JP4976931B2 - Photosensitive composition, photosensitive film, permanent pattern forming method, and printed circuit board - Google Patents

Description

  The present invention relates to a photosensitive composition capable of efficiently forming a high-definition permanent pattern, a photosensitive film, a method for forming a permanent pattern, and a printed board.

  Conventionally, when forming a permanent pattern such as a solder resist, a photosensitive film in which a photosensitive layer is formed by applying and drying a photosensitive composition on a support has been used. As the method for producing the permanent pattern, for example, a laminate is formed by laminating the photosensitive film on a substrate such as a copper-clad laminate on which the permanent pattern is formed, and the photosensitive layer in the laminate is formed on the photosensitive layer. The permanent pattern is formed by exposing to light, developing the photosensitive layer after the exposure to form a pattern, and then performing a curing process or the like.

Here, in the photosensitive composition, regardless of its use, to improve the surface hardness of the permanent pattern, or to keep the coefficient of linear expansion low, or to keep the dielectric constant or dielectric loss tangent of the cured film itself low. For the purpose, an inorganic pigment is generally used. It is known that the surface treatment of this inorganic pigment can impart dispersibility of the coating liquid and low water absorption and toughness of the obtained cured product.
For solder resist applications, a proposal has been made that the inorganic pigment is subjected to a surface treatment for the purpose of preventing development residue from remaining and deterioration of developability when barium sulfate is used as the inorganic pigment (Patent Document 1). ).
However, the above proposal has a problem that it is difficult to obtain a permanent pattern with high definition and efficiency because the sensitivity is not always sufficient depending on the photopolymerization initiator used.
Furthermore, in order to make the permanent pattern high definition, it is also important to improve the adhesion after development (adhesion of fine lines).

  Therefore, a photosensitive composition, a photosensitive film, a method for forming a permanent pattern with good sensitivity, developability, and adhesion, and capable of efficiently forming a high-definition permanent pattern, a method for forming a permanent pattern using the photosensitive composition, and the permanent At present, development of a printed circuit board on which a pattern is formed by a pattern forming method is desired.

Japanese Patent Application Laid-Open No. 2002-296771

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, the present invention provides a photosensitive composition, a photosensitive film, and a method for forming a permanent pattern using the photosensitive composition, which have good sensitivity, developability and adhesion, and can efficiently form a high-definition permanent pattern. And a printed circuit board on which a pattern is formed by the permanent pattern forming method.

Means for solving the problems are as follows. That is,
<1> A binder, a polymerizable compound, a photopolymerization initiator, a thermal crosslinking agent, and an inorganic pigment, the photopolymerization initiator includes an oxime derivative, and the inorganic pigment is surface-treated with a silane coupling agent. It is the photosensitive composition characterized by these.
<2> The silane coupling agent is at least one functional group selected from an alkoxysilyl group, a chlorosilyl group, and an acetoxysilyl group, a vinyl group, an amino group, a mercapto group, an epoxy group, and a (meth) acryloyl group. It is a photosensitive composition as described in said <1> which has at least 1 sort (s) of functional group selected from these.
<3> The photosensitive composition according to any one of <1> to <2>, wherein the inorganic pigment is silica.
<4> The photosensitive composition according to any one of <1> to <3>, wherein the oxime derivative is a compound having at least an aromatic group.
<5> The oxime derivative according to any one of <1> to <4>, wherein the oxime derivative has a partial structure represented by any one of the following general formula (I), general formula (II), and general formula (X): It is a photosensitive composition.
However, in said general formula (I) and (II), Ar represents either an aromatic group or a heterocyclic group. Y ¹ represents any ^one of a hydrogen atom and a monovalent substituent, and Y ² represents any one of an aliphatic group, an aromatic group, a heterocyclic group, COY ³ , CO ₂ Y ³ , and CONY ⁴ Y ^5. . Y ³ , Y ⁴ , and Y ^{5 each} represent an aliphatic group, an aromatic group, or a heterocyclic group. m represents an integer of 1 or more.
In the general formula (X), R ¹⁰⁰ represents any of an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group, and these substituents may further have a substituent. α represents any integer of 0 or more. R ²⁰⁰ represents a substituent, and when α is 2 or more, the R ²⁰⁰ may be the same or different. Ar represents either an aromatic ring or a heteroaromatic ring. A represents any of 4, 5, 6, and 7-membered rings, and each of these rings may contain a hetero atom.
<6> The photosensitive composition according to <5>, wherein Ar in the general formula (I), the general formula (II), and the general formula (X) has a phenyl group or a naphthyl group.
<7> The photosensitive composition according to <6>, wherein Ar in the general formula (I), the general formula (II), and the general formula (X) has a naphthyl group.
<8> The photosensitive composition according to any one of <5> to <7>, wherein the general formula (I) is further represented by any one of the following general formula (III) and general formula (IV): .
However, the general formula (III) and the general formula _{(IV), R 101} represents the same meaning as ^{Y 1} in the general formulas (I) and ^{(II), Y 12} is general formulas (I) and This represents the same meaning as Y ² in (II).
<9> The photosensitive composition according to any one of <1> to <8>, wherein the binder includes a polymer compound having an acidic group and an ethylenically unsaturated bond in a side chain.
<10> The photosensitive composition according to <9>, 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. .
<11> The photosensitive composition according to any one of <9> to <10>, wherein the polymer compound contains 0.5 to 3.0 meq / g of an ethylenically unsaturated bond.
<12> Any one of <9> to <11>, wherein the polymer compound has a carboxyl group in a side chain, and the content of the carboxyl group in the polymer compound is 1.0 to 4.0 meq / g. It is a photosensitive composition as described above.
<13> The photosensitive composition according to any one of <9> to <12>, wherein the polymer compound has a mass average molecular weight of 10,000 or more and less than 100,000.
<14> The photosensitive composition according to any one of <10> to <13>, wherein the polymer compound contains 20 mol% or more of a structural unit represented by the following general formula (A-3).
However, in the structural formula (A-3), R ₁ , R ₂ , and R _{3 each} represent a hydrogen atom or a monovalent organic group. L represents an organic group and may not be present. Ar represents an aromatic group.

<15> The photosensitive composition according to any one of <1> to <14>, wherein the polymerizable compound includes at least one selected from monomers having a (meth) acryl group.
<16> From <1> to <1>, wherein the thermal crosslinking agent is at least one selected from an epoxy compound, an oxetane compound, a polyisocyanate compound, a compound obtained by reacting a polyisocyanate compound with a blocking agent, and a melamine derivative. 15>. The photosensitive composition according to any one of 15>.
<17> The thermal crosslinking agent includes an epoxy compound, and the epoxy compound is at least one selected from a bisphenol type epoxy resin, a novolac type epoxy resin, an alicyclic group-containing type epoxy resin, and a poorly soluble epoxy resin. <16> The photosensitive composition according to <16>.
<18> The photosensitive composition according to any one of <1> to <17>, including a sensitizer.
<19> The photosensitive composition according to <18>, wherein the sensitizer includes a hetero-fused ring compound.
<20> The photosensitive composition according to <19>, wherein the hetero-fused ring compound is a thioxanthone compound.

<21> A photosensitive film comprising a photosensitive layer made of the photosensitive composition according to any one of <1> to <20> on a support.
<22> The photosensitive film according to <21>, wherein the photosensitive layer has a thickness of 1 to 100 μm.
<23> The photosensitive film according to any one of <21> to <22>, wherein the support includes a synthetic resin and is transparent.
<24> The photosensitive film according to any one of <21> to <23>, wherein the support has an elongated shape.
<25> The photosensitive film according to any one of <21> to <24>, which is long and wound in a roll.
<26> The photosensitive film according to any one of <21> to <25>, having a protective film on the photosensitive layer.

<27> A method for forming a permanent pattern, comprising exposing a photosensitive layer formed of the photosensitive composition according to any one of <1> to <20>.
<28> The method for forming a permanent pattern according to <27>, wherein the photosensitive layer is formed of the photosensitive film according to any one of <21> to <26>.
<29> The permanent pattern forming method according to any one of <27> to <28>, wherein the exposure is performed without using a photomask.
<30> The method for forming a permanent pattern according to <29>, wherein the exposure is performed while relatively moving the exposure light and the photosensitive layer.
<31> Exposure is emitted from the light irradiation unit to the photosensitive layer while moving at least one of the exposure head including at least a light irradiation unit and a light modulation unit, and the photosensitive layer. The permanent pattern forming method according to any one of <29> to <30>, wherein the light is irradiated from the exposure head while modulating light according to pattern information by the light modulation unit.
<32> The light modulation unit according to <31>, wherein the light modulation means can control any less than n pixel elements arranged continuously from n pixel elements in accordance with pattern information. This is a permanent pattern forming method.
<33> The method for forming a permanent pattern according to any one of <31> to <32>, wherein the light modulator is a spatial light modulator.
<34> The method for forming a permanent pattern according to <33>, wherein the spatial light modulation element is a digital micromirror device (DMD).
<35> The method for forming a permanent pattern according to any one of <31> to <34>, wherein the exposure is performed through an aperture array.
<36> The permanent pattern forming method according to any one of <31> to <35>, wherein the light irradiation unit can synthesize and irradiate two or more lights.
<37> The light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that collects and couples the laser beams irradiated from the plurality of lasers to the multimode optical fiber. The permanent pattern forming method according to any one of <31> to <36>.
<38> The method for forming a permanent pattern according to any one of <27> to <37>, wherein the exposure is performed using a laser beam having a wavelength of 350 to 420 nm.

<39> The permanent pattern forming method according to any one of <27> to <38>, wherein the photosensitive layer is developed after the exposure.
<40> The method for forming a permanent pattern according to <39>, wherein the permanent pattern is formed after the development.
<41> The method for forming a permanent pattern according to <40>, wherein after the development, the photosensitive layer is cured.
<42> The method for forming a permanent pattern according to <41>, 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.

<43> A permanent pattern formed by the method for forming a permanent pattern according to any one of <27> to <42>.
<44> The pattern according to <43>, which is at least one of a protective film, an interlayer insulating film, and a solder resist pattern.

  <45> A printed circuit board wherein a permanent pattern is formed by the permanent pattern forming method according to any one of <27> to <42>.

  The photosensitive composition of the present invention includes a binder, a polymerizable compound, a photopolymerization initiator, a thermal crosslinking agent, and an inorganic pigment, the photopolymerization initiator includes an oxime derivative, and the inorganic pigment is a silane coupling agent. Surface treatment. For this reason, sensitivity, developability, and adhesiveness are favorable, and a high-definition permanent pattern can be formed efficiently.

  According to the present invention, a photosensitive composition, a photosensitive film, and the photosensitive property capable of solving conventional problems, having good sensitivity, developability and adhesion, and capable of efficiently forming a high-definition permanent pattern. A permanent pattern forming method using the composition, and a printed board on which a pattern is formed by the permanent pattern forming method can be provided.

(Photosensitive composition)
The photosensitive composition of the present invention contains a binder, a polymerizable compound, a photopolymerization initiator, a thermal crosslinking agent, and an inorganic pigment, and further contains other components as necessary.

-Inorganic pigment-
The inorganic pigment is added for the purpose of improving the surface hardness of the permanent pattern, suppressing the linear expansion coefficient, or suppressing the dielectric constant or dielectric loss tangent of the cured film itself.
The inorganic pigment is surface-treated with a silane coupling agent after thermosetting in order to improve the adhesion between the inorganic pigment and the pattern. Examples of the silane coupling agent include at least one functional group selected from an alkoxysilyl group, a chlorosilyl group, and an acetoxysilyl group (hereinafter also referred to as “first functional group”), a vinyl group, and an amino group. , A group having at least one functional group selected from a mercapto group, an epoxy group, and a (meth) acryloyl group (hereinafter, also referred to as “second functional group”). ) More preferred is an acrylate group or an epoxy group.

  Further, as described in JP-B-7-68256, the first functional group is at least one selected from an alkoxysilyl group, a chlorosilyl group, and an acetoxysilyl group, and the second functional group is an imidazole group or an alkyl group. Those having at least one selected from an imidazole group and a vinylimidazole group can also be preferably used.

  The silane coupling agent is not particularly limited, and examples thereof include vinyltrichlorosilane, vinyltriethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-methacryloxypropyl Trimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, vinyltriacetoxysilane, α-[[3- (trimethoxysilyl) propoxy] methyl] -imidazole-1-ethanol described in JP-B-7-68256 2-ethyl-4- Methyl-α-[[3- (trimethoxysilyl) propoxy] methyl] -imidazole-1-ethanol, 4-vinyl-α-[[3- (trimethoxysilyl) propoxy] methyl] -imidazole-1-ethanol, Preferable examples include 2-ethyl-4-methylimidazopropyltrimethoxysilane and salts thereof, intramolecular condensates, intermolecular condensates and the like. These may be used individually by 1 type and may be used in combination of 2 or more types.

The surface treatment of the inorganic pigment with the silane coupling agent may be performed only on the inorganic pigment in advance (this case is hereinafter also referred to as “pretreatment”), or one of the components in the other photosensitive composition. You may carry out together with a part or all.
There is no restriction | limiting in particular as the method of performing the said pretreatment, For example, methods, such as a dry method, the aqueous solution method, the organic-solvent method, a spray method, are mentioned. The temperature at which the pretreatment is performed is not particularly limited, but is preferably from room temperature to 200 ° C.
It is also preferable to add a catalyst during the pretreatment. There is no restriction | limiting in particular as this catalyst, For example, an acid, a base, a metal compound, an organometallic compound etc. are mentioned.

  The amount of the silane coupling agent added in the pretreatment is not particularly limited, but is preferably in the range of 0.01 to 50 parts by weight, and 0.05 to 50 parts by weight with respect to 100 parts by weight of the inorganic pigment. The range of is more preferable. When the addition amount is less than 0.01 parts by mass, the surface treatment may not be sufficient and a desired effect may not be obtained. When the addition amount exceeds 50 parts by mass, the inorganic filler tends to aggregate and handleability May decrease.

  In the silane coupling agent, the first functional group reacts with the substrate surface, the inorganic filler surface, and the active group of the binder, and the second functional group further includes a carboxyl group and an ethylenically unsaturated group of the binder. In order to react, there exists an effect | action which improves the adhesiveness of a base material and a photosensitive layer. On the other hand, since the silane coupling agent is highly reactive, when it is added to the photosensitive composition, the second functional group mainly reacts or deactivates during storage due to the diffusion action, Shelf life and pot life may be shortened.

