JP2007286487A - Photosensitive composition, photosensitive film, permanent pattern forming method and printed circuit board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition for solder resist having high sensitivity, high resolution, good storage stability and good various properties required and enabling a high-definition permanent pattern to be formed by using a photopolymerization initiation system compound containing a neutral heterocyclic ketone compound and a neutral o-acyloxime compound, and to provide a photosensitive film, a permanent pattern forming method using the photosensitive composition, and a printed circuit board on which a pattern is formed by the permanent pattern forming method. <P>SOLUTION: The photosensitive composition contains a binder, a polymerizable compound, a photopolymerization initiation system compound and a heat crosslinking agent, wherein the photopolymerization initiation system compound contains the neutral heterocyclic ketone compound and the neutral o-acyloxime compound. There are also provided the photosensitive film, the permanent pattern forming method using the photosensitive composition, and the printed circuit board on which the pattern is formed by the permanent pattern forming method. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a photosensitive composition, a photosensitive film, a method for forming a permanent pattern, and a printed board suitable for forming a high-definition permanent pattern (such as a protective film, an interlayer insulating film, and a solder resist pattern).

  In the photoresist for manufacturing printed circuit boards, switching from a liquid resist to a dry film is progressing. This may be because, for example, high sensitivity and high resolution are easily obtained and handling properties are excellent. On the other hand, with regard to the formation of a permanent pattern such as a solder resist, even today, liquid resist is mostly used, and dry film formation is delayed.

One of the causes is that the solder resist contains a carboxylic acid group-containing resin and an epoxy resin.
More specifically, in the production of the solder resist, an alkali development system is generalized, the carboxylic acid group-containing resin is an essential component for the alkali development treatment, and an epoxy resin is obtained. It is an essential component for realizing heat resistance, hardness, substrate adhesion and the like.

That is, it is necessary that the originally reactive epoxy group and carboxyl group coexist in the solder resist, which limits the storage stability of the solder resist film. In particular, when applying a blue-violet laser (wavelength 405 ± 5 nm) exposure system with excellent light stability under a yellow safety light and capable of maskless exposure, storage stability is required to realize a highly sensitive solder resist. One of the major issues is improving the performance.
Moreover, the solder resist as a permanent pattern is required to have various properties such as pencil hardness, adhesion, electrical insulation, acid resistance, alkali resistance, electroless gold plating resistance, and PCT resistance.

Here, acyl oximes (see Patent Document 1) have been proposed as highly sensitive photopolymerization initiators. Moreover, as a solder resist application, a curable composition using oxime ether and an epoxy acrylate oligomer in combination (see Patent Document 2), a curable composition using oxime ether (see Patent Document 3), acyl oxime and sulfur. A curable composition using a combination of benzophenone having atoms (see Patent Document 4) has been proposed. Furthermore, as a lithographic printing plate precursor, a photopolymerizable composition using a combination of a thiazolyl ketone sensitizing dye and a specific activator to improve sensitivity, storage stability, etc. has been proposed (Patent Document 5). reference).
However, a photosensitive composition using a combination of a heterocyclic compound and an O-acyloxime compound and using a neutral compound in both has not yet been proposed for use as a solder resist.

  Therefore, as a solder resist application, a photopolymerization initiating system compound containing a neutral heterocyclic ketone compound and a neutral O-subjux oxime compound has high sensitivity and high resolution, good storage stability, and requirements. A pattern is formed by a photosensitive composition, a photosensitive film, a permanent pattern forming method using the photosensitive composition, and the permanent pattern forming method. The printed circuit board has not been provided yet, and the present situation is that further improvement and development are desired.

JP 2000-80068 A JP 2001-302871 A International Publication No. 02/96969 Pamphlet JP 2005-182004 A JP-A-3-296759

  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 has high sensitivity and high resolution and good storage stability by using a photopolymerization initiation system compound including a neutral heterocyclic ketone compound and a neutral O-acyloxime compound as a solder resist application. And a photosensitive composition capable of forming a high-definition permanent pattern with good required properties, a photosensitive film, a permanent pattern forming method using the photosensitive composition, and a pattern formed by the permanent pattern forming method. It aims at providing the printed circuit board formed.

