film strength of the surface of the permanent pattern is increased.
120-250 degreeC is preferable and the heating temperature in the said whole surface heating has more preferable 120-200 degreeC. If the heating temperature is less than 120 ° C, the film strength may not be improved by heat treatment. If the heating temperature exceeds 250 ° C, the resin in the photosensitive composition may be decomposed, resulting in weak and brittle film quality. There is.
The heating time in the entire surface heating is preferably 10 to 120 minutes, and more preferably 15 to 60 minutes.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface heating, According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, IR heater etc. are mentioned.

When the substrate is a printed wiring board such as a multilayer wiring board, the permanent pattern of the present invention can be formed on the printed wiring board, and further soldered as follows.
That is, the development step forms a hardened layer that is the permanent pattern, and the metal layer is exposed on the surface of the printed wiring 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. At this time, the permanent pattern by the hardened layer exhibits a function as a protective film or an insulating film (interlayer insulating film), and prevents external impact and conduction between adjacent electrodes.

  In the permanent pattern forming method of the present invention, it is preferable to form at least one of a protective film and an interlayer insulating film. When the permanent pattern formed by the permanent pattern forming method is the protective film or the interlayer insulating film, the wiring can be protected from external impact and bending, particularly when the interlayer insulating film is the interlayer insulating film. Is useful for high-density mounting of semiconductors and components on, for example, multilayer wiring boards and build-up wiring boards.

The permanent pattern forming method of the present invention can be widely used for forming various patterns because the pattern can be formed at a high speed, and can be particularly suitably used for forming a wiring pattern.
In addition, the permanent pattern formed by the method for forming a permanent pattern of the present invention has excellent surface hardness, insulation, heat resistance, moisture resistance, etc., and is suitably used as a protective film, interlayer insulation film, solder resist pattern, etc. can do.

  Examples of the present invention will be described below, but the present invention is not limited to the following examples.

(Synthesis Example 1)
In a 1,000 mL three-necked flask, 159 g of 1-methoxy-2-propanol was placed and heated to 85 ° C. under a nitrogen stream. To this, a solution of 159 g of 1-methoxy-2-propanol containing 63.4 g of benzyl methacrylate, 72.3 g of methacrylic acid, and 4.15 g of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped over 2 hours. After completion of the dropwise addition, the reaction was further continued by heating for 5 hours. Subsequently, the heating was stopped to obtain a copolymer of benzyl methacrylate / methacrylic acid (ratio of 30/70 mol%).
Next, 120.0 g of the copolymer solution was transferred to a 300 mL three-necked flask, and 16.6 g of glycidyl methacrylate and 0.16 g of p-methoxyphenol were added and stirred to dissolve. After dissolution, 2.4 g of triphenylphosphine was added and heated to 100 ° C. to carry out an addition reaction. The disappearance of glycidyl methacrylate was confirmed by gas chromatography, and heating was stopped. 1-Methoxy-2-propanol was added to prepare a solution of polymer compound 1 represented by the following structural formula having a solid content of 45% by mass.
The mass average molecular weight (Mw) of the obtained polymer compound was 15,000 as a result of measurement by gel permeation chromatography (GPC) using polystyrene as a standard substance. From the titration with sodium hydroxide, the acid value (carboxyl group content) per solid content was 2.2 meq / g.
Furthermore, the content of ethylenically unsaturated bonds per solid (C = C value) determined by iodine value titration was 2.1 meq / g.

Example 1
-Production of photosensitive composition-
<Preparation of dispersion>
110 parts by mass of silica (Admafine SO-C2 manufactured by Admatechs)
Thermosetting accelerator (dicyandiamide) 1.30 parts by mass,
HELIOGEN BLUE D7086 (manufactured by BASF) 2.0 parts by mass,
PALIOTOL YELLOW D0960 (manufactured by BASF) 0.55 parts by weight,
Polymer compound 1 represented by (Synthesis Example 1) (solid content in the 1-methoxy-2-propanol solution: 45% by mass) 175 parts by mass n-propyl acetate 215 parts by mass

  The dispersion was prepared by previously mixing the above components and then dispersing the mixture for 3 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 1.0 mm using a minimotor mill M-250 (manufactured by Eiger).