  However, if the inorganic pigment pretreated with the silane coupling agent is used as described above, the diffusion effect is suppressed, so that the shelf life and pot life problems are greatly improved, and the one-pack type is obtained. It becomes possible. Furthermore, when pre-treating an inorganic pigment, conditions such as stirring conditions, temperature conditions, and use of a catalyst can be freely selected, so that the silane coupling agent can be used in comparison with the case of adding without pre-treatment. The reaction rate between the first functional group and the active group in the inorganic pigment can be remarkably increased. Therefore, very good results can be obtained particularly in severe required characteristics such as electroless gold plating, electroless solder plating, and moisture resistance load test. Moreover, the amount of the silane coupling agent used can be reduced by performing the pretreatment, and the shelf life and pot life can be further improved.

The inorganic pigment is not particularly limited and can be appropriately selected from known ones. For example, kaolin, barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, vapor phase method silica, amorphous Examples thereof include silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica.
The average particle diameter of the inorganic pigment is preferably less than 10 μm, and more preferably 3 μm or less. When the average particle size is 10 μm or more, resolution may be deteriorated due to light scattering.

If necessary, organic fine particles may be added to the photosensitive composition. There is no restriction | limiting in particular as said organic fine particle, According to the objective, it can select suitably, For example, a melamine resin, a benzoguanamine resin, a crosslinked polystyrene resin etc. are mentioned. Further, silica having an average particle diameter of 0.01 to 5 μm and an oil absorption of about 100 to 200 m ² / g, spherical porous fine particles made of a crosslinked resin, and the like can be used.

  The added amount of the inorganic pigment and the organic fine particles is preferably 1 to 60% by mass with respect to all the components of the photosensitive composition. When the addition amount is less than 1% by mass, the linear expansion coefficient may not be sufficiently reduced. When the addition amount exceeds 60% 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.

-Photopolymerization initiator-
An oxime derivative is used as the photopolymerization initiator. Moreover, you may contain another photoinitiator as needed.

  There is no restriction | limiting in particular as said oxime derivative, Although it can select suitably according to the objective, It is preferable that it is a compound which has an aromatic group at least, and either of the following general formula (I) and general formula (II) More preferably, the compound has a partial structure represented by Two or more oxime derivatives may be used in combination.

However, in said general formula (I) and (II), Ar represents either an aromatic group or a heterocyclic group. Y ¹ represents any ^one of a hydrogen atom and a monovalent substituent, and Y ² represents any one of an aliphatic group, an aromatic group, a heterocyclic group, COY ³ , CO ₂ Y ³ , and CONY ⁴ Y ^5. . Y ³ , Y ⁴ , and Y ^{5 each} represent an aliphatic group, an aromatic group, or a heterocyclic group. m represents an integer of 1 or more.

Y ¹ is preferably a hydrogen atom, an aliphatic group, or an aromatic group.
Y ² includes an aliphatic group, —CO— (aliphatic group), —CO— (aromatic group), —CO— (heterocyclic group), —CO ₂ — (aliphatic group), —CO _2. - (aromatic group), and -CO ₂ - is preferably any one of (heterocyclic group).
Y ³ and Y ⁴ are preferably either an aliphatic group or an aromatic group.

  The oxime derivative may be a compound in which a plurality of structures represented by the general formula (I) and the general formula (II) are bonded via a linking group.

  In the general formula (I) and the general formula (II), the aliphatic group represents an alkyl group, an alkenyl group, or an alkynyl group, each of which may have a substituent, and the aromatic group is Represents an aryl group or a heterocyclic (heterocyclic) group which may have a substituent. Examples of the monovalent substituent include a halogen atom, an amino group which may have a substituent, an alkoxycarbonyl group, and a hydroxyl group. , An ether group, a thiol group, a thioether group, a silyl group, a nitro group, and a cyano group, each representing an optionally substituted alkyl group, alkenyl group, alkynyl group, aryl group, and heterocyclic group.

Examples of the aromatic group include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples include phenyl Group, naphthyl group, anthryl group, phenanthryl group, indenyl group, acenaphthenyl group and fluorenyl group can be mentioned. Among them, a group having any of phenyl group and naphthyl group is preferable, and a group having naphthyl group is particularly preferable.
In addition, these aromatic groups may have a substituent, and examples of such a substituent include a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom. For example, what was shown as a substituent in the below-mentioned alkyl group, a substituted alkyl group, or a substituted alkyl group can be mentioned.

The heterocyclic (heterocyclic) group includes a pyrrole ring group, a furan ring group, a thiophene ring group, a benzopyrrole ring group, a benzofuran ring group, a benzothiophene ring group, a pyrazole ring group, an isoxazole ring group, and an 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, piperidine ring group, piperazine ring group, morpholine ring group, India Ring group, indolizine ring group, chromene ring group, cinnoline ring group, acridine ring group, phenothiazine ring group, tetrazole ring group, triazine ring group, etc., among which furan ring group, thiophene ring group, imidazole ring group , Thiazole ring group, benzothiazole ring group, pyridine ring group, indole ring group, and acridine ring group are particularly preferable.
Moreover, these heterocyclic groups may have a substituent, and examples of such a substituent include a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom. For example, what was shown as a substituent in the below-mentioned alkyl group, a substituted alkyl group, or a substituted alkyl group can be mentioned.

  Examples of the monovalent substituent include a halogen atom, an amino group that 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, and a cyano group. An alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group which may have a hydrogen atom is preferred.

  In addition, the monovalent substituent composed of the nonmetal atom is preferably an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, each of which may have a substituent.

  Examples of the alkyl group that may have a substituent include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group. Ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl A 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 Can do. Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

Examples of the substituent of the alkyl group which may have a substituent include a substituent composed of a monovalent nonmetallic atom excluding a hydrogen atom, and preferable examples include a halogen atom (-F, -Br, -Cl, -I), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio 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-dialkyl Carbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcal Moyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkyl Ureido 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'-diary Ru-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, al Killsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N— Alkylsulfinamoyl group, N, N-dialkylsulfinamoyl 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, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group _(-PO 3 _{H 2)} and its conjugated base group (a phosphonato group Referred), a dialkyl phosphono group _(-PO 3 _{(alkyl) 2)} "alkyl = alkyl group, hereinafter the" diarylphosphono group _(-PO 3 _{(aryl) 2)} "aryl = aryl group, hereinafter the" alkyl An arylphosphono group (—PO ₃ (alkyl) (aryl)), a monoalkylphosphono group (—PO ₃ (alkyl)) and its conjugate base group (referred to as an alkylphosphonato group), a monoarylphosphono group (— PO ₃ H (aryl)) and its conjugate base group (referred to as arylphosphonate group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (referred to as phosphonatoxy group), dialkylphosphonooxy group (—OPO) ₃ H _{(alkyl) 2),} diaryl phosphono group _{(-OPO 3 (aryl) 2)} , alkylaryl Suhonookishi group _(-OPO 3 (alkyl) (aryl)), monoalkyl phosphono group _(-OPO 3 H (alkyl)) and (referred to as alkylphosphonato group) a conjugate base group thereof, monoarylphosphono group (—OPO ₃ H (aryl)) and its conjugate base group (referred to as arylphosphonatoxy 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 above-described alkyl groups, and specific examples of the aryl group in the substituent include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, and a mesityl group. , Cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group , Methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylpheny Group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group, phosphate Hona preparative phenyl group.

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. Examples of the alkynyl group in the substituent Examples thereof include ethynyl group, 1-propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like.
Examples of the heterocyclic group in the substituent include a pyridyl group and a piperidinyl group.
Examples of the silyl group in the substituent include a trimethylsilyl group.
The substituent may include an acyl group (R ⁰¹ CO—), and examples of the acyl group include those in which R ⁰¹ is a hydrogen atom, the above alkyl group, or an aryl group.

The ^{R 01} of the acyl group ^(R 01 CO-), a hydrogen atom, and the alkyl group, and an aryl group. Among these substituents, more preferred are a halogen atom (—F, —Br, —Cl, —I), an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an N-alkylamino group, N, N. -Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group Group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfa group Moyl group, N-arylsulfur Amoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonato group, dialkylphosphono group, diarylphosphono group, monoalkylphosphono group, alkylphosphonato group, monoarylphosphono group, arylphospho Examples thereof include a nato group, a phosphonooxy group, a phosphonatooxy group, an aryl group, and an alkenyl group.

  On the other hand, examples of the alkylene group in the substituted alkyl group include divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms. 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 a propenylmethyl group, a 2-butenyl group, a 2-methylallyl group, a 2-methylpropenylmethyl group, a 2-propynyl group, a 2-butynyl group, and a 3-butynyl group.

Examples of the aryl group include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples include a phenyl group , A naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable.
As the substituted aryl group, those having a group consisting of a monovalent non-metallic atomic group excluding a hydrogen atom as a substituent on the ring-forming carbon atom of the aryl group described above are used. Examples of preferred substituents include the alkyl groups, substituted alkyl groups, and those previously shown as substituents in the substituted alkyl group.

  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, the substituted alkenyl group, the alkynyl group, and the substituted alkynyl group (-C (R ⁰² ) = C (R ⁰³ ) (R ⁰⁴ ) and -C≡C (R ⁰⁵ )) include R ^{A group in which 02} , R ⁰³ , R ⁰⁴ and R ⁰⁵ are monovalent non-metallic atoms can be used.
R ⁰² , R ⁰³ , R ⁰⁴ , and R ⁰⁵ are preferably a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group, and specific examples thereof are shown in the above examples. Things can be mentioned. Among these, a hydrogen atom, a halogen atom, and a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms are more preferable.
Specifically, 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, phenylethynyl group and the like.
Examples of the heterocyclic group include the pyridyl group exemplified as the substituent of the substituted alkyl group.

As the substituted oxy group (R ⁰⁶ O—), a group in which R ⁰⁶ is a group composed of a monovalent nonmetallic atom excluding a hydrogen atom can be used. Preferred substituted oxy groups include alkoxy groups, aryloxy groups, acyloxy groups, carbamoyloxy groups, N-alkylcarbamoyloxy groups, N-arylcarbamoyloxy groups, N, N-dialkylcarbamoyloxy groups, N, N-diarylcarbamoyloxy groups. Groups, N-alkyl-N-arylcarbamoyloxy groups, alkylsulfoxy groups, arylsulfoxy groups, phosphonooxy groups, and phosphonatoxy groups. 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 substituted oxy groups include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, pentyloxy, hexyloxy, dodecyloxy, benzyloxy, allyloxy, phenethyloxy, Carboxyethyloxy 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, chlorophenyl Alkoxy group, bromophenyl group, acetyloxy group, benzoyloxy group, naphthyloxy, phenylsulfonyloxy group, a phosphonooxy groups, phosphonatooxy group, and the like.

As the substituted amino group (R ⁰⁸ NH—, (R ⁰⁹ ) (R ⁰¹⁰ ) N—) including an amide group, R ⁰⁸ , R ⁰⁹ , and R ⁰¹⁰ are a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom. Can be used. R ⁰⁹ and R ⁰¹⁰ may be bonded to form a ring. Preferred examples of the substituted amino group include an N-alkylamino group, an N, N-dialkylamino group, an N-arylamino group, an N, N-diarylamino group, an N-alkyl-N-arylamino group, an 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 ′, '-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, aryloxy A carbonylamino group, an N-alkyl-N-alkoxycarbonylamino group, an N-alkyl-N-aryloxycarbonylamino group, an N-aryl-N-alkoxycarbonylamino group, and an N-aryl-N-aryloxycarbonylamino group. Can be mentioned. Examples of the alkyl group and aryl group include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group, such as acylamino group, N-alkylacylamino group, and N-arylacylamino. R ⁰⁷ of the base definitive acyl group (R ⁰⁷ CO-) is as described above. Of these, more preferred are an N-alkylamino group, an N, N-dialkylamino group, an N-arylamino group, and an acylamino group. Specific examples of preferred substituted amino groups include methylamino group, ethylamino group, diethylamino group, morpholino group, piperidino group, pyrrolidino group, phenylamino group, benzoylamino group, acetylamino group and the like.

As the substituted sulfonyl group (R ⁰¹¹ —SO ₂ —), those in which R ⁰¹¹ is a group composed of a monovalent nonmetallic atomic group can be used. More preferable examples include an alkylsulfonyl group and an arylsulfonyl group. 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 such a substituted sulfonyl group include a butylsulfonyl group, a phenylsulfonyl group, a chlorophenylsulfonyl group, and the like.

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

As the substituted carbonyl group (R ⁰¹³ —CO—), a group in which R ⁰¹³ is a monovalent nonmetallic atom can be used. Preferred examples of the substituted carbonyl group include 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 may be 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, more preferred substituted carbonyl groups include formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-ary. A rucarbamoyl group can be mentioned, and even more preferred are a formyl group, an acyl group, an alkoxycarbonyl group and an aryloxycarbonyl group. Specific examples of preferred substituted carbonyl groups include formyl group, acetyl group, benzoyl group, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, allyloxycarbonyl group, dimethylaminophenylethenylcarbonyl group, methoxycarbonylmethoxycarbonyl group, N -Methylcarbamoyl group, N-phenylcarbamoyl group, N, N-diethylcarbamoyl group, morpholinocarbonyl group and the like.

As the substituted sulfinyl group (R ⁰¹⁴ —SO—), a group in which R ⁰¹⁴ is a monovalent nonmetallic atomic group can be used. Preferable examples include alkylsulfinyl group, arylsulfinyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl. Group, N-alkyl-N-arylsulfinamoyl group. 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. Of these, more preferred examples include an alkylsulfinyl group and an arylsulfinyl group. Specific examples of such a substituted sulfinyl group include a hexylsulfinyl group, a benzylsulfinyl group, and a tolylsulfinyl group.

  The substituted phosphono group means a group in which one or two hydroxyl groups on the phosphono group are substituted with other organic oxo groups, and preferred examples thereof include the above-mentioned dialkylphosphono group, diarylphosphono group, alkylarylphospho group. Group, monoalkylphosphono group and monoarylphosphono group. Of these, dialkylphosphono groups and diarylphosphono groups are more preferred. Specific examples thereof include a diethyl phosphono group, a dibutyl phosphono group, a diphenyl phosphono group, and the like.

As described above, the phosphonate group (—PO ₃ H ₂ ^— , —PO ₃ H ⁻ ) is a conjugate base anion derived from the acid first dissociation or acid second dissociation of the phosphono group (—PO ₃ H ₂ ). Means group. Usually, it is preferable to use it with a counter cation. Examples of such counter cations include those generally known, that is, various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.), and metal ions (Na ⁺ , K ⁺ , Ca). ²⁺ , Zn ^{2+ and the} like).