Means for solving the problems are as follows. That is,
<1> A binder, a polymerizable compound, a photopolymerization initiation system compound, and a thermal crosslinking agent, wherein the photopolymerization initiation system compound includes a neutral heterocyclic ketone compound and a neutral O-acyloxime compound. Is a photosensitive composition. In the photosensitive composition according to <1>, the neutral heterocyclic ketone compound absorbs light as a sensitizing dye, and promotes initiation radical generation from the coexisting neutral O-acyloxime compound. it is conceivable that.
<2> The photosensitive heterocyclic composition according to <1>, wherein the neutral heterocyclic ketone compound is represented by the following general formula (I).
However, in said general formula (I), X < ₁ > and X < ₂ > represent either the alkyl group, the aryl group, and heteroaryl group which may have a substituent each independently, X < ₁ > and X < ₂ >. And may combine with each other to form a 5- to 7-membered ring. X represents a monovalent nonmetallic atomic group. Y represents either an oxygen atom or a sulfur atom.
<3> The photosensitive composition according to <2>, wherein the neutral O-acyloxime compound is represented by the following general formulas (II-1) to (II-4).
However, the general formula (II-1) in ~ (II-4), R 1 is a phenyl group, an alkyl group, a cycloalkyl group, a halogenated alkyl group, an alkanoyl group, a benzoyl group, an alkoxycarbonyl group, a phenoxycarbonyl group , CONR ¹⁴ R ¹⁵ , CN, NO ₂ , an aryl group, and a diphenylphosphinoyl group. R ² represents any one of an alkanoyl group, an alkenoyl group, a benzoyl group, an alkoxycarbonyl group, and a phenoxycarbonyl group. R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are each independently a hydrogen atom, halogen atom, alkyl group, cyclopentyl group, cyclohexyl group, phenyl group, benzyl group, benzoyl group, alkanoyl group, alkoxycarbonyl Represents any of a group, a phenoxycarbonyl group, OR ¹² , SR ¹³ , SOR ¹³ , and SO ₂ R ¹³ . R ⁸ represents any of an alkoxycarbonyl group, a phenoxycarbonyl group, a cycloalkyl group, CONR ¹⁴ R ¹⁵ , CN, a phenyl group, and an alkyl group. R ⁹ , R ¹⁰ , and R ¹¹ are each independently a hydrogen atom, halogen atom, alkyl group, cyclopentyl group, cyclohexyl group, phenyl group, benzyl group, benzoyl group, alkanoyl group, alkoxycarbonyl group, phenoxycarbonyl group, One of OR ¹² , SR ¹³ , SOR ¹³ , and SO ₂ R ¹³ is represented. R ¹² represents a hydrogen atom, an alkyl group, (CH ₂ CH ₂ O) nH, an alkanoyl group, an alkenyl group, an alkenoyl group having 3 to 6 carbon atoms, and a phenyl group, and n represents an integer of 1 to 20. R ¹³ represents either an alkyl group or a phenyl group. R ¹⁴ and R ¹⁵ each independently represents any of a hydrogen atom, an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkenyl group, a cycloalkyl group, a phenyl group, an alkanoyl group, an alkenoyl group, and a benzoyl group. M represents any one of an alkylene group, a cyclohexylene group, and a phenylene group.
<4> The neutral heterocyclic ketone compound is 2-β-naphthothiazolylphenyl ketone, 2-benzothiazolyl-2-thienyl ketone, bis (2-benzothiazolyl) ketone, 2-benzothiazolyl-p-methoxy-α-. Styryl ketone, 5-chloro-2-benzothiazolyl-p-methylphenyl ketone, 2-benzoxazolyl-p-methoxy-α-styryl ketone, 4,5-bis (2-furyl) thiazolyl phenyl ketone, and The photosensitive composition according to any one of <1> to <3>, which is any one of γ-naphth-2-thiazolyl phenyl ketone.
<5> The photosensitive composition according to any one of <1> to <4>, wherein the neutral O-acyloxime compound is (2-acetyloxyiminomethyl) -thioxanthen-9-one. .
<6> The photosensitive composition according to any one of <1> to <5>, wherein the photopolymerization initiating compound includes a hydrogen donor compound.
<7> The <6>, wherein the hydrogen donor compound is any one of 1-phenyl-2-mercapto-1,3-benzimidazole and tetra (n-butyl) ammonium-n-butyltriphenylborate. Of the photosensitive composition.
<8> The content ratio between the neutral heterocyclic ketone compound and the neutral O-acyloxime compound is 1: 6 to 6: 1, according to any one of <1> to <7> above. It is a photosensitive composition.

<9> The photosensitive composition according to any one of <1> to <8>, wherein the binder is an alkali-soluble crosslinkable resin.
<10> The photosensitive composition according to any one of <1> to <9>, wherein the polymerizable compound includes a monomer having a (meth) acryl group.
<11> 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. 10>. The photosensitive composition according to any one of 10>.
<12> The photosensitive composition according to any one of <1> to <11>, including a thermosetting accelerator.
<13> The photosensitive composition according to any one of <1> to <12>, including an inorganic filler.