<Measurement of average particle diameter of dispersed particles in dispersion>
The average particle size of the dispersed particles in the prepared dispersion was measured by a particle size measuring device (LB-500: manufactured by Horiba, Ltd.) and found to be 0.50 μm.

<Filtration of dispersion>
The above dispersion was filtered through a filter (average pore size 20 μm, trade name “Ulple Pleat Profile, Model No. PUY01UY200J” (manufacturer “Nihon Pall Co., Ltd.”). Using a gear pump (model number KA1-2.92-09, manufacturer “Kawasaki Heavy Industries, Ltd.”), the pump housing (model M01SS-01G4H1, Nippon Pole Co., Ltd.) with a flow rate of 0.2 mL / min and mounted with the filter Through the company), a filtered dispersion was obtained.

<Preparation of coating solution>
Each of the following components was mixed with 38 parts by mass of the filtered dispersion to prepare a coating solution.
[Each component amount of photosensitive composition solution]
-Polymer compound 1 shown in (Synthesis Example 1) (solid content of 45% by mass in the 1-methoxy-2-propanol solution) ... 40 parts by mass-Polymerizable compound (dipentaerythritol hexaacrylate) ... 9.6 parts by mass-Photopolymerization initiator (Ciba Specialty Chemicals, Irgacure 819 (acylphosphine oxide compound)) ... 0.41 parts by mass-Increase represented by the following formula S-1 Sensitizer (diethylthioxanthone): 0.42 parts by mass Fluorosurfactant (Megafac F-780F, manufactured by Dainippon Ink & Chemicals, Inc., 30% by mass 2-butanone solution) 2 parts by mass, methyl ethyl ketone, 10 parts by mass, thermal crosslinking agent (the following structural formula B), 5.3 parts by mass

-Production of photosensitive film-
The obtained photosensitive composition is used as a support 1 shown in FIG. 1 using a polyethylene terephthalate (PET) film (manufactured by Toray Industries, Inc., 16FB50) having a thickness of 16 μm. The support 1 is dried by a bar coater. The photosensitive layer 2 was continuously applied to a thickness of about 30 μm, dried in a hot air circulating dryer at 80 ° C. for 30 minutes, and then a protective film 3 having a thickness of 20 μm on the photosensitive layer. A polypropylene film was laminated with a laminate to produce a photosensitive film.
The coated surface shape of the photosensitive layer of the obtained photosensitive film was evaluated by the following evaluation method, and the results are shown in Table 1.

<Formation of permanent pattern>
-Preparation of laminate-
Next, the substrate was prepared by subjecting the surface of a copper-clad laminate (printed wiring board having no through hole and a copper thickness of 12 μm) on which wiring had been formed to chemical polishing. A vacuum laminator (MVLP500, manufactured by Meiki Seisakusho Co., Ltd.) was used on the copper-clad laminate while peeling off the protective film from the photosensitive film so that the photosensitive layer of the photosensitive film was in contact with the copper-clad laminate. Lamination was performed to prepare a laminate in which the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) were laminated in this order.
The pressure bonding conditions were a pressure bonding temperature of 90 ° C., a pressure bonding pressure of 0.4 MPa, and a laminating speed of 1 m / min.

-Exposure process-
A predetermined pattern can be obtained with a laser beam of 405 nm from the polyethylene terephthalate film (support) side using a pattern forming apparatus by blue-violet laser exposure having a predetermined pattern with respect to the photosensitive layer in the prepared laminate. In this way, an energy amount of 40 mJ / cm ² was irradiated for exposure, and a partial region of the photosensitive layer was cured.

-Development process-
After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) is peeled off from the laminate, and a 1% by mass aqueous sodium carbonate solution is used as an alkaline developer on the entire surface of the photosensitive layer on the copper clad laminate. Spray development was performed at 30 ° C. for 60 seconds at a pressure of 0.18 MPa (1.8 kgf / cm ² ) to dissolve and remove unexposed areas. Thereafter, it was washed with water and dried to form a permanent pattern.