Of the substituents phosphonato group foregoing substituted phosphono group, but was replaced a hydroxyl group on one organic oxo group is the conjugate base anion group, as specific examples, the aforementioned monoalkyl phosphono group (-PO 3 _H ( alkyl)), and a conjugate base of a monoarylphosphono group (—PO ₃ H (aryl)).

As said oxime derivative, the compound represented by either the following general formula (III) and general formula (IV) is still more preferable.
However, the general formula (III) and the general formula _{(IV), R 101} represents the same meaning as ^{Y 1} in the general formulas (I) and ^{(II), Y 12} is general formulas (I) and This represents the same meaning as Y ² in (II).

As R ₁₀₁ , either a hydrogen atom or an aliphatic group is more preferable, and an aliphatic group having 1 to 10 carbon atoms is particularly preferable.
Examples of the aliphatic group include a methyl group, an ethyl group, a propyl group, an octyl group, and an allyl group.
Y ¹² is particularly preferably —CO— (aliphatic group). The aliphatic group in Y ¹² is preferably an aliphatic group having 1 to 10 carbon atoms.
Specifically, for example, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a cyclohexyl group, a benzyl group and the like are preferable.

  Other specific examples of the oxime derivative include, for example, compounds disclosed in JP-A No. 2001-233842, JP-A No. 2004-534797, JP-A No. 2002-519732, and the following structural formula The compound etc. which are represented by these are mentioned.

In the structural _formulas, R represents _{n-C 3 H 7, n} -C 8 H 17, camphor, and one of the _{p-CH 3 C 6 H 4} .

In the above structural formula, R represents either nC ₃ H ₇ or p-CH ₃ C ₆ H ₄ .

As the oxime compound, an oxime compound represented by the following general formula (X) is also preferably used.
In the general formula (X), R ¹⁰⁰ represents any of an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group, and these substituents may further have a substituent. α represents any integer of 0 or more. R ²⁰⁰ represents a substituent, and when α is 2 or more, the R ²⁰⁰ may be the same or different. Ar represents either an aromatic ring or a heteroaromatic ring. A represents any of 4, 5, 6, and 7-membered rings, and each of these rings may contain a hetero atom.
Among the oxime compounds represented by the general formula (X), a compound represented by the following general formula (XI) is more preferable, and a compound represented by any one of the following general formulas (XII) and (XIII) is particularly preferable. preferable.
In the general formula ^{(XI), R 100, R} 200, α, and Ar represent the same meaning as in the general formula (X). X represents either O or S. A represents either a 5- or 6-membered ring.
However, R ^<300 > represents the alkyl group which may have a substituent in the said general formula (XII) and general formula (XIII). l represents an integer of 0 to 6. R ⁴⁰⁰ represents any of an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a sulfonyl group, and an acyloxy group. When l is 2 or more, the R ⁴⁰⁰ may be the same or different. It may be. X and A represent the same meaning as in the general formula (XI).
In the general formulas (X) and (XI), the acyl group represented by R ¹⁰⁰ may be any of aliphatic, aromatic, and heterocyclic, and may further have a substituent.
Examples of the aliphatic acyl group include an acetyl group, a propanoyl group, a butanoyl group, a hexanoyl group, a decanoyl group, a phenoxyacetyl group, and a chloroacetyl group. Examples of the aromatic acyl group include a benzoyl group, a naphthoyl group, a methoxybenzoyl group, and a nitrobenzoyl group. Examples of the heterocyclic acyl group include a furanoyl group and a thiophenoyl group. As the substituent, for example, any of an alkoxy group, an aryloxy group, and a halogen atom is preferable.
The acyl group preferably has 2 to 30 total carbon atoms, more preferably 2 to 20 total carbon atoms, and particularly preferably 2 to 16 total carbon atoms. Examples of the acyl group include acetyl group, propanoyl group, methylpropanoyl group, butanoyl group, pivaloyl group, hexanoyl group, cyclohexanecarbonyl group, octanoyl group, decanoyl group, dodecanoyl group, octadecanoyl group, benzylcarbonyl Group, phenoxyacetyl group, 2-ethylhexanoyl group, chloroacetyl group, benzoyl group, paramethoxybenzoyl group, 2,5-dibutoxybenzoyl group, 1-naphthoyl group, 2-naphthoyl group, pyridylcarbonyl group, furanoyl group, A thiophenoyl group, a methacryloyl group, an acryloyl group, and the like can be given.
In the general formulas (X) and (XI), the alkyloxycarbonyl group represented by R ¹⁰⁰ may have a substituent, and is preferably an alkoxycarbonyl group having 2 to 30 total carbon atoms. More preferably, those having 2 to 20 carbon atoms are more preferable, and those having 2 to 16 carbon atoms are particularly preferable. Examples of such alkoxycarbonyl groups include methoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonylbutoxycarbonyl group, isobutyloxycarbonyl group, aryloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, ethoxyethoxycarbonyl group. , Etc.
In the general formulas (X) and (XI), the aryloxycarbonyl group represented by R ¹⁰⁰ may have a substituent, and is preferably an alkoxycarbonyl group having 7 to 30 carbon atoms in total. Those having 7 to 20 total carbon atoms are more preferable, and those having 7 to 16 total carbon atoms are particularly preferable. Examples of such aryloxycarbonyl groups include phenoxycarbonyl group, 2-naphthoxycarbonyl group, paramethoxyphenoxycarbonyl group, 2,5-diethoxyphenoxycarbonyl group, parachlorophenoxycarbonyl group, paranitrophenoxycarbonyl group. And paracyanophenoxycarbonyl group.
In the general formulas (X) and (XI), the substituent represented by R ²⁰⁰ is not particularly limited, and examples thereof include alkyl groups, alkoxy groups, aryloxy groups, halogen atoms, sulfonyl groups, acyloxy groups, nitro groups. Group, acylamino group, and the like. Among these, any of an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a sulfonyl group, and an acyloxy group is preferable.
Here, specific examples of the oxime compound represented by the general formula (X) include compounds represented by the following structural formulas (1) to (54). However, the present invention is not limited to these. It is not something.
However, in the structural formulas (1) to (54), Me represents a methyl group. Ph represents a phenyl group. Ac represents an acetyl group.

-Other photopolymerization initiators-
The other photopolymerization initiator is not particularly limited as long as it has the ability to initiate the polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. It is preferable that it has photosensitivity to visible light, and may be an activator that generates an active radical by generating 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 wavelength range of about 300 to 800 nm. The wavelength is more preferably 330 to 500 nm.

  Examples of the other photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton), hexaarylbiimidazoles, organic peroxides, thio compounds, ketones. Compounds, acridine compounds, metallocenes and the like. Specific examples include compounds described in JP-A-2005-258431. Among these, ketone compounds and acridine compounds are preferable from the viewpoints of sensitivity of the photosensitive layer, storage stability, and adhesion between the photosensitive layer and the substrate. The said other photoinitiator may be used individually by 1 type, and may use 2 or more types together.

  The solid content of the photopolymerization initiator in the photosensitive composition is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and particularly preferably 0.5 to 15% by mass. .

-Sensitizer-
The photosensitive composition may contain a sensitizer.
The sensitizer is used in combination when the photosensitive layer is exposed and developed to improve the minimum energy (sensitivity) of the light that does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development. It is particularly preferred.
The sensitizer can be appropriately selected according to the light irradiation means (for example, visible light, ultraviolet light, visible light laser, etc.).
The sensitizer is excited by active energy rays and interacts with other substances (for example, radical generator, acid generator, etc.) (for example, energy transfer, electron transfer, etc.), thereby generating radicals, acids, etc. It is possible to generate a useful group of
The sensitizer is at least one selected from a condensed ring compound, an aminophenyl ketone compound, a polynuclear aromatic, an acid nucleus, a basic nucleus, and a fluorescent brightener nucleus. It contains seeds and may contain other sensitizers as needed. As the sensitizer, a hetero-fused compound and an aminobenzophenone compound are more preferable in terms of improving sensitivity, and a hetero-fused compound is particularly preferable.

--Condensed ring compound--
Among the above exemplary compounds, hetero-fused ring compounds are preferred as compounds in which an aromatic ring or a heterocyclic ring is fused (fused ring-based compounds). The hetero-fused ring compound means a polycyclic compound having a hetero element in the ring, and preferably contains a nitrogen atom in the ring. Examples of the hetero-fused ring compound include a hetero-fused ring ketone compound. Among the hetero-fused ketone compounds, an acridone compound and a thioxanthone compound are more preferable, and among these, a thioxanthone compound is particularly preferable.
Specific examples of the hetero-fused ketone compound include acridone compounds such as acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone; thioxanthone, Thioxanthone compounds such as isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propyloxythioxanthone, QuantacureQTX; 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′-carboni Bis (5,7-di-n-propoxycoumarin), 3,3′-carbonylbis (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, 7-diethylamino-4-methylcoumarin, JP-A-5-19475, JP-A-7-271028, JP-A-2002-363206, JP-A-2002-363207, JP-A-2002-363208, JP-A-2002-2002 Coumarin compounds such as coumarin compounds described in Japanese Patent No. 363209; It is.
In addition, known polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (for example, indocarbocyanine, thiacarbocyanine, oxacarbanine) Cyanine), merocyanines (for example, merocyanine, carbomerocyanine), thiazines (for example, thionine, methylene blue, toluidine blue), anthraquinones (for example, anthraquinone), squaliums (for example, squalium), and the like.

The content of the sensitizer is preferably 0.01 to 4% by mass, more preferably 0.02 to 2% by mass, and 0.05 to 1% by mass with respect to the total solid content of the photosensitive composition. Particularly preferred.
When the content is less than 0.01% by mass, the sensitivity may decrease, and when it exceeds 4% by mass, the shape of the pattern may be deteriorated.

The mass ratio between the sensitizer and the photopolymerization initiator content in the photosensitive composition is [(sensitizer) / (oxime derivative)] = 1 / 0.1 to 1/100. Is preferable, and it is more preferable that it is 1/1 to 1/50.
When the mass ratio between the content of the sensitizer and the content of the photopolymerization initiator is outside the above range, the sensitivity may be lowered and the change in sensitivity over time may be deteriorated.

-Binder-
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.
The binder is preferably a compound that is insoluble in water and swells or dissolves in an alkaline aqueous solution.
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, or 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. Furthermore, a compound having a skeleton derived from an epoxy compound and containing an ethylenic double bond and a carboxyl group in the molecule is also included. Such a compound can be obtained, for example, by a method of reacting a polyfunctional epoxy compound with a carboxyl group-containing monomer and further adding a polybasic acid anhydride.
Examples of these include Japanese Patent No. 2763775, Japanese Patent Application Laid-Open No. 3-172301, Japanese Patent Application Laid-Open No. 2000-232264, Japanese Patent Application Laid-Open No. 1-54390, 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 compound 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" is to mean an alkyl group . ), A diarylphosphono group (—PO ₃ (aryl) ₂ ) (hereinafter “aryl” means an aryl group), an alkylarylphosphono group (—PO ₃ (alkyl) (aryl)), a monoalkylphosphone 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 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.
Examples of the heterocyclic group in the substituent include a pyridyl group and 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. Examples of the substituent on the atom include a group having a monovalent nonmetallic atomic group other than a hydrogen atom.
As the substituent that the aryl group may have, for example, the above-described alkyl group, substituted alkyl group, and the substituents that 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 ^Examples include a group in which ⁰⁵ is a monovalent nonmetallic atomic group.
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 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, an N-alkyl-N-arylcarbamoyloxy group, an alkylsulfoxy group, an arylsulfoxy group, a phosphonooxy group, a 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 the alkyl group, substituted alkyl group, aryl group, and 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 conjugate 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 ^{(e.g., Na +, K +, Ca} 2+, Zn 2+ etc.).

Examples of the carbonyl group (R ⁰¹³ —CO—) include groups in which R ⁰¹³ is 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- Preferable examples include a methylcarbamoyl group, an N-phenylcarbamoyl group, an N, N-diethylcarbamoyl group, a morpholinocarbonyl group, and the like.

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 hexylsulfinyl group, benzylsulfinyl group, tolylsulfinyl group and the like.

The phosphono group means a group 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 a counter cation, 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 a normal radical polymerization method using at least one radical polymerizable compound containing an aromatic group and, if necessary, at least one other radical polymerizable compound 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 general formula (A-1) and a compound represented by the general formula (A-2) are preferable.
However, in said general formula (A-1), 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 general formula (A-2), R < ₁ >, R < ₂ >, R < ₃ > and Ar represent the same meaning as the said general formula (A-1).

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, polyvalent anthracene and the like.

  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 general formula (A-1) and the compound represented by the general formula (A-2), the general formula (A-1) is preferable in terms of sensitivity. Of the general formula (A-1), 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 in the non-image area. It is preferable in terms of removability (developability).
The compound represented by the general formula (A-1) is a compound including a structural unit represented by the following general formula (A-3). Moreover, the compound represented by the general formula (A-2) is a compound containing a structural unit of the following general formula (A-4). Among these, the structural unit of the general formula (A-3) is preferable in terms of storage stability.

However, in said general formula (A-3) and general formula (A-4), R < ₁ >, R < ₂ > and R < ₃ > and Ar are said general formula (A-1) and general formula (A-2). Means the same.
In the general formulas (A-3) and (A-4), R ₁ and R ₂ are hydrogen atoms, and R ₃ is a methyl group, from the viewpoint of removal (developability) of non-image areas. preferable.
In addition, L in the general formula (A-3) is preferably an alkylene group having 1 to 4 carbon atoms in terms of removability (developability) of non-image areas.

  The compound represented by the general formula (A-1) or the compound represented by the general formula (A-2) is not particularly limited, and examples thereof include the following exemplary compounds (1) to (30). It is done.

  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 in terms of the property and developability.

  The content of the aromatic group that may contain the heterocyclic ring in the binder is not particularly limited, but is represented by the general formula (A-3) when the total structural unit of the polymer compound is 100 mol%. It is preferable to contain 20 mol% or more of structural units, more preferably 30 to 45 mol%. When the content is less than 20 mol, storage stability may be lowered, and when it exceeds 45 mol%, developability may be lowered.

--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 the following general formula (A-5)-(A-7) is preferable.