<14> A photosensitive film comprising a support and a photosensitive layer comprising the photosensitive composition according to any one of <1> to <13> on the support.
<15> The photosensitive film according to <14>, wherein the support includes a synthetic resin and is transparent.
<16> The photosensitive film according to any one of <14> to <15>, wherein the support has a long shape.
<17> The photosensitive film according to any one of <14> to <16>, which is long and wound in a roll shape.
<18> The photosensitive film according to any one of <14> to <17>, which has a protective film on the photosensitive layer.
<19> The photosensitive film according to any one of <14> to <18>, wherein the photosensitive layer has a thickness of 1 to 100 μm.

<20> A light irradiation unit capable of irradiating light, and a photosensitive layer formed of the photosensitive composition according to any one of <1> to <13>, wherein light from the light irradiation unit is modulated. And a light modulation means for performing exposure. In the pattern forming apparatus according to <20>, the light irradiation unit irradiates light toward the light modulation unit. The light modulation unit modulates light received from the light irradiation unit. The light modulated by the light modulator is exposed to the photosensitive layer. For example, when the photosensitive layer is subsequently developed, a high-definition pattern is formed.
<21> The light modulation means further includes pattern signal generation means for generating a control signal based on the pattern information to be formed, and the control signal generated by the pattern signal generation means is emitted from the light irradiation means. It is a pattern formation apparatus as described in said <20> modulated according to. In the pattern forming apparatus according to <21>, since the light modulation unit includes the pattern signal generation unit, light emitted from the light irradiation unit corresponds to a control signal generated by the pattern signal generation unit. Modulated.
<22> The light modulation means has n pixel parts, and forms any less than n pixel elements arranged continuously from the n pixel parts. The pattern forming apparatus according to any one of <20> to <21>, which is controllable according to pattern information. In the pattern forming apparatus according to <22>, an arbitrary less than n pixel portions arranged continuously from n pixel portions in the light modulation unit are controlled according to pattern information. Thereby, the light from the light irradiation means is modulated at high speed.
<23> The pattern forming apparatus according to any one of <20> to <22>, wherein the light modulation unit is a spatial light modulation element.
<24> The pattern forming apparatus according to <23>, wherein the spatial light modulation element is a digital micromirror device (DMD).
<25> The pattern forming apparatus according to any one of <22> to <24>, wherein the drawing element portion is a micromirror.
<26> The pattern forming apparatus according to any one of <20> to <25>, wherein the light irradiation unit is capable of combining and irradiating two or more lights. In the pattern forming apparatus according to <26>, since the light irradiation unit can synthesize and irradiate two or more lights, exposure is performed with exposure light having a deep focal depth. As a result, the exposure of the photosensitive layer is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.
<27> The light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that collects the laser beams irradiated from the plurality of lasers and couples the laser beams to the multimode optical fiber. <20> to the pattern forming apparatus according to any one of <26>. In the pattern forming apparatus according to <27>, the light irradiation unit can condense the laser beams irradiated from the plurality of lasers by the collective optical system and couple the laser beams to the multimode optical fiber. Thus, exposure is performed with exposure light having a deep focal depth. As a result, the exposure of the photosensitive layer is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.

<28> A method for forming a permanent pattern, comprising exposing a photosensitive layer formed of the photosensitive composition according to any one of <1> to <13>.
<29> The method for forming a permanent pattern according to <28>, wherein the photosensitive layer is formed of the photosensitive film according to any one of <14> to <19>.
<30> The method for forming a permanent pattern according to any one of <28> to <29>, wherein the exposure is performed using a laser beam having a wavelength of 350 to 415 nm.
<31> The permanent pattern forming method according to any one of <28> to <30>, wherein the exposure is performed imagewise based on pattern information to be formed.