-Curing process-
The entire surface of the laminate on which the permanent pattern was formed was heat treated at 150 ° C. for 1 hour to cure the surface of the permanent pattern and increase the film strength.
According to the permanent pattern resist thus obtained, the insulation resistance after being left for 168 hours in an environment having the above composition and a temperature of 85 ° C. and a relative humidity of 85% is processed to be 10 ¹⁰ Ω or more. Therefore, even when used in a high temperature and high humidity atmosphere, the wiring conductor layers are not short-circuited, and the wiring conductor layers are not corroded, and are excellent in moisture resistance. Further, since the obtained printed wiring board is formed by depositing a wiring conductor layer on the surface of the insulating substrate and covering the part of the insulating substrate, the permanent pattern is deposited. However, it is possible to protect the insulating layer from heat when mounting electronic components on a printed wiring board, and to protect the wiring conductor layer from oxidation and corrosion due to moisture. As a result, the heat resistance and moisture resistance are excellent.

<Evaluation of coated surface>
The coated surface of the photosensitive layer after coating and drying was visually observed to inspect the smoothness of the surface. The results are shown in Table 1.
○: Smooth.
Δ: Some have streaks, foreign matter, or repellency.
X: There are stripes, foreign matter, or repellency on the entire surface.

<Resolution>
The surface of the obtained printed circuit board on which the permanent pattern had been formed was observed with an optical microscope, and the minimum hole diameter with no residual film in the hole portion of the cured layer pattern was measured. The smaller the numerical value, the better the resolution. The results are shown in Table 1.

<Evaluation of chipped pattern after development>
Pattern chipping after development was observed with a microscope. The results are shown in Table 1.
○: No pattern missing.
Δ: Some pattern missing.
X: There are many pattern defects.

<Evaluation of thermal shock resistance (crack generation after TCT test)>
In addition, the permanent pattern was subjected to a heat cycle treatment (a treatment in which 500 cycles of heat treatment was performed by cooling at −65 ° C. for 30 minutes and heating at 125 ° C. for 30 minutes), and a 2 mm square hole pattern (grating A thermal cycle test was conducted to observe how cracks occurred (how many patterns out of 27 lattice patterns would crack). The results are shown in Table 1.
○: No crack occurred.
Δ: Some cracks occurred.
X: Many cracks are generated.

(Example 2)
Example 1 is the same as Example 1 except that the filter having an average pore diameter of 20 μm is changed to a filter having an average pore diameter of 10 μm (trade name “Ulple Pleat Profile, Model No. PUY01UY100J”, manufacturer “Nippon Pole Co., Ltd.”). A photosensitive composition, a photosensitive film, and a permanent pattern, measurement of the average particle diameter of dispersed particles in the dispersion, evaluation of the coated surface of the photosensitive layer, measurement of resolution, evaluation of pattern defects after development, The thermal shock resistance was evaluated. These results are shown in Table 1.

(Example 3)
Example 1 is the same as Example 1 except that the filter having an average pore diameter of 20 μm is changed to a filter having an average pore diameter of 30 μm (trade name “Ulchipleat Profile, Model No. PUY01UY300J”, manufacturer “Nihon Pall Co., Ltd.”). A photosensitive composition, a photosensitive film, and a permanent pattern, measurement of the average particle diameter of dispersed particles in the dispersion, evaluation of the coated surface of the photosensitive layer, measurement of resolution, evaluation of pattern defects after development, The thermal shock resistance was evaluated. These results are shown in Table 1.

Example 4
In Example 1, the photosensitive composition and the photosensitive film were the same as Example 1 except that the peripheral speed of the disperser was changed from 9 m / s to 8 m / s and the dispersion time was changed from 3 hours to 30 minutes. A permanent pattern was prepared, and the average particle diameter of dispersed particles in the dispersion, evaluation of the coated surface of the photosensitive layer, measurement of resolution, evaluation of pattern chipping after development, and evaluation of thermal shock resistance were performed. These results are shown in Table 1.