However, in the general formulas (A-5) to (A-7), 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 general formula (A-5), as R ₁ , for example, a hydrogen atom or an optionally substituted alkyl group is preferable, and the hydrogen atom or methyl group has high radical reactivity. This is more preferable.
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 general formula (A-6), 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 alkyl group that may have a group, an aryl group that may have a substituent, an alkoxy group that may have a substituent, an aryloxy group that may have a substituent, and a substituent An alkylamino group which may have a 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, etc. are preferred, 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.
Examples of the substituent that can be introduced include those listed in the general formula (A-5).

In the general formula (A-7), as R ₉ , for example, a hydrogen atom, an alkyl group which may have a substituent, and the like are preferable, and a hydrogen atom and a methyl group are 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 are preferable, 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 general formula (A-5) 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 general formulas (A-5) to (A-7), those having the general formula (A-5) have high polymerization reactivity and high sensitivity. preferable.
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.

The method for introducing an ethylenically unsaturated bond represented by the general formula (A-5) into the side chain is not particularly limited, but for example, a polymer compound containing a carboxyl group in the side chain and ethylenically unsaturated It can be obtained by addition reaction of a compound having a bond and 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. The compounds represented are preferred.
However, in said general formula (A-8), R < ₁ > represents a hydrogen atom or a methyl group. L ₁ represents an organic group.
In the general formula (A-9), _{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 general formula (A-8) and the compound represented by the general formula (A-9), the compound represented by the general formula (A-8) is preferable, and the general formula (A- In 8), L ₁ is more preferably an alkylene group having 1 to 4 carbon atoms.

The compound represented by the general formula (A-8) or the compound represented by the general formula (A-9) is not particularly limited, and examples thereof include the following exemplified compounds (31) to (40). It is done.

  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.

Although there is no restriction | limiting in particular as a structural unit which has an ethylenically unsaturated bond in the said side chain, For example, the structure represented by the following general formula (A-10), the structure represented by general formula (A-11) And those represented by a mixture thereof are preferred.
However, in said general formula (A-10) and general formula (A-11), 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 of the polymer compound having the structure represented by the general formula (A-10) to the structure represented by the general formula (A-11) is preferably 20 mol% or more, more preferably 20 to 50 mol%, 25 -45 mol% is 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. Examples thereof include 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 individually by 1 type and may use 2 or more types together.

  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 compound 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. When the solid content is less than 5% by mass, the film strength of the photosensitive layer tends to be weak, and the tackiness of the surface of the photosensitive layer may be deteriorated. When it exceeds 80% by mass, the exposure sensitivity is increased. May decrease.

-Polymerizable compound-
The polymerizable compound is not particularly limited and may be appropriately selected depending on the intended purpose. A compound is preferable, for example, at least 1 sort (s) selected from the monomer which has a (meth) acryl group is mentioned suitably. In the present invention, the “polymerizable compound” does not include a polymerizable compound that can be contained in the binder.

  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 hexa (Meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin Poly (functional) alcohols such as tri (meth) acrylate, trimethylolpropane, glycerin, bisphenol, etc., which are subjected to addition reaction with ethylene oxide and propylene oxide, and converted to (meth) acrylate, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50- Urethane acrylates described in JP-A-6034, JP-A-51-37193, etc .; JP-A-48-64183, JP-B-49-43191, JP-B-52-30 Polyester acrylates described in each publication of such 90 No.; and epoxy resin and (meth) polyfunctional acrylates or methacrylates such as epoxy acrylates which are reaction products of acrylic acid. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are particularly preferable.

  5-50 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 of developability and reduction in exposure sensitivity may occur, and if it exceeds 50% by mass, the adhesiveness of the photosensitive layer may become too strong. Yes, not preferred.

-Thermal crosslinking agent-
The thermal crosslinking agent is not particularly limited and may be appropriately selected depending on the purpose. In order to improve the film strength after curing of the photosensitive layer formed using the photosensitive film, developability, etc. For example, an epoxy compound having at least two oxirane groups in one molecule and an oxetane compound having at least two oxetanyl groups in one molecule can be used.
Examples of the epoxy compound having at least two oxirane groups in one molecule include, for example, a bixylenol type or biphenol type epoxy resin (“YX4000 Japan Epoxy Resin” etc.) or a mixture thereof, a complex having an isocyanurate skeleton, etc. Cyclic epoxy resins ("TEPIC; manufactured by Nissan Chemical Industries", "Araldite PT810; manufactured by Ciba Specialty Chemicals"), bisphenol A type epoxy resin, novolac type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, halogenated epoxy resin (for example, low brominated epoxy resin, high halogenated epoxy resin, Hydrogenated phenol novolac type epoxy resin, etc.), allyl group-containing bisphenol A type epoxy resin, trisphenol methane type epoxy resin, diphenyldimethanol type epoxy resin, phenol biphenylene type epoxy resin, dicyclopentadiene type epoxy resin ("HP-7200") , HP-7200H; manufactured by Dainippon Ink & Chemicals, Inc.), glycidylamine type epoxy resin (diaminodiphenylmethane type epoxy resin, diglycidylaniline, triglycidylaminophenol, etc.), glycidyl ester type epoxy resin (diglycidyl phthalate) Ester, adipic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer acid diglycidyl ester, etc.) Hydantoin type epoxy resin, alicyclic epoxy resin (3,4) Epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, dicyclopentadiene diepoxide, “GT-300, GT-400, ZEHPE3150; manufactured by Daicel Chemical Industries”, etc. )), Imide type alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A novolak type epoxy resin, tetraphenylolethane type epoxy resin, glycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group-containing epoxy Resin (naphthol aralkyl type epoxy resin, naphthol novolac type epoxy resin, tetrafunctional naphthalene type epoxy resin, commercially available products are “ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.”) "HP-4032, EXA-4750, EXA-4700; manufactured by Dainippon Ink & Chemicals, Inc."), polyphenol compounds obtained by addition reaction of phenol compounds with diolefin compounds such as divinylbenzene and dicyclopentadiene, and epichlorohydrin Reaction product of 4-vinylcyclohexene-1-oxide ring-opened polymer with peracetic acid or the like, epoxy resin having a linear phosphorus-containing structure, epoxy resin having a cyclic phosphorus-containing structure, α-methyl Stilbene liquid crystal epoxy resin, dibenzoyloxybenzene liquid crystal epoxy resin, azophenyl liquid crystal epoxy resin, azomethine phenyl liquid crystal epoxy resin, binaphthyl liquid crystal epoxy resin, azine epoxy resin, glycidyl methacrylate copolymer epoxy resin (“CP − 50S, CP-50M; manufactured by NOF Corporation, etc.), copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, bis (glycidyloxyphenyl) fluorene type epoxy resin, bis (glycidyloxyphenyl) adamantane type epoxy resin, etc. Although it is mentioned, it is not restricted to these. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.

In addition to the epoxy compound having at least two oxirane groups in one molecule, an epoxy compound containing at least two epoxy groups having an alkyl group at the β-position can be used, and the β-position is an alkyl group. Particularly preferred is a compound containing an epoxy group substituted with a (specifically, a β-alkyl-substituted glycidyl group or the like).
In the epoxy compound containing at least an epoxy group having an alkyl group at the β-position, all of two or more epoxy groups contained in one molecule may be a β-alkyl-substituted glycidyl group, and at least one epoxy group May be a β-alkyl-substituted glycidyl group.

From the viewpoint of storage stability at room temperature, the epoxy compound containing an epoxy group having an alkyl group at the β-position is substituted with β-alkyl in all epoxy groups in the total amount of the epoxy compound contained in the photosensitive composition. The proportion of glycidyl groups is preferably 30% or more, more preferably 40% or more, and particularly preferably 50% or more.
The β-alkyl-substituted glycidyl group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, β-methylglycidyl group, β-ethylglycidyl group, β-propylglycidyl group, β-butylglycidyl Among them, a β-methylglycidyl group is preferable from the viewpoint of improving the storage stability of the photosensitive composition and from the viewpoint of ease of synthesis.

  As the epoxy compound containing an epoxy group having an alkyl group at the β-position, for example, an epoxy compound derived from a polyhydric phenol compound and a β-alkylepihalohydrin is preferable.

  The β-alkylepihalohydrin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, β-methylepichlorohydrin, β-methylepibromohydrin, β-methylepifluorohydrin, etc. Β-methyl epihalohydrin, β-ethyl epichlorohydrin, β-ethyl epibromohydrin, β-ethyl epihalohydrin, such as β-ethyl epihalohydrin, β-propyl epichlorohydrin, β-propyl epibromohydrin Β-propyl epihalohydrin such as phosphorus and β-propyl epifluorohydrin; β-butyl epihalohydrin such as β-butyl epichlorohydrin, β-butyl epibromohydrin, β-butyl epifluorohydrin; . Among these, β-methylepihalohydrin is preferable from the viewpoint of reactivity with the polyhydric phenol and fluidity.

  The polyhydric phenol compound is not particularly limited as long as it is a compound containing two or more aromatic hydroxyl groups in one molecule, and can be appropriately selected according to the purpose. For example, bisphenol A, bisphenol F Bisphenol compounds such as bisphenol S, biphenol compounds such as biphenol and tetramethylbiphenol, naphthol compounds such as dihydroxynaphthalene and binaphthol, phenol novolac resins such as phenol-formaldehyde polycondensates, cresol-formaldehyde polycondensates 1 1-10 monoalkyl-substituted phenol-formaldehyde polycondensate, xylenol-formaldehyde polycondensate and the like, and C1-C10 dialkyl-substituted phenol-formaldehyde polycondensate, bisphenol A-formalde De polycondensates such bisphenol compounds of - formaldehyde polycondensates, phenol and copolycondensates of monoalkyl-substituted phenol and formaldehyde having 1 to 10 carbon atoms, and phenolic compounds and polyaddition products of divinylbenzene. Among these, when selecting for the purpose of improving fluidity | liquidity and storage stability, the said bisphenol compound is preferable, for example.

Examples of the epoxy compound containing an epoxy group having an alkyl group at the β-position include di-β-alkyl glycidyl ether of bisphenol A, di-β-alkyl glycidyl ether of bisphenol F, and di-β-alkyl glycidyl of bisphenol S. Di-β-alkyl glycidyl ethers of bisphenol compounds such as ethers; Β-alkyl glycidyl ethers of naphthol compounds such as di-β-alkyl glycidyl ether of dinaphthol, di-β-alkyl glycidyl ether of binaphthol; poly- of phenol-formaldehyde polycondensate β-alkyl glycidyl ethers; poly-β-alkyl glycidyl ethers of monoalkyl substituted phenol-formaldehyde polycondensates of 1 to 10 carbon atoms such as poly-β-alkyl glycidyl ethers of cresol-formaldehyde polycondensates; xylenol-formaldehyde C1-C10 dialkyl-substituted phenol-formaldehyde polycondensate poly-β-alkyl glycidyl ethers such as poly-β-alkyl glycidyl ethers of condensates; poly-β-alkyl glycidyl ethers of bisphenol A-formaldehyde polycondensates Bisphenol compounds such as poly-β-alkyl glycidyl ethers of formaldehyde polycondensates; poly-β-alkyl glycidyl ethers of polyaddition products of phenol compounds and divinylbenzene; The
Among these, β-alkylglycidyl ether derived from a bisphenol compound represented by the following general formula (D-1) and a polymer obtained from this and epichlorohydrin, and the following general formula (D-2) Poly-β-alkyl glycidyl ether of a phenol compound-formaldehyde polycondensate represented by
However, in said general formula (D-1), R represents either a hydrogen atom or a C1-C6 alkyl group, and n represents the integer of 0-20.
However, the general formula (D-2), R represents any of an alkyl group having 1 to 6 carbon hydrogen and carbon, R "represents either hydrogen atoms, and CH _3, n is 0 Represents an integer of 20.
These epoxy compounds containing an epoxy group having an alkyl group at the β-position may be used alone or in combination of two or more. It is also possible to use together an epoxy compound having at least two oxirane rings in one molecule and an epoxy compound containing an epoxy group having an alkyl group at the β-position.

  The skeleton of the epoxy compound is preferably at least one selected from bisphenol type epoxy resins, novolac type epoxy resins, alicyclic group-containing type epoxy resins, and poorly soluble epoxy resins.

  Examples of the oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, 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) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate, oligomers or copolymers thereof, and compounds having an oxetane group , Novolac resin, poly (p-hydroxystyrene), potassium Bisphenols, calixarenes, calixresorcinarenes, ether compounds with hydroxyl group resins such as silsesquioxane, etc. In addition, unsaturated monomers having an oxetane ring and alkyl (meth) acrylates And a copolymer thereof.

Further, in order to promote the thermal curing of the epoxy compound or the oxetane compound, for example, an amine compound (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N , N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (eg, dimethylamine, etc.), imidazole derivatives Cyclic amidine compounds and salts thereof (for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenyl) Midazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, etc.), phosphorus compounds (eg triphenylphosphine etc.), guanamine compounds (eg melamine, guanamine, acetoguanamine, benzoguanamine etc.), S- Triazine derivatives (for example, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric An acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. The epoxy resin compound or the oxetane compound is a curing catalyst, or any compound that can accelerate the reaction between the epoxy resin compound and the oxetane compound and a carboxyl group. May be.
Solid content in the said photosensitive composition solid content of the said epoxy compound, the said oxetane compound, and the compound which can accelerate | stimulate thermosetting with these and carboxylic acid is 0.01-15 mass% normally.

  Further, as the thermal crosslinking agent, a polyisocyanate compound described in JP-A-5-9407 can be used, and the polyisocyanate compound is aliphatic, cycloaliphatic or aromatic containing at least two isocyanate groups. It may be derived from a group-substituted aliphatic compound. Specifically, bifunctional isocyanate (for example, 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.), the bifunctional isocyanate, trimethylolpropane, pentalithol tol Polyfunctional alcohols such as glycerin; alkylene oxide adducts of the polyfunctional alcohols and adducts of the bifunctional isocyanates; hexamethylene diisocyanate, hexamethylene-1,6-di Isocyanate and cyclic trimers thereof derivatives; and the like.