<32> The photosensitive layer has light irradiation means and n (where n is a natural number of 2 or more) two-dimensionally arranged pixel parts that receive and emit light from the light irradiation means. An exposure head provided with a light modulation means capable of controlling the picture element unit according to pattern information, wherein the column direction of the picture element part is a predetermined set inclination angle θ with respect to the scanning direction of the exposure head. Using an exposure head arranged to form
With respect to the exposure head, the usable pixel part designating means designates the pixel part to be used for N double exposure (where N is a natural number of 2 or more) among the usable graphic elements.
For the exposure head, the pixel part control means controls the pixel part so that only the pixel part specified by the used pixel part specifying means is involved in exposure,
The permanent pattern forming method according to any one of <28> to <31>, wherein the exposure head is moved relative to the photosensitive layer in a scanning direction. In the method for forming a permanent pattern according to <32>, the exposure head is subjected to N multiple exposures (where N is a natural number of 2 or more) among the usable pixel parts by the used pixel part specifying means. The pixel part to be used is specified, and the pixel part is controlled by the pixel part control unit so that only the pixel part specified by the used pixel part specifying unit is involved in exposure. . By performing exposure by moving the exposure head relative to the photosensitive layer in the scanning direction, the exposure head is formed on the exposed surface of the photosensitive layer due to a shift in the mounting position or mounting angle of the exposure head. Variations in the resolution of the pattern and unevenness in density are leveled. As a result, the photosensitive layer is exposed with high definition, and then the photosensitive layer is developed to form a high-definition pattern.
<33> The exposure is performed by a plurality of exposure heads, and the drawing element specifying unit is related to the exposure of the head-to-head connection region, which is an overlapping exposure region on the exposed surface formed by the plurality of exposure heads. The permanent pattern forming method according to the above <32>, wherein among the element parts, the image element part used for realizing N double exposure in the inter-head connecting region is designated. In the method for forming a permanent pattern according to <33>, exposure is performed by a plurality of exposure heads, and a used pixel portion designating unit is an overlapping exposure region on an exposed surface formed by the plurality of exposure heads. Of the picture element parts involved in the exposure of the connection area between the heads, by specifying the picture element part used for realizing the N-fold exposure in the connection area between the heads, the mounting position of the exposure head, Variations in the resolution and density unevenness of the pattern formed in the connecting area between the heads on the exposed surface of the photosensitive layer due to the mounting angle deviation are leveled. As a result, the photosensitive layer is exposed with high definition, and then the photosensitive layer is developed to form a high-definition pattern.
<34> The exposure is performed by a plurality of exposure heads, and the used picture element specifying means is involved in exposure other than the inter-head connection region, which is an overlapping exposure region on the exposed surface formed by the plurality of exposure heads. The permanent pattern forming method according to <33>, wherein the image element portion used for realizing N double exposure in an area other than the inter-head connection area in the image element area is designated. In the method for forming a permanent pattern according to <34>, exposure is performed by a plurality of exposure heads, and the used image element designating unit is an overlapping exposure region on an exposed surface formed by the plurality of exposure heads. Mounting of the exposure head by designating the picture element part used for realizing N double exposure in areas other than the inter-head connection area among the image element parts related to exposure other than the inter-head connection area Variations in the resolution and density unevenness of the pattern formed in areas other than the joint area between the heads on the exposed surface of the photosensitive layer due to a shift in position and mounting angle are leveled. As a result, the photosensitive layer is exposed with high definition, and then the photosensitive layer is developed to form a high-definition pattern.
<35> When the set inclination angle θ is N, the number N of the multiple exposures, the number s of the pixel parts in the column direction, the interval p of the pixel parts in the column direction, and the exposure head tilted. the relative row direction pitch δ of pixel parts in the direction perpendicular to the scanning direction, the following equation with respect to theta _ideal satisfying spsinθ _ideal ≧ Nδ, which is set so as to satisfy the relation of θ ≧ θ _ideal <32> to <34>.
<36> The permanent pattern forming method according to any one of <32> to <35>, wherein N in N-fold exposure is a natural number of 3 or more. In the permanent pattern forming method according to <36>, multiple drawing is performed when N in N double exposure is a natural number of 3 or more. As a result, due to the effect of filling, variations in the resolution and density unevenness of the pattern formed on the exposed surface of the photosensitive layer due to a shift in the mounting position and mounting angle of the exposure head are more precisely leveled.

<37> Use pixel part designation means,
A light spot position detecting means for detecting a light spot position on a surface to be exposed as a pixel unit generated by a picture element unit and constituting an exposure area on the surface to be exposed;
<32> to <36>, further comprising: a pixel part selection unit that selects a pixel part to be used for realizing N double exposure based on a detection result by the light spot position detection unit. This is a permanent pattern forming method.
<38> The permanent pattern forming method according to any one of <32> to <37>, wherein the used pixel part specifying unit specifies, in line units, the used pixel part to be used for realizing N double exposure. It is.