(Example 5)
In Example 1, except that the peripheral speed of the disperser was changed from 9 m / s to 6 m / s and the dispersion time was changed from 3 hours to 10 minutes, the photosensitive composition and the photosensitive film were the same as in Example 1. A permanent pattern was prepared, and the average particle diameter of dispersed particles in the dispersion, evaluation of the coated surface of the photosensitive layer, measurement of resolution, evaluation of pattern chipping after development, and evaluation of thermal shock resistance were performed. These results are shown in Table 1.

(Example 6)
In Example 1, a photosensitive composition was prepared in the same manner as in Example 1 except that silica (Admafine SO-C2 manufactured by Admatechs Co., Ltd.) was changed to silica (RAF-1000 manufactured by Tatsumori Co., Ltd.) Prepare photosensitive film and permanent pattern, measure average particle size of dispersed particles in dispersion, evaluate coated surface of photosensitive layer, measure resolution, evaluate pattern chipping after development, and evaluate thermal shock resistance. did. These results are shown in Table 1.

(Comparative Example 1)
In Example 1, a photosensitive composition, a photosensitive film, and a permanent pattern were prepared in the same manner as in Example 1 except that the dispersion liquid was not filtered, and the average particle diameter of the dispersed particles in the dispersion liquid was measured. The evaluation of the coated surface of the photosensitive layer, the measurement of resolution, the evaluation of chipping after development, and the evaluation of thermal shock resistance were performed. These results are shown in Table 1.

(Comparative Example 2)
Example 1 is the same as Example 1 except that the filter having an average pore size of 20 μm is changed to a filter having an average pore size of 40 μm (trade name “Ulple Pleat Profile, Model No. PUY01UY400J”, manufacturer “Nihon Pall Co., Ltd.”). A photosensitive composition, a photosensitive film, and a permanent pattern, measurement of the average particle diameter of dispersed particles in the dispersion, evaluation of the coated surface of the photosensitive layer, measurement of resolution, evaluation of pattern defects after development, The thermal shock resistance was evaluated. These results are shown in Table 1.

(Comparative Example 3)
Example 1 is the same as Example 1 except that the filter having an average pore diameter of 20 μm is changed to a filter having an average pore diameter of 70 μm (trade name “Ulple Pleat Profile, Model No. PUY01UY700J”, manufacturer “Nippon Pole Co., Ltd.”). A photosensitive composition, a photosensitive film, and a permanent pattern, measurement of the average particle diameter of dispersed particles in the dispersion, evaluation of the coated surface of the photosensitive layer, measurement of resolution, evaluation of pattern defects after development, The thermal shock resistance was evaluated. These results are shown in Table 1.

(Comparative Example 4)
Example 1 is the same as Example 1 except that the filter having an average pore diameter of 20 μm is changed to a filter having an average pore diameter of 6 μm (trade name “Ulple Pleat Profile, Model No. PUY01UY060J”, manufacturer “Nippon Pole Co., Ltd.”). A photosensitive composition, a photosensitive film, and a permanent pattern, measurement of the average particle diameter of dispersed particles in the dispersion, evaluation of the coated surface of the photosensitive layer, measurement of resolution, evaluation of pattern defects after development, The thermal shock resistance was evaluated. These results are shown in Table 1.

(Comparative Example 5)
In Example 1, a photosensitive composition, a photosensitive film, and a permanent composition were prepared in the same manner as in Example 1 except that the coating liquid was prepared without filtering the dispersion, and the prepared coating liquid was filtered. A pattern was prepared, and the average particle diameter of the dispersed particles in the dispersion, evaluation of the coated surface of the photosensitive layer, measurement of resolution, evaluation of pattern chipping after development, and evaluation of thermal shock resistance were performed. These results are shown in Table 1.

In Table 1, “buzz” means that there was foreign matter on the entire surface.

  From the results shown in Table 1, after preparing a dispersion containing a binder, a thermosetting accelerator, and a filler, the dispersion was prepared by passing through a filter having an average pore size of 10 to 30 μm and performing filtration. It was found that when the photosensitive compositions of Examples 1 to 6 were used, a stable planar photosensitive layer free from foreign matter failure (pattern chip after development, occurrence of cracks after TCT test) could be obtained. For this reason, it was found that a permanent pattern with good resolution and high reliability can be obtained.