Furthermore, for the purpose of improving the storage stability of the photosensitive film of the present invention, a compound obtained by reacting a blocking agent with the isocyanate group of the polyisocyanate and its derivative may be used.
Examples of the isocyanate group blocking agent include alcohols (eg, isopropanol, tert-butanol, etc.), lactams (eg, ε-caprolactam, etc.), phenols (eg, phenol, cresol, p-tert-butylphenol, p-sec). -Butylphenol, p-sec-amylphenol, p-octylphenol, p-nonylphenol, etc.), heterocyclic hydroxyl compounds (eg, 3-hydroxypyridine, 8-hydroxyquinoline, etc.), active methylene compounds (eg, dialkyl malonate, Methyl ethyl ketoxime, acetylacetone, alkyl acetoacetate oxime, acetoxime, cyclohexanone oxime, etc.). 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, a melamine derivative can be used as the thermal crosslinking agent. Examples of the melamine derivative include methylol melamine, alkylated methylol melamine (a compound obtained by etherifying a methylol group with methyl, ethyl, butyl, or the like). These may be used individually by 1 type and may use 2 or more types together. Among these, alkylated methylol melamine is preferable and hexamethylated methylol melamine is particularly preferable in that it has good storage stability and is effective in improving the surface hardness of the photosensitive layer or the film strength itself of the cured film.

  1-50 mass% is preferable and, as for solid content in the said photosensitive composition solid content of the said thermal crosslinking agent, 3-30 mass% is more preferable. When the solid content is less than 1% by mass, improvement in the film strength of the cured film is not recognized, and when it exceeds 50% by mass, developability and exposure sensitivity may be deteriorated.

-Other ingredients-
Examples of the other components include thermal polymerization inhibitors, plasticizers, colorants (color pigments or dyes), and further adhesion promoters and other auxiliaries (for example, conductive materials). Particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, perfumes, surface tension modifiers, chain transfer agents, etc.) may be used in combination. By appropriately containing these, properties such as the stability, photographic properties, and film properties of the intended photosensitive film can be adjusted.

-Thermal polymerization inhibitor-
The thermal polymerization inhibitor may be added to prevent thermal polymerization or temporal polymerization of the polymerizable compound in the photosensitive layer.
Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine. , Chloranil, naphthylamine, β-naphthol, 2,6-di-tert-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, chelate of nitroso compound and Al, and the like.

The content of the thermal polymerization inhibitor is preferably 0.001 to 5 mass%, more preferably 0.005 to 2 mass%, and particularly preferably 0.01 to 1 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.

-Plasticizer-
The plasticizer may be added to control film physical properties (flexibility) of the photosensitive layer.
Examples of the plasticizer include dimethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diheptyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diphenyl phthalate, diallyl phthalate, octyl capryl phthalate, and the like. Phthalic acid esters: Triethylene glycol diacetate, tetraethylene glycol diacetate, dimethylglycol phthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, triethylene glycol dicabrylate, etc. Glycol esters of tricresyl phosphate, triphenyl phosphate, etc. Acid esters; Amides such as 4-toluenesulfonamide, benzenesulfonamide, Nn-butylbenzenesulfonamide, Nn-butylacetamide; diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sepacate, dioctyl Aliphatic dibasic acid esters such as sepacate, dioctyl azelate, dibutyl malate; triethyl citrate, tributyl citrate, glycerin triacetyl ester, butyl laurate, 4,5-diepoxycyclohexane-1,2-dicarboxylic acid Examples include glycols such as dioctyl acid, polyethylene glycol, and polypropylene glycol.

  The content of the plasticizer is preferably 0.1 to 50% by mass, more preferably 0.5 to 40% by mass, and particularly preferably 1 to 30% by mass with respect to all components of the photosensitive composition.

-Color pigment-
There is no restriction | limiting in particular as said coloring pigment, According to the objective, it can select suitably, For example, Victoria pure blue BO (CI. 42595), auramine (CI. 41000), fat black HB (CI. 26150), Monolite Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow HR). 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 Supra (CI Pigment Red 81) Monastral Fa Strike 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. Moreover, the dye suitably selected from well-known dye can be used as needed.

  The solid content of the color pigment in the photosensitive composition can be determined in consideration of the exposure sensitivity, resolution, etc. of the photosensitive layer during permanent pattern formation, and varies depending on the type of the color pigment. Generally, 0.01 to 10% by mass is preferable, and 0.05 to 5% by mass is more preferable.

-Adhesion promoter-
In order to improve the adhesion between the layers or the adhesion between the photosensitive layer and the substrate, a known so-called adhesion promoter can be used for each layer.

  Preferable examples of the adhesion promoter include adhesion promoters described in JP-A Nos. 5-11439, 5-341532, and 6-43638. Specifically, benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione, 3-morpholino Methyl-5-phenyl-oxadiazole-2-thione, 5-amino-3-morpholinomethyl-thiadiazole-2-thione, and 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole Amino group-containing benzotriazole, silane coupling agents, and the like.

  The content of the adhesion promoter is preferably 0.001% by mass to 20% by mass, more preferably 0.01% by mass to 10% by mass, and 0.1% by mass to 5% by mass with respect to all components of the photosensitive layer. Is particularly preferred.

-Photosensitive layer-
When the photosensitive layer formed of the photosensitive composition is exposed and developed, the minimum energy of light used for the exposure that does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development is: it is preferably 0.1~200mJ / cm ^2, more preferably 0.2~100mJ / cm ^2, and particularly preferably 0.5~50mJ / cm ^2.
The minimum energy is less than 0.1 mJ / cm ^2, may fogging in process step occurs, it exceeds 200 mJ / cm ^2, increases the time necessary for exposure, processing speed is slow Sometimes.

Here, the “minimum energy of light used for the exposure in which the thickness of the exposed portion of the photosensitive layer is not changed after the exposure and development” (hereinafter sometimes simply referred to as “minimum energy of light”). The so-called development sensitivity, for example, the relationship between the amount of energy (exposure amount) of light used for the exposure when the photosensitive layer is exposed and the thickness of the cured layer generated by the development process following the exposure It can obtain | require from the graph (sensitivity curve) which shows.
The thickness of the cured layer increases as the amount of exposure increases, and then becomes substantially the same and substantially constant as the thickness of the photosensitive layer before the exposure. The development sensitivity is a value obtained by reading the minimum exposure when the thickness of the cured layer becomes substantially constant.
Here, when the difference between the thickness of the cured layer and the thickness of the photosensitive layer before the exposure is within ± 1 μm, it is considered that the thickness of the cured layer is not changed by exposure and development.
A method for measuring the thickness of the cured layer and the photosensitive layer before exposure is not particularly limited and may be appropriately selected depending on the intended purpose. However, a film thickness measuring device, a surface roughness measuring machine (for example, Surfcom) 1400D (manufactured by Tokyo Seimitsu Co., Ltd.)) and the like.

Further, the variation rate (%) of the minimum energy of light in light having a wavelength of 400 to 410 nm (hereinafter also referred to as “sensitivity variation”) is preferably within 20%. If the variation rate exceeds 20%, the pattern shape in the surface may vary.
Here, for example, after measuring the minimum energy of the light in a light having a wavelength of 400 nm, the variation rate is measured by sequentially measuring the minimum energy of the light up to a light having a wavelength of 410 nm by shifting the wavelength by 1 nm. From the difference between the maximum value (Emax) and the minimum value (Emin) of the minimum energy, the following equation can be used.
〔formula〕
(Emax-Emin) / Emax

  There is no restriction | limiting in particular in the thickness of the said photosensitive layer, Although it can select suitably according to the objective, For example, 1-100 micrometers is preferable, 2-50 micrometers is more preferable, and 4-30 micrometers is especially preferable.

(Photosensitive film)
The photosensitive film of the present invention has at least a support and a photosensitive layer made of the photosensitive composition of the present invention formed on the support, and if necessary, such as a thermoplastic resin layer. It is preferable to have other layers. The photosensitive layer is as described above.
<Support>
The support is not particularly limited and may be appropriately selected depending on the intended purpose. However, it is preferable that the photosensitive layer is peelable and has good light transmittance, and further has a smooth surface. Is more preferable.

  The support is preferably made of 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, a cellulose film, and a nylon film, are mentioned, Among these, polyethylene terephthalate is particularly preferable. These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular in the thickness of the said support body, Although it can select suitably according to the objective, For example, 2-150 micrometers is preferable, 5-100 micrometers is more preferable, and 8-50 micrometers is especially preferable. The support may be a single layer or may have a multilayer structure.

  There is no restriction | limiting in particular as a shape of the said support body, Although it can select suitably according to the objective, 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 10-20,000m length is mentioned.

<Protective film>
The photosensitive film may form a protective film on the photosensitive layer.
Examples of the protective film include those used for the support, paper, paper laminated with polyethylene, polypropylene, and the like. Among these, polyethylene film and polypropylene film are preferable.
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, 8-50 micrometers is more preferable, 10-30 micrometers is especially preferable.
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, interlayer adhesion can be adjusted by surface-treating at least one of the support and the 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 a discharge irradiation process, an active plasma irradiation process, and a laser beam irradiation process.

Moreover, 0.3-1.4 are preferable and the static friction coefficient of the said support body and the said protective film has more preferable 0.5-1.2.
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.

  For example, the photosensitive film is preferably wound around a cylindrical core, wound into a long roll, and stored. 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. From the viewpoint of protecting the end face and preventing edge fusion during storage, it is preferable to install a separator (especially moisture-proof and desiccant-containing) on the end face, and use a low moisture-permeable material for packaging. It is preferable.

  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. for 1 to 30 minutes. The drying temperature is particularly preferably 50 to 120 ° C.

<Other layers>
The other layers in the photosensitive film are not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a cushion layer, an oxygen barrier layer (PC layer), a release layer, an adhesive layer, a light absorption layer, You may have layers, such as a surface protective layer. These layers may be used alone or in combination of two or more. Moreover, you may have a protective film on the said photosensitive layer.

−Cushion layer−
There is no restriction | limiting in particular as said cushion layer, According to the objective, it can select suitably, Swelling thru | or soluble with respect to alkaline liquid may be sufficient, and it may be insoluble.

  When the cushion layer is swellable or soluble in an alkaline liquid, examples of the thermoplastic resin include a saponified product of ethylene and an acrylate ester copolymer, a copolymer of styrene and a (meth) acrylate ester Saponification of coalescence, saponification of vinyltoluene and (meth) acrylic acid ester copolymer, poly (meth) acrylic acid ester, (meth) acrylic acid ester copolymer such as (meth) acrylic acid butyl and vinyl acetate And a copolymer of (meth) acrylic acid ester and (meth) acrylic acid, a copolymer of styrene, (meth) acrylic acid ester and (meth) acrylic acid, and the like.

The softening point (Vicat) of the thermoplastic resin in this case is not particularly limited and can be appropriately selected according to the purpose. For example, it is preferably 80 ° C. or lower.
As the thermoplastic resin having a softening point of 80 ° C. or lower, in addition to the above-mentioned thermoplastic resin, “Plastic Performance Handbook” (edited by the Japan Plastics Industry Federation, All Japan Plastics Molding Industry Federation, published by the Industrial Research Council, October 1968) Among those organic polymers having a softening point of about 80 ° C. or less, which are soluble in an alkaline solution. In addition, even in an organic polymer substance having a softening point of 80 ° C. or higher, various plasticizers compatible with the organic polymer substance are added to the organic polymer substance so that a substantial softening point is 80 ° C. or lower. It is also possible to lower it.

  Further, when the cushion layer is swellable or soluble in an alkaline liquid, the interlayer adhesive force of the photosensitive film is not particularly limited and can be appropriately selected according to the purpose. Of the interlayer adhesive strength of each layer, it is preferable that the interlayer adhesive strength between the support and the cushion layer is the smallest. By setting such an interlayer adhesive force, only the support is peeled off from the photosensitive film, the photosensitive layer is exposed through the cushion layer, and then the photosensitive layer is developed using an alkaline developer. can do. In addition, after exposing the photosensitive layer while leaving the support, only the support is peeled off from the photosensitive film, and the photosensitive layer can be developed using an alkaline developer.

  The method for adjusting the interlayer adhesion is not particularly limited and can be appropriately selected according to the purpose. For example, a known polymer, supercooling substance, adhesion improver, surfactant in the thermoplastic resin, The method of adding a mold release agent etc. is mentioned.

  The plasticizer is not particularly limited and may be appropriately selected depending on the intended purpose.For example, polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl Examples thereof include alcohols and esters such as phosphate and biphenyldiphenyl phosphate; amides such as toluenesulfonamide.

When the cushion layer is insoluble in an alkaline liquid, examples of the thermoplastic resin include a copolymer whose main component is ethylene as an essential copolymer component.
The copolymer having ethylene as an essential copolymer component is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethylene-vinyl acetate copolymer (EVA) and ethylene-ethyl acrylate. A copolymer (EEA) etc. are mentioned.

  When the cushion layer is insoluble in the alkaline liquid, the interlayer adhesive force of the photosensitive film is not particularly limited and may be appropriately selected depending on the intended purpose. Of the adhesive strength, it is preferable that the adhesive force between the photosensitive layer and the cushion layer is the smallest. With such an interlayer adhesive strength, the support and the cushion layer are peeled off from the photosensitive film, and after the photosensitive layer is exposed, the photosensitive layer can be developed using an alkaline developer. . Further, after exposing the photosensitive layer while leaving the support, the support and the cushion layer are peeled off from the photosensitive film, and the photosensitive layer can be developed using an alkaline developer. .

  The method for adjusting the interlayer adhesion is not particularly limited and can be appropriately selected depending on the purpose. For example, various polymers, supercooling substances, adhesion improvers, surfactants in the thermoplastic resin, Examples thereof include a method of adding a release agent and the like, and a method of adjusting an ethylene copolymerization ratio described below.

The ethylene copolymerization ratio in the copolymer containing ethylene as an essential copolymerization component is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 60 to 90% by mass is preferable, and 60 to 80 is preferable. % By mass is more preferable, and 65 to 80% by mass is particularly preferable.
When the ethylene copolymerization ratio is less than 60% by mass, the interlayer adhesive force between the cushion layer and the photosensitive layer increases, and it becomes difficult to peel off at the interface between the cushion layer and the photosensitive layer. When the amount exceeds 90% by mass, the interlayer adhesive force between the cushion layer and the photosensitive layer becomes too small, so that the cushion layer and the photosensitive layer are very easily peeled off, including the cushion layer. Production of the photosensitive film may be difficult.

There is no restriction | limiting in particular in the thickness of the said cushion layer, Although it can select suitably according to the objective, For example, 5-50 micrometers is preferable, 10-50 micrometers is more preferable, and 15-40 micrometers is especially preferable.
If the thickness is less than 5 μm, unevenness on the surface of the substrate and unevenness followability to bubbles and the like may be deteriorated, and a high-definition permanent pattern may not be formed. Such a problem may occur.