<39> Based on at least two light spot positions detected by the light spot position detection means, an actual direction formed by the column direction of the light spots on the surface to be exposed and the scanning direction of the exposure head when the exposure head is tilted. The inclination angle θ ′ is specified, and the picture element selection means selects the use picture element part so as to absorb the error between the actual inclination angle θ ′ and the set inclination angle θ. The permanent pattern forming method according to any one of the above.
<40> The actual inclination angle θ ′ is an average value, a median value, and a plurality of actual inclination angles formed by the row direction of the light spots on the surface to be exposed and the scanning direction of the exposure head when the exposure head is inclined. The permanent pattern forming method according to <39>, wherein the permanent pattern forming method is one of a maximum value and a minimum value.
<41> The pixel part selection means derives a natural number T close to t satisfying a relationship of ttan θ ′ = N (where N represents N of N double exposure numbers) based on the actual inclination angle θ ′, and m <37> to <40> in which the pixel elements in the first to the Tth rows are selected as the used pixel elements in a line element (where m represents a natural number of 2 or more). The permanent pattern forming method according to any one of the above.
<42> The pixel part selection means derives a natural number T close to t satisfying a relationship of ttan θ ′ = N (where N represents N of N double exposure numbers) based on the actual inclination angle θ ′, and m In the picture element part arranged in a row (where m represents a natural number of 2 or more), the picture element part from line (T + 1) to m-th line is specified as an unused picture element part, and the unused picture element part is specified. The permanent pattern forming method according to any one of <37> to <40>, wherein the pixel part excluding the element part is selected as a use pixel part.

<43> In a region including at least an overlapped exposure region on an exposed surface formed by a plurality of pixel part columns,
(1) Means for selecting a used pixel portion so that a total area of an overexposed region and an underexposed region is minimized with respect to an ideal N-fold exposure;
(2) Means for selecting a pixel part to be used so that the number of pixel units in an overexposed area and the number of pixel units in an underexposed area are equal to each other with respect to an ideal N double exposure;
(3) Means for selecting a pixel part to be used so that an area of an overexposed area is minimized and an underexposed area does not occur with respect to an ideal N double exposure, and (4) an ideal From <37>, which is one of means for selecting a used pixel portion so that the area of the underexposed region is minimized and no overexposed region is generated with respect to typical N double exposure <42> The permanent pattern forming method according to any one of the above.
<44> In the joint region between the heads, which is an overlapping exposure region on the exposed surface formed by the plurality of exposure heads,
(1) With respect to the ideal N-multiple exposure, from the pixel part involved in the exposure of the inter-head connection region, the total area of the overexposed region and the underexposed region is minimized. Means for identifying a used pixel part and selecting the pixel part excluding the unused pixel part as a used pixel part;
(2) Involvement in the exposure of the head-to-head connecting region so that the number of pixel units in the overexposed region and the number of pixel units in the underexposed region are equal to the ideal N-double exposure. Means for identifying an unused pixel part from the pixel part to be selected, and selecting the pixel part excluding the unused pixel part as a used pixel part;
(3) For the ideal N-multiple exposure, from the pixel part involved in the exposure of the inter-head connecting region, the area of the overexposed region is minimized and the underexposed region is not generated. A means for identifying an unused pixel part and selecting the pixel part excluding the unused pixel part as a used pixel part; and
(4) For the ideal N-multiple exposure, from the pixel part involved in the exposure of the inter-head connecting region, the area of the underexposed region is minimized and the region that is overexposed is not generated. , Means for identifying an unused pixel part and selecting the pixel part excluding the unused pixel part as a used pixel part;
The method for forming a permanent pattern according to any one of <37> to <43>.
<45> The permanent pattern forming method according to <44>, wherein the unused pixel parts are specified in units of rows.

<46> In order to specify the used pixel part in the used pixel part specifying means, among the usable pixel elements, N (N-1) pixel element columns for N multiple exposures The permanent pattern forming method according to any one of <32> to <45>, wherein the reference exposure is performed using only the image element portion that constitutes. In the permanent pattern forming method according to <46>, in order to specify the used pixel part in the used pixel part specifying means, among the usable pixel parts, N-1) Reference exposure is performed using only the pixel part constituting the pixel part column for each column, and a simple pattern of substantially single drawing is obtained. As a result, the picture element portion in the head-to-head connection region is easily specified.
<47> In order to specify the used pixel part in the used pixel part specifying means, among the usable pixel parts, a pixel part row is formed every 1 / N lines for N of N multiple exposures. The method for forming a permanent pattern according to any one of <32> to <46>, wherein the reference exposure is performed using only the picture element portion. In the permanent pattern forming method according to <47>, in order to designate the use pixel part in the use pixel part designating unit, among the usable picture element parts, N is one for N double exposure. / A reference exposure is performed using only the pixel part constituting the pixel part column for every N rows, and a simple pattern of substantially single drawing is obtained. As a result, the picture element portion in the head-to-head connection region is easily specified.