  The photosensitive film obtained by the method for producing a photosensitive film of the present invention has an extremely stable coated surface, excellent storage stability, and exhibits excellent chemical resistance, surface hardness, heat resistance, etc. after development. To do. In addition, even if the permanent pattern (protective film, interlayer insulating film, solder resist, etc.) formed by the method for forming a permanent pattern of the present invention is thinned, it has high surface hardness, insulation, heat resistance, and moisture resistance. Since a fine permanent pattern can be obtained, it can be suitably used as a protective film and interlayer insulating film, and can be used for printed wiring boards (multilayer wiring boards, build-up wiring boards, etc.), color filters, pillar materials, rib materials, spacers, It can be widely used for the formation of permanent patterns such as display members such as partition walls, holograms, micromachines, and proofs.

FIG. 1 is an explanatory view showing the layer structure of the photosensitive film. FIG. 2 is an example of a partially enlarged view showing a configuration of a digital micromirror device (DMD). FIG. 3A is an example of a diagram illustrating an example of a DMD usage area (part 1). FIG. 3B is an example of a diagram illustrating an example of a DMD usage area (part 2). FIG. 4A is an example of a cross-sectional view along the optical axis showing the configuration of another exposure head having a different coupling optical system. FIG. 4B is an example of a plan view showing a light image projected on the exposure surface when a microlens array or the like is not used. FIG. 4C is an example of a plan view showing an optical image projected on the exposure surface when a microlens array or the like is used. FIG. 5A is a perspective view showing a configuration of a fiber array light source. FIG. 5B is an example of a partially enlarged view of FIG. 5A. FIG. 5C is an example of a front view showing the arrangement of light emitting points in the laser emitting section of the fiber array light source (part 1). FIG. 5D is an example of a front view showing the arrangement of light emitting points in the laser emitting section of the fiber array light source (part 2). FIG. 6 is an example of a diagram illustrating a configuration of a multimode optical fiber. FIG. 7 is an example of a plan view showing the configuration of the combined laser light source. FIG. 8 is an example of a plan view showing the configuration of the laser module. FIG. 9 is an example of a side view showing the configuration of the laser module shown in FIG. FIG. 10 is a partial side view showing the configuration of the laser module shown in FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Support body 2 Photosensitive layer 3 Protective film B1-B7 Laser beam LD1-LD7 GaN type semiconductor laser 10 Heat block 11-17 Collimator lens 20 Condensing lens 30-31 Multimode optical fiber 30a-31a Core 44 Collimator lens holder 45 Collection Optical lens holder 46 Fiber holder 50 Digital micromirror device (DMD)
60 Memory cell 62 Micro mirror 63 Protection plate 64 Laser module 65 Support plate 66 Fiber array light source 68 Laser emitting unit 454 Lens system 468 Exposure area 472 Micro lens array 476 Aperture array 478 Aperture 480 Lens system

Claims (7)

A dispersion preparation step for preparing a dispersion containing a silica compound as a binder, a thermosetting accelerator, and a filler;
A filtration step of filtering the prepared dispersion with a filter having an average pore size of 10 to 30 μm;
A photosensitive composition preparation step of preparing a photosensitive composition by adding a polymerizable compound and a thermal crosslinking agent to the filtered dispersion;
And a photosensitive layer forming step of forming a photosensitive layer by applying the prepared photosensitive composition on a support.   The method for producing a photosensitive film according to claim 1, wherein the silica compound is silica produced by a combustion method.   The method for producing a photosensitive film according to claim 1, wherein the average particle diameter of the dispersed particles in the dispersion is 0.1 to 5 μm.   A photosensitive film produced by the method for producing a photosensitive film according to claim 1.   A method for forming a permanent pattern, wherein the photosensitive layer of the photosensitive film according to claim 4 is transferred to the surface of a substrate, and then exposed and developed.   The permanent pattern formation method according to claim 5, wherein the exposure is performed using a laser beam having a wavelength of 395 to 415 nm.   The permanent pattern forming method according to claim 5, wherein at least one of a protective film, an interlayer insulating film, and a solder resist pattern is formed.