-Oxygen barrier layer (PC layer)-
The oxygen barrier layer is preferably formed usually with polyvinyl alcohol as a main component, and is preferably a film having a thickness of about 0.5 to 5 μm.

[Method for producing photosensitive film]
The said photosensitive film can be manufactured as follows, for example.
First, the material contained in the photosensitive composition is dissolved, emulsified or dispersed in water or a solvent to prepare a photosensitive composition solution for a photosensitive film.

  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, and ethylbenzene; halogenated carbonization such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, and 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.

  Next, the photosensitive composition solution is applied on the support and dried to form a photosensitive layer, whereby a photosensitive film can be produced.

The method for applying the photosensitive composition solution is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a spray method, a roll coating method, a spin coating method, a slit coating method, and an extrusion coating method. And various coating methods such as a curtain coating method, a die coating method, a gravure coating method, a wire bar coating method, and a knife coating method.
The drying conditions vary depending on each component, the type of solvent, the use ratio, and the like, but are usually about 60 to 110 ° C. for about 30 seconds to 15 minutes.

For example, the photosensitive film is preferably wound around a cylindrical core, wound into a long roll, and stored.
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.

(Photosensitive laminate)
The photosensitive laminate is formed by laminating at least the photosensitive layer on the substrate and other layers appropriately selected according to the purpose.

<Substrate>
The substrate is a substrate to be processed on which a photosensitive layer is formed, or a substrate to which at least the photosensitive layer of the photosensitive film of the present invention is transferred, and is not particularly limited, and is appropriately selected depending on the purpose. For example, it can be arbitrarily selected from those having high surface smoothness to those having a rough surface. A plate-like substrate is preferable, and a so-called substrate is used. Specific examples include known printed wiring board manufacturing substrates (printed substrates), glass plates (soda glass plates, etc.), synthetic resin films, paper, metal plates, and the like.

[Method for producing photosensitive laminate]
Examples of the method for producing the photosensitive laminate include, as the first aspect, a method of applying the photosensitive composition to the surface of the substrate and drying, and as the second aspect, at least the photosensitive film of the present invention. Examples of the method include transferring and laminating the photosensitive layer while performing at least one of heating and pressing.

In the method for producing a photosensitive laminate of the first aspect, a photosensitive layer is formed by applying and drying the photosensitive composition on the substrate.
The method for applying and drying is not particularly limited and can be appropriately selected depending on the purpose. For example, the photosensitive composition is dissolved, emulsified or dispersed in water or a solvent on the surface of the substrate. And a method of laminating by preparing a photosensitive composition solution, applying the solution directly, and drying the solution.

  There is no restriction | limiting in particular as a solvent of the said photosensitive composition solution, According to the objective, it can select suitably, The same solvent as what was used for the said photosensitive film is mentioned. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.

  There is no restriction | limiting in particular as said coating method and drying conditions, According to the objective, it can select suitably, It carries out by the same method and conditions as what was used for the said photosensitive film.

In the method for producing a photosensitive laminate of the second aspect, the photosensitive film of the present invention is laminated on the surface of the substrate while performing at least one of heating and pressing. 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 | substrate.
There is no restriction | limiting in particular in the said heating temperature, According to the objective, it can select suitably, For example, 15-180 degreeC is preferable and 60-140 degreeC is more preferable.
There is no restriction | limiting in particular in the said pressurization pressure, According to the objective, it can select suitably, For example, 0.1-1.0 MPa is preferable and 0.2-0.8 MPa is more preferable.

  There is no restriction | limiting in particular as an apparatus which performs at least any one of the said heating, According to the objective, it can select suitably, For example, Laminator (For example, Taisei Laminator VP-II, Nichigo Morton VP130) Etc. are preferable.

  Since the photosensitive film and the photosensitive laminate of the present invention use the photosensitive composition of the present invention, the sensitivity, developability, and adhesion are good, and a high-definition permanent pattern can be efficiently formed. Yes, for forming various patterns such as protective films, interlayer insulating films, and permanent patterns such as solder resist patterns, for manufacturing liquid crystal structural members such as color filters, pillar materials, rib materials, spacers, partition walls, holograms, micromachines, It can be suitably used for forming a pattern such as a proof, and can be particularly suitably used for forming a permanent pattern on a printed circuit board.

  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, the high acceleration test is performed. In (HAST), there is no occurrence of ion migration, and a high-definition permanent pattern excellent in heat resistance and moisture resistance can be obtained.

(Pattern forming apparatus and permanent pattern forming method)
The pattern forming apparatus of the present invention includes the photosensitive layer and includes at least light irradiation means and light modulation means.

The permanent pattern forming method of the present invention includes at least an exposure step, and includes other steps such as an appropriately selected development step.
In addition, the said pattern formation apparatus of this invention is clarified through description of the said permanent pattern formation method of this invention.

[Exposure process]
The said exposure process is a process of exposing with respect to the photosensitive layer of this invention. The photosensitive layer and substrate material of the present invention are as described above.

  The subject of the exposure is not particularly limited as long as it is the photosensitive layer, and can be appropriately selected according to the purpose. For example, as described above, the photosensitive composition is heated and pressurized on the substrate. It is preferable to carry out with respect to the photosensitive layer in the photosensitive laminate formed by laminating while performing at least one of the above.

  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 analog exposure is not particularly limited and can be appropriately selected depending on the purpose. For example, exposure with a (super) high pressure mercury lamp, xenon lamp, halogen lamp, etc. through a photomask having a predetermined pattern. The method of performing is mentioned.

  The digital exposure is not particularly limited as long as it is performed without using the photomask, and can be appropriately selected according to the purpose. For example, an exposure head including at least a light irradiation unit and a light modulation unit; The exposure head irradiates the photosensitive layer with light emitted from the light irradiation means while modulating at least one of the photosensitive layers according to pattern information by the light modulation means. It is preferable.

  The light source used in the digital exposure is not particularly limited as long as it is a light source that emits ultraviolet to near infrared rays, and can be appropriately selected according to the purpose. For example, (ultra) high pressure mercury lamp, xenon lamp, carbon arc lamp , Fluorescent lamps for use in halogen lamps and copying machines, or known light sources such as laser light are used. Among these, (ultra) high pressure mercury lamps and laser light are preferable, and laser light is more preferable.

  The (super) high pressure mercury lamp is a discharge lamp in which mercury is enclosed in a quartz glass tube or the like, and has a higher vapor pressure to increase luminous efficiency. Among the emission line spectra, an emission line spectrum of only one wavelength may be used using an ND filter or the like, or a light beam having a plurality of emission line spectra may be used.

“Laser” of the laser light is an acronym for Light Amplification by Stimulated Emission of Radiation. As an apparatus for emitting the laser light, an oscillator and an amplifier that generate monochromatic light having higher coherence and directivity by amplification and oscillation of light waves, utilizing the phenomenon of stimulated emission that occurs in a material having an inversion distribution, are preferably used. Can be mentioned.
Examples of the excitation medium for the laser light include crystals, glass, liquid, pigment, gas, and the like, and known lasers such as solid laser, liquid laser, gas laser, and semiconductor laser can be used.
Specifically, examples of the gas laser include an Ar ion laser (364 nm, 351 nm), a Kr ion laser (356 nm, 351 nm), and a He—Cd laser (325 nm), and examples of the solid laser include a YAG laser and a YVO ₄ laser (1, 064 nm), YAG laser or YVO ₄ laser, 2nd harmonic (532 nm), 3rd harmonic (355 nm), 4th harmonic (266 nm), a combination of a waveguide wavelength conversion element and an AlGaAs or InGaAs semiconductor (380 nm to 400 nm) ), A combination of a waveguide wavelength conversion element and AlGaInP or an AlGaAs semiconductor t (300 nm to 350 nm), AlGaInN (350 nm to 470 nm), and the like. Among these, preferable laser light includes an AlGaInN semiconductor laser (commercially available InGaN-based semiconductor laser 375 nm or 405 nm) in terms of cost, and a 355 nm laser having high output in terms of productivity.

  The wavelength of the laser beam is, for example, preferably 200 to 1,500 nm, more preferably 300 to 800 nm, still more preferably 330 to 500 nm, and particularly preferably 350 to 420 nm.

-Light modulation means-
As the light modulation means, a typical method is a method having n pixel parts and controlling the pixel parts according to the pattern information. Specifically, a digital micromirror device (DMD), a MEMS (Micro Electro Mechanical Systems) type spatial light modulator (SLM), an optical element (PLZT element) that modulates transmitted light by an electro-optic effect. And liquid crystal light shutter (FLC). Among these, DMD is preferable.

When the DMD is used, light from a light source is irradiated onto the DMD by an appropriate optical system, and reflected light from each mirror arranged two-dimensionally on the DMD is exposed to light through another optical system. An image of light spots arranged in two dimensions is formed on the layer. If the light spot is not exposed between the light spots, the image of the light spots arranged in two dimensions is moved in a direction slightly inclined with respect to the two-dimensional arrangement direction. The light spot in the rear row exposes between the light spot and the light spot, so that the entire surface of the photosensitive layer can be exposed. The DMD can form an image pattern by controlling the angle of each mirror and controlling the light spot on and off. By using such exposure heads having the DMD side by side, it is possible to deal with substrates of various widths.
In the DMD, the brightness of the light spot has only two gradations, ON or OFF, but exposure with 256 gradations can be performed by using a mirror gradation spatial modulation element.

Moreover, it is preferable that the said light modulation means has a pattern signal generation means which produces | generates a control signal based on the pattern information to form. In this case, the light modulation unit modulates light according to the control signal generated by the pattern signal generation unit.
There is no restriction | limiting in particular as said control signal, According to the objective, it can select suitably, For example, a digital signal is mentioned suitably.

  On the other hand, another typical method of the light modulation means is a method using a polygon mirror. Here, the polygon mirror is a rotating member having a series of plane reflecting surfaces around it. The polygon mirror reflects and irradiates light from the light source onto the photosensitive layer, and the light spot of the reflected light is scanned by the rotation of the plane mirror. By moving the substrate at right angles to the scanning direction, the entire surface of the photosensitive layer on the substrate can be exposed. Then, an image pattern can be formed by controlling the intensity of light from the light source to ON-OFF or halftone by an appropriate method. At this time, the scanning time can be shortened by using a plurality of lights from the light source.

  As the light modulation means of the present invention, in addition, an example of drawing using a polygon mirror described in JP-A-5-150175, as described in JP-T-2004-523101 (International Publication No. 2002/039793 pamphlet). An example in which a part of the image of the lower layer is visually acquired, and exposure is performed by aligning the position of the upper layer with the position of the lower layer with an apparatus using a polygon mirror, and exposure with the DMD described in JP-A-2004-56080 For example, an exposure apparatus provided with a polygon mirror described in JP-T-2002-523905, an exposure apparatus provided with a polygon mirror described in JP-A-2001-255661, DMD, LD, and multiple exposure described in JP-A-2003-50469 An example of a combination of an exposure method in which the exposure amount is changed depending on the part of the substrate described in JP-A-2003-156653 , Etc. Examples of an exposure method for performing a positional deviation adjustment described in JP 2005-43576 Publication and the like.

-Light irradiation means-
There is no restriction | limiting in particular as said light irradiation means, ie, the light irradiation method, Although the above-mentioned exposure light source can be selected suitably according to the objective, Two or more light from these light sources is synthesize | combined and irradiated. It is particularly preferable to irradiate a laser beam (combined laser beam) obtained by combining two or more lights.

  There is no restriction | limiting in particular as the irradiation method of the said combined laser beam, Although it can select suitably according to the objective, A laser irradiated from a several laser light source, a multimode optical fiber, and this several laser light source A method of composing and irradiating a combined laser beam with a collective optical system that collects light and couples it to the multimode optical fiber is preferable.

The beam diameter of the laser light is not particularly limited and may be appropriately selected depending on the purpose. From the viewpoint of the resolution of the dark color separation partition wall, the Gaussian beam 1 / e ² value is preferably 5 to 30 μm, 7-20 micrometers is more preferable.
In the present invention, it is preferable to spatially modulate laser light according to image data. Therefore, it is preferable to use the DMD which is a spatial light modulator for this purpose.

  Examples of the exposure apparatus having the light modulating unit and the light irradiating unit are described in JP-A-2005-222039, JP-A-2005-258431, JP-A-2006-30966, and the like. However, the exposure apparatus in the present invention is not limited to this.

[Development process]
The development is performed by removing an unexposed portion of the photosensitive layer.
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.

  There is no restriction | limiting in particular as said developing solution, Although it can select suitably according to the objective, For example, alkaline aqueous solution, an aqueous developing solution, an organic solvent etc. are mentioned, Among these, weakly alkaline aqueous solution is preferable. Examples of the basic component of the weak alkaline aqueous solution include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, phosphorus Examples include potassium acid, sodium pyrophosphate, potassium pyrophosphate, and borax.

For example, the pH of the weakly alkaline aqueous solution is preferably about 8 to 12, and more preferably about 9 to 11. Examples of the weak alkaline aqueous solution include a 0.1 to 5% by mass aqueous sodium carbonate solution or an aqueous potassium carbonate solution.
The temperature of the developer can be appropriately selected according to the developability of the photosensitive layer, and is preferably about 25 to 40 ° C., for example.

  The developer includes a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.) and development. Therefore, it 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 aqueous alkali solution and an organic solvent, or may be an organic solvent alone.

  In the formation of the pattern, for example, a curing process, an etching process, a plating process, and the like may be included. These may be used alone or in combination of two or more.

[Curing process]
When the pattern forming method is a permanent pattern forming method for forming a permanent pattern such as a protective film, an interlayer insulating film, a solder resist pattern, or a color filter, the photosensitive layer is cured after the developing step. It is preferable to provide the hardening process process which processes.
There is no restriction | limiting in particular as said hardening process, Although it can select suitably according to the objective, 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 development. 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.
An apparatus for performing the entire surface exposure is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a UV exposure machine such as an ultra-high pressure mercury lamp, an exposure machine using a xenon lamp, a laser exposure machine and the like are preferable. It is mentioned in. The exposure amount is usually 10 to 2,000 mJ / cm ² .

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 development. 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. When the heating temperature is less than 120 ° C., the film strength may not be improved by heat treatment. When the heating temperature exceeds 250 ° C., the resin in the photosensitive composition is decomposed, and the film quality is weak and brittle. Sometimes.
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.

  The pattern forming method can be used for forming various patterns that require prevention of sensitivity reduction of the photosensitive layer by oxygen in direct writing by laser exposure of 405 nm, and has high density and high productivity. It can be suitably used for forming a compatible pattern.