<48> From the above <32> to <47>, the used pixel part specifying unit includes a slit and a photodetector as a light spot position detecting unit, and an arithmetic unit connected to the photodetector as a pixel unit selecting unit. The permanent pattern forming method according to any one of the above.
<49> The method for forming a permanent pattern according to any one of <32> to <48>, wherein N in N-exposure is a natural number of 3 or more and 7 or less.
<50> Any one of the items <32> to <49>, wherein the pattern information is converted so that a dimension of a predetermined part of the pattern represented by the pattern information matches a dimension of a corresponding part that can be realized by the designated used pixel part This is a method for forming a permanent pattern as described above.

<51> The method for forming a permanent pattern according to any one of <28> to <50>, wherein the photosensitive layer is developed after the exposure.
<52> The method for forming a permanent pattern according to <51>, wherein after the development, the photosensitive layer is subjected to a curing treatment.
<53> The method for forming a permanent pattern according to <52>, wherein the curing treatment is at least one of a whole surface exposure treatment and a whole surface heat treatment performed at 120 to 200 ° C. In the method for forming a permanent pattern according to <53>, curing of the resin in the photosensitive composition is promoted in the overall exposure process. Moreover, the film | membrane intensity | strength of a cured film is raised in the whole surface heat processing performed on the said temperature conditions.

<54> A permanent pattern formed by the pattern forming method according to any one of <28> to <53>. Since the permanent pattern according to <54> is formed by the pattern forming method, it has excellent chemical resistance, surface hardness, heat resistance, and the like, and has high definition, and is a multilayer wiring board for semiconductors and components. It is useful for high-density mounting on PCBs and build-up wiring boards.
<55> The pattern according to <54>, which is at least one of a protective film, an interlayer insulating film, and a solder resist pattern. Since the permanent pattern according to <55> is at least one of a protective film, an interlayer insulating film, and a solder resist pattern, the wiring may be subjected to an impact or bending from the outside due to the insulation property, heat resistance, etc. of the film. Protected from.

  <56> A printed circuit board wherein a permanent pattern is formed by the permanent pattern forming method according to any one of <28> to <53>.

  According to the present invention, conventional problems can be solved. As a solder resist application, a photopolymerization initiating system compound including a neutral heterocyclic ketone compound and a neutral O-acyl oxime compound provides high sensitivity and high resolution. A photosensitive composition capable of forming a high-definition permanent pattern with good storage stability and good properties required, a photosensitive film, and a permanent pattern forming method using the photosensitive composition, In addition, a printed circuit 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 at least a binder, a polymerizable compound, a photopolymerization initiating compound, and a thermal crosslinking agent, preferably contains a thermosetting accelerator, and, if necessary, other appropriately selected Contains ingredients.

<Photopolymerization initiation compound>
The photopolymerization initiating compound contains a neutral heterocyclic ketone compound and a neutral O-acyloxime compound, and preferably further contains a hydrogen donor compound. Here, “neutral” represents one having a pH of 6.4 to 7.4 when dissolved in water or a solution of a solvent miscible with water.

-Heterocyclic ketone compound-
The heterocyclic ketone compound of the present invention is not particularly limited as long as it is neutral and does not contain an acidic group and a basic group, but a compound represented by the following general formula (I) is preferable.
However, in said general formula (I), X < ₁ > and X < ₂ > represent either the alkyl group, the aryl group, and heteroaryl group which may have a substituent each independently, X < ₁ > and X < ₂ >. And may combine with each other to form a 5- to 7-membered ring. X represents a monovalent nonmetallic atomic group. Y represents either an oxygen atom or a sulfur atom.

The nitrogen-containing 5-membered ring in the general formula (I) includes thiazoles, benzothiazoles, naphthothiazoles, thianaphtheno-7 ′, 6 ′, 4,5-thiazoles, oxazoles, benzoxazoles, naphtho Oxazoles are mentioned.
Examples of the thiazoles include thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 4,5-di- (P-methoxyphenylthiazole), 4- (2-thienyl) thiazole, and the like.
Examples of the benzothiazoles include benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6- Methylbenzothiazole, 5-bromobenzothiazole, 4-phenylbenzothiazole, 5-phenylbenzothiazole, 4-methoxybenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-iodobenzothiazole, 6-iodobenzo Thiazole, 4-ethoxybenzothiazole, 5-ethoxybenzothiazole, tetrahydrobenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-dioxymethylenebenzothiazole, 5-hydro Shi benzothiazole, 6-hydroxy-benzothiazole, 6-1-dimethylamino-benzothiazole, 5-ethoxycarbonyl-benzothiazole, and the like.
Examples of the naphthothiazoles include naphtho [1,2] thiazole, naphtho [2,1] thiazole, 5-methoxynaphtho [2,1] thiazole, 5-ethoxynaphtho [2,1] thiazole, and 8-methoxy. Examples include naphtho [1,2] thiazole, 7-methoxynaphtho [1,2] thiazole and the like.
Examples of the thianaphtheno-7 ′, 6 ′, 4,5-thiazoles include 4′-methoxythianaphtheno-7 ′, 6 ′, 4,5-thiazole.
Examples of the oxazoles include 4-methyl oxazole, 5-methyl oxazole, 4-phenyl oxazole, 4,5-diphenyl oxazole, 4-ethyl oxazole, 4,5-dimethyl oxazole, and 5-phenyl oxazole. .
Examples of the benzoxazoles include benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzox Examples include oxazole, 6-methoxybenzoxazole, 5-methoxybenzoxazole, 4-ethoxybenzoxazole, 5-chlorobenzoxazole, 6-methoxybenzoxazole, 5-hydroxybenzoxazole, and 6-hydroxybenzoxazole.
Examples of the naphthoxazoles include naphtho [1,2] oxazole, naphtho [2,1] oxazole, and the like.