  In the permanent pattern forming method, if 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 impact and bending from the outside. In the case of the interlayer insulating film, for example, it is useful for high-density mounting of semiconductors and components on a multilayer wiring board, a build-up wiring board, and the like.

  Since the method for forming a permanent pattern of the present invention uses the photosensitive composition of the present invention, it is used for forming various patterns such as a protective film, an interlayer insulating film, a permanent pattern such as a solder resist pattern, a color filter, and a column material. It can be suitably used for the production of liquid crystal structural members such as ribs, spacers, partition walls, etc., and the production of holograms, micromachines, proofs, etc., and in particular, it can be suitably used for the formation of permanent patterns on printed boards.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

(Surface treatment example 1)
-Preparation of surface-treated inorganic pigment 1-
In 1000 parts by mass of dichloromethane containing 5 parts by mass of water and 5 parts by mass of hydrochloric acid (hydrolysis catalyst), 15 parts by mass of γ-mercaptopropyltrimethoxysilane was dissolved and barium sulfate (Sakai Chemical Co., Ltd.) was stirred vigorously. Manufactured, B30) 100 parts by mass was gradually added. After sufficiently stirring, it was filtered and dried to obtain a surface-treated inorganic pigment 1.

(Surface treatment example 2)
-Preparation of surface-treated inorganic pigment 2-
Surface-treated inorganic pigment 2 was obtained in the same manner as in Surface Treatment Example 1 except that 100 parts by mass of silica (produced by sol-gel method) (“Aerosil 130” manufactured by Nippon Aerosil Co., Ltd.) instead of barium sulfate was added. .

(Surface treatment example 3)
-Preparation of surface-treated inorganic pigment 3-
Surface-treated inorganic pigment 3 was obtained in the same manner as in Surface Treatment Example 1, except that 98 parts by mass of talc (“LMS # 200” manufactured by Fuji Talc Industrial Co., Ltd.) was added instead of barium sulfate.

(Surface treatment example 4)
-Preparation of surface-treated inorganic pigment 4-
Surface-treated inorganic pigment 4 was obtained in the same manner as in Surface Treatment Example 1 except that 15 parts by mass of γ-glycidoxypropyltrimethoxysilane was dissolved instead of γ-mercaptopropyltrimethoxysilane.

(Surface treatment example 5)
-Preparation of surface-treated inorganic pigment 5-
Surface-treated inorganic pigment 5 was obtained in the same manner as in Surface Treatment Example 1 except that 30 parts by mass of γ-aminopropyltriethoxysilane was dissolved instead of γ-mercaptopropyltrimethoxysilane.

(Surface treatment example 6)
-Preparation of surface-treated inorganic pigment 6-
Surface-treated inorganic pigment 6 was obtained in the same manner as in Surface Treatment Example 1 except that 30 parts by mass of γ-methacryloxypropyltrimethoxysilane was dissolved instead of γ-mercaptopropyltrimethoxysilane.

(Surface treatment agent 7)
-Preparation of surface-treated inorganic pigment 7-
In surface treatment example 1, instead of γ-mercaptopropyltrimethoxysilane, α-[[3- (trimethoxysilyl) propoxy] methyl] -imidazole-1-ethanol (“IS-1000” manufactured by Japan Energy Co., Ltd.) ) A surface-treated inorganic pigment 7 was obtained in the same manner except that 20 parts by mass were dissolved.

(Surface treatment example 8)
-Preparation of surface-treated inorganic pigment 8-
In surface treatment example 1, instead of γ-mercaptopropyltrimethoxysilane, 20 parts by mass of 2-ethyl-4-methylimidazopropyltrimethoxysilane hydrochloride (“AZ-6160” manufactured by Nihon Unicar Co., Ltd.) was dissolved. In the same manner as above, surface-treated inorganic pigment 8 was obtained.

(Surface treatment example 9)
-Preparation of surface-treated inorganic pigment 9-
Surface-treated inorganic pigment 9 was obtained in the same manner as in Surface Treatment Example 1 except that 15 parts by mass of vinyltriacetoxysilane was dissolved instead of γ-mercaptopropyltrimethoxysilane.
(Surface treatment example 10)
-Preparation of surface-treated inorganic pigment 10-
In surface treatment example 1, spherical silica (prepared by a combustion method) instead of barium sulfate (“Admafine SO-C1” manufactured by Admatechs Co., Ltd., average particle size of 0.25 μm) was added 50 parts by mass, and γ-mercapto Surface-treated inorganic pigment 10 was obtained in the same manner except that 2.5 parts by mass of γ-glycidoxypropyltrimethoxysilane (“KBM403” manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved instead of propyltrimethoxysilane. It was.
(Surface treatment example 11)
-Preparation of surface-treated inorganic pigment 11-
In surface treatment example 1, spherical silica (prepared by a combustion method) instead of barium sulfate (“Admafine SO-C1” manufactured by Admatechs Co., Ltd., average particle size of 0.25 μm) was added 50 parts by mass, and γ-mercapto Surface-treated inorganic pigment 11 was obtained in the same manner except that 2.5 parts by mass of γ-methacryloxypropyltrimethoxysilane (“KBM503” manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved instead of propyltrimethoxysilane. .
(Surface treatment example 12)
-Preparation of surface-treated inorganic pigment 12-
In surface treatment example 1, spherical silica (produced by a combustion method) instead of barium sulfate (“Admafine SO-C2” manufactured by Admatechs Co., Ltd., average particle size 0.5 μm) was added 50 parts by mass, and γ-mercapto Surface-treated inorganic pigment 12 was obtained in the same manner except that 2.5 parts by mass of γ-glycidoxypropyltrimethoxysilane (“KBM403” manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved instead of propyltrimethoxysilane. It was.
(Surface treatment example 13)
-Preparation of surface-treated inorganic pigment 13-
In surface treatment example 1, spherical silica (produced by a combustion method) instead of barium sulfate (“Admafine SO-C2” manufactured by Admatechs Co., Ltd., average particle size 0.5 μm) 25 parts by mass was added, and γ-mercapto Surface-treated inorganic pigment 13 was obtained in the same manner except that 2.5 parts by mass of γ-methacryloxypropyltrimethoxysilane (“KBM503” manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved instead of propyltrimethoxysilane. .
(Surface treatment example 14)
-Preparation of surface-treated inorganic pigment 14-
In Surface Treatment Example 1, 50 parts by mass of spherical silica (produced by a combustion method) (“SFP-30M” manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size 0.7 μm) was added instead of barium sulfate, and γ-mercaptopropyl Surface-treated inorganic pigment 14 was obtained in the same manner except that 2.5 parts by mass of γ-glycidoxypropyltrimethoxysilane (“KBM403” manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved instead of trimethoxysilane. .
(Surface treatment example 15)
-Preparation of surface-treated inorganic pigment 15-
In Surface Treatment Example 1, 50 parts by mass of spherical silica (produced by a combustion method) (“SFP-30M” manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size 0.7 μm) was added instead of barium sulfate, and γ-mercaptopropyl Surface-treated inorganic pigment 15 was obtained in the same manner except that 2.5 parts by mass of γ-methacryloxypropyltrimethoxysilane (“KBM503” manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved instead of trimethoxysilane.
(Surface treatment example 16)
-Preparation of surface-treated inorganic pigment 16-
In surface treatment example 1, spherical silica (produced by a combustion method) instead of barium sulfate (“SFP-20M” manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size 0.3 μm) was added 50 parts by mass, and γ-mercaptopropyl Surface-treated inorganic pigment 16 was obtained in the same manner except that 2.5 parts by mass of γ-glycidoxypropyltrimethoxysilane (“KBM403” manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in place of trimethoxysilane. .
(Surface treatment example 17)
-Preparation of surface-treated inorganic pigment 17-
In surface treatment example 1, spherical silica (produced by a combustion method) instead of barium sulfate (“SFP-20M” manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size 0.3 μm) was added 50 parts by mass, and γ-mercaptopropyl Surface-treated inorganic pigment 17 was obtained in the same manner except that 2.5 parts by mass of γ-methacryloxypropyltrimethoxysilane (“KBM503” manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved instead of trimethoxysilane.

(Synthesis Example 1)
-Synthesis of binder 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, 3.0 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 binder 1 solution represented by the following structural formula having a solid content of 30% by mass.
The mass average molecular weight (Mw) of the obtained binder was 15,000 as a result of measurement by gel permeation chromatography (GPC) using polystyrene as a standard substance.
Moreover, the acid value per solid content was 2.2 meq / g from the titration using sodium hydroxide.
Furthermore, the content of ethylenically unsaturated bonds per solid (C = C value) determined by iodine value titration was 2.1 meq / g.

Binder 1
However, * 1 in the polymer compound 1 represents a mixture of the structure represented by the following structural formula (a) and the structure represented by (b) (mixing ratio is unknown).

(Synthesis Example 2)
-Synthesis of binder 2-
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 was added dropwise a solution of 159 g of 1-methoxy-2-propanol containing 36 g of methyl methacrylate, 72.3 g of methacrylic acid, and 4.15 g of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) over 2 hours. After completion of the dropwise addition, the reaction was further continued by heating for 5 hours. Next, the heating was stopped to obtain a copolymer of methyl methacrylate / methacrylic acid (30/70 mol% ratio).
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 binder 2 solution represented by the following structural formula having a solid content of 30% by mass.
The mass average molecular weight (Mw) of the obtained binder was 15,000 as a result of measurement by gel permeation chromatography (GPC) using polystyrene as a standard substance.
Moreover, the acid value per solid content was 2.3 meq / g from the titration using sodium hydroxide.
Furthermore, the content of ethylenically unsaturated bonds (C = C value) per solid content determined by iodine value titration was 2.6 meq / g.

Binder 2
However, * 1 in the polymer compound 1 represents the same meaning as the polymer compound 1.

(Synthesis Example 3)
-Synthesis of binder 3-
110 parts by mass of phenol novolac type epoxy resin (manufactured by Toto Kasei Co., Ltd., YDPN-702) was dissolved in 150 parts by mass of propylene glycol monomethyl ether acetate, and then 34 parts by mass of acrylic acid and 0.8 parts by mass of benzyldimethylamine were dissolved. In addition, after continuing the reaction at 100 to 120 ° C. for 8 hours, 35 parts by mass of tetrahydrophthalic anhydride was added and reacted at 100 ° C. for 8 hours to obtain an epoxy acrylate compound (medium 3) having an acid value of 70 mg KOH / g. .

Example 1
-Preparation of photosensitive composition-
Each component was mix | blended in the following quantity and the photosensitive composition solution was prepared.
[Each component amount of photosensitive composition solution]
The binder 1 (solid content 30% by mass in the 1-methoxy-2-propanol solution) ... 87.4 parts by mass, dipentaerythritol hexaacrylate (polymerizable compound) ... 13 parts by mass, the following formula Photoinitiator represented by I-1 2.6 parts by mass, sensitizer represented by the following formula S-1 0.5 parts by mass Epototo YD-8125 (epoxy equivalent 170 g / Eq., Manufactured by Toto Kasei Co., Ltd., bisphenol A epoxy resin) ... 8 parts by mass, thermosetting agent (dicyandiamide) ... 0.77 parts by mass, fluorosurfactant (Megafac F-176, Dainippon Ink Chemical Industry Co., Ltd., 30 mass% 2-butanone solution) ... 0.2 parts by mass / surface-treated inorganic pigment 1 ... 21.98 parts by mass / methyl ethyl ketone ... 15 parts by mass

-Production of photosensitive film-
The obtained photosensitive composition solution was applied with a bar coater onto a PET (polyethylene terephthalate) film (manufactured by Toray Industries, Inc., 16FB50) having a thickness of 16 μm, a width of 300 mm, and a length of 200 m as the support, and hot air at 80 ° C. It dried in the circulation type dryer, and formed the 30-micrometer-thick photosensitive layer. Next, a polypropylene film (E-200, manufactured by Oji Paper Co., Ltd.) having a thickness of 20 μm, a width of 310 mm, and a length of 210 m was laminated as a protective film on the photosensitive layer by lamination to produce a photosensitive film.

-Preparation of photosensitive laminate-
Next, the substrate was prepared by subjecting a surface of a copper-clad laminate (no through hole, copper thickness 12 μm) on which a wiring was formed as a printed board to a chemical polishing treatment. A vacuum laminator (VP130, manufactured by Nichigo Morton Co., Ltd.) was peeled off on the copper clad laminate while peeling off the protective film on the photosensitive film so that the photosensitive layer of the photosensitive film was in contact with the copper clad laminate. The photosensitive laminate was prepared by laminating the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) in this order.
The pressure bonding conditions were a vacuum drawing time of 40 seconds, a pressure bonding temperature of 70 ° C., a pressure bonding pressure of 0.2 MPa, and a pressure application time of 10 seconds.
The photosensitive laminate was evaluated for developability, sensitivity, resolution, and adhesion. The results are shown in Table 2.

<Development evaluation>
Immediately after the preparation of the photosensitive laminate, the polyethylene terephthalate film (support) is peeled off from the photosensitive laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. is 0.15 MPa on the entire surface of the photosensitive layer on the copper clad laminate. The time required from the start of spraying of the aqueous sodium carbonate solution until the photosensitive layer on the copper clad laminate was dissolved and removed was measured as the shortest development time, and the developability was evaluated. The shorter the shortest development time, the better the developability. Further, the developability was similarly evaluated when the photosensitive laminate was prepared and stored at 40 ° C. for 3 days.

<Evaluation of sensitivity>
Using the pattern forming apparatus described in JP-A-2006-30966 having a 405 nm laser light source as the light irradiation unit from the support side to the photosensitive layer of the photosensitive film in the prepared photosensitive laminate. A double exposure was performed by irradiating light having different light energy amounts from 0.1 mJ / cm ² to 100 mJ / cm ² at 2 ¹ / ^2- fold intervals to cure a partial region of the photosensitive layer. After standing at room temperature for 10 minutes, the support was peeled off from the photosensitive laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. was sprayed onto the entire surface of the photosensitive layer on the copper clad laminate at a spray pressure of 0.15 MPa. And sprayed for twice the minimum development time to dissolve and remove the uncured area, and the thickness of the remaining cured area was measured. Subsequently, the relationship between the light irradiation amount and the thickness of the cured layer was plotted to obtain a sensitivity curve. From the sensitivity curve, the amount of light energy when the thickness of the cured region was the same 30 μm as that of the photosensitive layer before exposure was determined as the amount of light energy necessary for curing the photosensitive layer.

<Evaluation of resolution>
The photosensitive laminate was allowed to stand at room temperature (23 ° C., 55% RH) for 10 minutes. From the obtained polyethylene terephthalate film (support) of the photosensitive laminate, exposure was performed for each line width in increments of 1 μm from line / space = 1/1 to a line width of 10 to 100 μm using the pattern forming apparatus. .
The exposure amount at this time is the amount of light energy necessary for curing the photosensitive layer of the photosensitive film in the sensitivity evaluation. After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) was peeled off from the photosensitive laminate.
The entire surface of the photosensitive layer on the copper clad laminate is sprayed with a 1% by weight sodium carbonate aqueous solution at 30 ° C. as the developer at a spray pressure of 0.15 MPa for twice the shortest development time to dissolve the uncured region. Removed.
The surface of the copper-clad laminate with a cured resin pattern obtained in this way is observed with an optical microscope, and the cured resin pattern line is free of irregularities such as lumps and twists, and the minimum line width that allows space formation is measured. This is the resolution. The smaller the numerical value, the better the resolution.

<Evaluation of adhesion>
The photosensitive laminate was allowed to stand at room temperature (23 ° C., 55% RH) for 10 minutes. From the obtained photosensitive laminate polyethylene terephthalate film (support), using the pattern forming apparatus, line / space = 1/5, and line widths of 10 to 50 μm, each line width being exposed in 5 μm increments. The same exposure as in the evaluation was performed.
After dissolving and removing the uncured region in the same manner as in the evaluation of resolution, the surface of the obtained copper-clad laminate with a cured resin pattern is observed with an optical microscope, and the cured resin pattern is not peeled off from the copper foil. The minimum line width that can confirm that the developer did not enter from the periphery of the resin pattern was measured, and this was used as the evaluation result of adhesion.

(Example 2)
In Example 1, the developability, sensitivity, resolution, and adhesion were the same except that the surface-treated inorganic pigment 1 was replaced with 21.98 parts by mass of the surface-treated inorganic pigment 2 as shown in Table 1. Evaluation was performed. The results are shown in Table 2.

Example 3
In Example 1, the developability, sensitivity, resolution, and adhesion were the same except that the surface-treated inorganic pigment 1 was replaced with 21.98 parts by mass of the surface-treated inorganic pigment 3 as shown in Table 1. Evaluation was performed. The results are shown in Table 2.

Example 4
In Example 1, developability, sensitivity, resolution, and adhesiveness were similarly changed except that the surface-treated inorganic pigment 1 was replaced with 21.98 parts by mass of the surface-treated inorganic pigment 4 as shown in Table 1. Evaluation was performed. The results are shown in Table 2.

(Example 5)
In Example 1, the developability, sensitivity, resolution, and adhesion were the same except that the surface-treated inorganic pigment 1 was replaced with 21.98 parts by mass of the surface-treated inorganic pigment 5 as shown in Table 1. Evaluation was performed. The results are shown in Table 2.

(Example 6)
In Example 1, developability, sensitivity, resolution, and adhesiveness were similarly changed except that the surface-treated inorganic pigment 1 was replaced with 21.98 parts by mass of the surface-treated inorganic pigment 6 as shown in Table 1. Evaluation was performed. The results are shown in Table 2.

(Example 7)
In Example 1, the developability, sensitivity, resolution, and adhesion were similarly changed except that the surface-treated inorganic pigment 1 was replaced with 21.98 parts by mass of the surface-treated inorganic pigment 7 as shown in Table 1. Evaluation was performed. The results are shown in Table 2.

(Example 8)
In Example 1, the developability, sensitivity, resolution, and adhesion were the same except that the surface-treated inorganic pigment 1 was replaced with 21.98 parts by mass of the surface-treated inorganic pigment 8 as shown in Table 1. Evaluation was performed. The results are shown in Table 2.

Example 9
In Example 1, the developability, sensitivity, resolution, and adhesion were the same except that the surface-treated inorganic pigment 1 was replaced with 21.98 parts by mass of the surface-treated inorganic pigment 9 as shown in Table 1. Evaluation was performed. The results are shown in Table 2.

(Example 10)
In Example 1, developability and sensitivity were the same except that the compound represented by the formula I-1 was replaced with 2.6 parts by mass of the compound represented by the following formula I-2 as shown in Table 1. , Resolution, and adhesion were evaluated. The results are shown in Table 2.

(Example 11)
In Example 1, developability and sensitivity were the same except that the compound represented by the formula I-1 was replaced with 2.6 parts by mass of the compound represented by the following formula I-3 as shown in Table 1. , Resolution, and adhesion were evaluated. The results are shown in Table 2.

(Example 12)
In Example 1, developability and sensitivity were the same except that the compound represented by the formula I-1 was replaced with 2.6 parts by mass of the compound represented by the following formula I-4 as shown in Table 1. , Resolution, and adhesion were evaluated. The results are shown in Table 2.

(Example 13)
In Example 1, developability and sensitivity were the same except that the compound represented by the formula I-1 was replaced with 2.6 parts by mass of the compound represented by the following formula I-5 as shown in Table 1. , Resolution, and adhesion were evaluated. The results are shown in Table 2.

( Reference Example 14)
In Example 1, developability and sensitivity were the same except that the compound represented by the formula I-1 was replaced with 2.6 parts by mass of the compound represented by the following formula I-6 as shown in Table 1. , Resolution, and adhesion were evaluated. The results are shown in Table 2.

(Example 15)
In Example 1, the compound represented by the formula I-1 as shown in Table 1, 1.3 parts by mass of the compound represented by the formula I-1 as shown in Table 1, and the compound represented by the formula I-2 The developability, sensitivity, resolution, and adhesion were evaluated in the same manner except that the amount was changed to 1.3 parts by mass. The results are shown in Table 2.

(Example 16)
In Example 1, development property, sensitivity, resolution, and adhesion were evaluated in the same manner except that the binder 1 was replaced with 87.4 parts by mass of the binder 2 as shown in Table 1. The results are shown in Table 2.

(Example 17)
In Example 1, development property, sensitivity, resolution, and adhesion were evaluated in the same manner except that binder 1 was replaced with 48.2 parts by mass of binder 3 as shown in Table 1. The results are shown in Table 2.
(Example 18)
In Example 1, the surface-treated inorganic pigment 1 was replaced with 11.0 parts by mass of the surface-treated inorganic pigment 10 as shown in Table 1, and the compounds represented by the formula I-1 The development, sensitivity, resolution, and adhesion were evaluated in the same manner except that 2.6 parts by mass of the compound represented by the following formula I-7 was used. The results are shown in Table 2.
(Example 19)
In Example 1, the surface-treated inorganic pigment 1 was replaced with 11.0 parts by mass of the surface-treated inorganic pigment 11 as shown in Table 1, and the compounds represented by the formula I-1 The development, sensitivity, resolution, and adhesion were evaluated in the same manner except that 2.6 parts by mass of the compound represented by the formula I-7 was used. The results are shown in Table 2.
(Example 20)
In Example 1, the surface-treated inorganic pigment 1 was replaced with 11.0 parts by mass of the surface-treated inorganic pigment 12 as shown in Table 1, and the compounds represented by Formula I-1 The development, sensitivity, resolution, and adhesion were evaluated in the same manner except that 2.6 parts by mass of the compound represented by the formula I-7 was used. The results are shown in Table 2.
(Example 21)
In Example 1, the surface-treated inorganic pigment 1 was replaced with 11.0 parts by mass of the surface-treated inorganic pigment 13 as shown in Table 1, and the compounds represented by Formula I-1 The development, sensitivity, resolution, and adhesion were evaluated in the same manner except that 2.6 parts by mass of the compound represented by the formula I-7 was used. The results are shown in Table 2.
(Example 22)
In Example 1, the developability, sensitivity, resolution, and adhesion were the same except that the surface-treated inorganic pigment 1 was replaced with 11.0 parts by mass of the surface-treated inorganic pigment 12 as shown in Table 1. Evaluation was performed. The results are shown in Table 2.
(Example 23)
In Example 1, the surface-treated inorganic pigment 1 was replaced with 11.0 parts by mass of the surface-treated inorganic pigment 14 as shown in Table 1, and the compounds represented by the formula I-1 The development, sensitivity, resolution, and adhesion were evaluated in the same manner except that 2.6 parts by mass of the compound represented by the formula I-7 was used. The results are shown in Table 2.
(Example 24)
In Example 1, the surface-treated inorganic pigment 1 was replaced with 11.0 parts by mass of the surface-treated inorganic pigment 15 as shown in Table 1, and the compound represented by the formula I-1 was further changed to Table 1. The development, sensitivity, resolution, and adhesion were evaluated in the same manner except that 2.6 parts by mass of the compound represented by the formula I-7 was used. The results are shown in Table 2.
(Example 25)
In Example 1, the surface-treated inorganic pigment 1 was replaced with 11.0 parts by mass of the surface-treated inorganic pigment 16 as shown in Table 1, and the compounds represented by the formula I-1 The development, sensitivity, resolution, and adhesion were evaluated in the same manner except that 2.6 parts by mass of the compound represented by the formula I-7 was used. The results are shown in Table 2.
(Example 26)
In Example 1, the surface-treated inorganic pigment 1 was replaced with 11.0 parts by mass of the surface-treated inorganic pigment 17 as shown in Table 1, and the compounds represented by the formula I-1 The development, sensitivity, resolution, and adhesion were evaluated in the same manner except that 2.6 parts by mass of the compound represented by the formula I-7 was used. The results are shown in Table 2.

(Comparative Example 1)
In Example 1, developability was similarly performed except that the surface-treated inorganic pigment 1 was replaced with 21.98 parts by mass of barium sulfate (B30, manufactured by Sakai Chemical Co., Ltd.) as shown in Table 1. Sensitivity, resolution, and adhesion were evaluated. The results are shown in Table 2.

(Comparative Example 2)
In Example 1, the compound represented by Formula I-1 was replaced with 6.1 parts by mass of Irgacure 369 (basic type photopolymerization initiator, manufactured by Ciba Specialty Chemicals) as shown in Table 1. Except for the above, development property, sensitivity, resolution, and adhesion were evaluated in the same manner. The results are shown in Table 2.

(Comparative Example 3)
In Example 1, the compound represented by Formula I-1 was replaced with 6.1 parts by mass of Irgacure 907 (basic type photopolymerization initiator, manufactured by Ciba Specialty Chemicals) as shown in Table 1. Except for the above, development property, sensitivity, resolution, and adhesion were evaluated in the same manner. The results are shown in Table 2.

From the results of Table 2, in Examples 1 to 13 , 15 to 26, and Reference Example 14 in which the photopolymerization initiator includes an oxime derivative and the inorganic pigment is surface-treated with a silane coupling agent, Thus, it was found that a high-definition permanent pattern can be efficiently formed with good sensitivity, developability after preparation of the photosensitive laminate, and adhesion. In particular, in Examples 1 to 13, 15, 16 and Reference Examples 14 and 18 to 26, in which the binder contains a polymer compound having an acidic group and an ethylenically unsaturated bond in the side chain, after storage at 40 ° C. for 3 days It was found that the developability was excellent.
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 performed to observe how cracks occurred (how many patterns out of 27 lattice patterns (TCT resistance)). As a result, in Comparative Examples 1 to 3, cracks were easy to enter from the corners of the hole pattern, whereas in Examples 1 to 13, 15 to 26, and Reference Example 14 , cracks were difficult to enter. In particular, when silica was used as the inorganic filler (Examples 2 and 18 to 26), the crack generation rate was low.

Since the photosensitive composition and photosensitive film of the present invention have good sensitivity, developability, and adhesion, and can efficiently form a high-definition permanent pattern, a protective film, an interlayer insulating film, and a solder resist pattern It can be suitably used for various pattern formation such as permanent patterns, color filters, column materials, rib materials, spacers, liquid crystal structural members such as partition walls, holograms, micromachines, proofs, etc. Can be suitably used for forming a permanent pattern.
Since the permanent pattern forming method of the present invention uses the photosensitive composition of the present invention, it is used for forming various patterns such as a protective film, an interlayer insulating film, and a permanent pattern such as a solder resist pattern, a color filter, a column material, It can be suitably used for the production of liquid crystal structural members such as ribs, spacers and partition walls, the production of holograms, micromachines, and proofs, and can be particularly suitably used for the formation of permanent patterns on printed boards.

Claims (9)

It contains a binder, a polymerizable compound, a photopolymerization initiator, a thermal crosslinking agent, and an inorganic pigment, and the photopolymerization initiator is represented by any one of the following general formula (I), general formula (II), and general formula (X). A photosensitive composition comprising an oxime derivative having a partial structure , wherein the inorganic pigment is surface-treated with a silane coupling agent.
However, in said general formula (I) and (II), Ar represents a naphthalene ring. Y ¹ represents either a hydrogen atom or a monovalent substituent, and Y ² represents either COY ³ or CO ₂ Y ³ . Y ³ represents an aliphatic group. m represents an integer of 1 or more.
In the general formula (X), R ¹⁰⁰ represents any of an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group, and these substituents may further have a substituent. α represents any integer of 0 or more. R ²⁰⁰ represents a substituent, and when α is 2 or more, the R ²⁰⁰ may be the same or different. Ar represents a naphthalene ring. A represents any of 4, 5, 6, and 7-membered rings, and each of these rings may contain a hetero atom.   The silane coupling agent is selected from at least one functional group selected from an alkoxysilyl group, a chlorosilyl group, and an acetoxysilyl group, a vinyl group, an amino group, a mercapto group, an epoxy group, and a (meth) acryloyl group. The photosensitive composition according to claim 1, having at least one functional group.   The photosensitive composition according to claim 1, wherein the inorganic pigment is silica. The photosensitive composition in any one of Claim 1 to 3 containing a fluorine-type surfactant . The photosensitive composition in any one of Claim 1 to 4 in which a binder contains the high molecular compound which has an acidic group and an ethylenically unsaturated bond in a side chain . The photosensitive composition of Claim 5 in which a binder contains the high molecular compound which has an acidic group, the aromatic group which may contain a heterocyclic ring, and an ethylenically unsaturated bond in a side chain . A photosensitive film comprising a photosensitive layer made of the photosensitive composition according to claim 1 on a support. A method for forming a permanent pattern, comprising exposing a photosensitive layer formed of the photosensitive composition according to claim 1 . A printed circuit board, wherein a permanent pattern is formed by the permanent pattern forming method according to claim 8.