Preferable examples of X ₁ and X _{2 in} the general formula (I) include an alkyl group, a substituted alkyl group, a halogen atom (—F, —Br, —Cl, —I), a hydroxyl group, an alkoxy group, and an aryloxy group. , Mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio 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, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group N′-alkylureido group, N ′, N′- Alkylureido 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, 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, dialkylphosphono group (—PO ₃ (alkyl) ₂ ), a diarylphosphono group (—PO ₃ (aryl) ₂ ), an alkylaryl phosphono group (—PO ₃ (alkyl) (aryl)), a dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ), diaryl phosphonooxy group _{(-OPO 3 (aryl) 2)} , alkylaryl phosphonooxy group ( _{OPO 3 (alkyl) (aryl)} ), a cyano group, a nitro group, an aryl group, a heteroaryl group, an alkenyl group, an alkynyl group.

Preferred examples of the alkyl group in these substituents include linear, branched and cyclic alkyl groups having 1 to 20 carbon atoms.
Specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, 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, A 2-norbornyl group is mentioned. 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 alkylene group in the substituted alkyl group include a divalent organic residue obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. The alkylene group is preferably a linear alkylene group having 1 to 12 carbon atoms, a branched chain having 3 to 12 carbon atoms, or a cyclic alkylene group having 5 to 10 carbon atoms.
The substituent of the substituted alkyl group is not particularly limited, but specific examples of a preferable substituted alkyl group include a chloromethyl group, a bromomethyl group, a 2-chloroethyl group, a trifluoromethyl group, a methoxymethyl group, and a methoxyethoxyethyl group. Allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl 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, chlorophenoxycarbonylmethyl group, carbamoylmethyl Group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group, sulfamoylbutyl group, N -Ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphonophenyl) sulfamoyloctyl group, diethylphosphonobutyl group , Diphenylphosphonopropyl group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenyl Ethyl group-p-methylbenzyl group, cinnami Group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group and the like.

Specific examples of the aryl group in the preferable substituent of X ₁ and X ₂ include those in which 1 to 3 benzene rings form a condensed ring, and the benzene ring and a 5-membered unsaturated ring form a condensed ring. Things.
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.

Specific examples of the aryl group having the substituent of X ₁ and X ₂ include those having a monovalent non-metallic atomic group excluding hydrogen as a substituent on the ring-forming carbon atom of the aforementioned aryl group. .
Preferable specific examples of the aryl group having a substituent include a biphenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a chlorophenyl group, a bromophenyl group, a fluorophenyl group, a chloromethylphenyl group, and a trifluoromethylphenyl group. Hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, acetyloxyphenyl group, benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, allyloxycarbonyl Phenyl 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, methylphosphonophenyl group, methylphosphonatophenyl group Tolylphosphonophenyl group, tolylphosphonatophenyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallylphenyl group, 2-methylpropenylphenyl group, 2-propynylphenyl group, 2-butynyl A phenyl group, 3-butynylphenyl group, etc. are mentioned.

Examples of the heteroaryl group in X ₁ and X ₂ include a monocyclic or polycyclic aromatic ring containing at least one of nitrogen, oxygen and sulfur atoms. For example, 5-membered or 6-membered aromatic substituents such as furan, pyrrole, and pyridine are preferable.
In these groups, examples of the alkenyl group include vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group and the like, and examples of the alkynyl group include ethynyl group. 1-propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like.

Examples of _{G 1} in the acyl group in the substituent of the _{X 1} and _{X 2 (G} 1 CO-), hydrogen, as well as alkyl and aryl groups described above. 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 acyloxy group, and an 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-ary Rucarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N-alkyl-N-arylsulfur Famoyl group, dialkylphosphine Amino group, a diaryl phosphono group, monoalkyl phosphono group, alkyl phosphonophenyl group, monoaryl phosphono group, aryl phosphonophenyl group, an aryl group, and an alkenyl group.

As X in the general formula (I), for example, any of those exemplified as the substituents in X ₁ and X ₂ , a hydrogen atom, and the like can be preferably used. Among these substituents, when an alkyl group that may be substituted, an aryl group that may be substituted, a heteroaryl group that may be substituted, or an alkenyl group that may be substituted is used, Since an inexpensive raw material can be synthesized in a short process, it is economical. In particular, Y is an aryl group that may be substituted, a heteroaryl group that may be substituted, or an alkenyl group that may be substituted, which is advantageous in terms of absorption wavelength and very excellent in storage stability. Give the pigment.

Specific examples of the aryl group particularly preferable as the X include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group.
Specific examples of the aryl group which may be particularly preferably substituted as X include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trityl group. Fluoromethylphenyl, hydroxyphenyl, methoxyphenyl, methoxyethoxyphenyl, allyloxyphenyl, phenoxyphenyl, methylthiophenyl, tolylthiophenyl, ethylaminophenyl, diethylaminophenyl, morpholinophenyl, acetyl Oxyphenyl group, benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylamino Phenyl group, carboxyphenyl 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-dipropylsulfa Moylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, di Phenylphosphonophenyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonophenyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallylphenyl group , 2-methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3-butynylphenyl group, and the like.

  As the particularly preferred heteroaryl group for X, for example, any of those exemplified as examples of the nitrogen-containing 5-membered ring in the general formula (I) can be suitably used. Others, thiophene, thiathrene, furan, pyran, isobenzofuran, chromene, xanthene, phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole, pyrazine, pyrimidine, pyridazine, indolizine, isoindolizine, indoir, indazole, purine, Quinolidine, isoquinoline, phthalazine, naphthyridine, quinazoline, cinolin, pteridine, carbazole, carboline, phenanthrine, acridine, perimidine, phenanthroline, phthalazine, phenalazine, phenoxazine, furazane, phenoxazine and the like. These may further be benzo-fused or have a substituent.

As the alkenyl group preferable as X, in addition to the examples of the alkenyl group described above, those represented by the partial structural formula A shown below are particularly preferable.
However, in said partial structural formula (A), M < ₁ > and M < ₂ > represent the methine carbon which may be substituted each independently. X ₃ represents either an aryl group or a heteroaryl group which may have a substituent, and n is an integer of 1 or more.

When M ₁ and M ₂ are each independently CH or CCH ₃ , the production of the dye is particularly easy, and when n is 1 or 2, a dye excellent in both absorption characteristics and stability can be obtained. .
As the aryl group and heteroaryl group which may have a substituent in X _3, any of those already exemplified can be used preferably.

Specific examples D1 to D32 of the neutral heterocyclic ketone compound represented by the general formula (I) of the present invention are shown below, but the present invention is not limited thereto.
D1: 2-β-naphthothiazolyl phenyl ketone D2: 2-β-naphthothiazolyl-p-methoxyphenyl ketone D3: 2-β-naphthothiazolyl-p-chlorophenyl ketone D4: 2-benzothiazolyl 3,4-dimethoxyphenyl ketone
D5: 2-benzothiazolyl-p-methoxy-α-styryl ketone
D6: 2-β-naphthothiazolyl-p-acetylaminophenyl ketone D7: 2-benzothiazolyl phenyl ketone D8: 2-quinoxanyl phenyl ketone D9: 5-phenyl-1,3,4-oxadiazole-2 -Ylphenylketone D10: 2-benzothiazolyl-p-methoxyphenylketone D11: 2-benzothiazolyl-p-chlorophenylketone D12: 2-quinoxanyl-p-chlorophenylketone D13: 2-quinoxanyl-p-methoxyphenylketone D14: 2, 4-bis (4-methoxybenzoyl) quinoxaline D15: 2-benzothiazolyl-3,4,5-trimethoxyphenyl ketone D16: 2-benzothiazolyl-2,4,6-trimethoxyphenyl ketone D17: 2-benzothiazolyl-p- Acetylamino Enyl ketone D18: 2-benzothiazolyl-p-bromophenyl ketone D19: 2-benzothiazolyl-p-methylphenyl ketone D20: 2-benzothiazolyl-2-thienyl ketone D21: bis (2-benzothiazolyl) ketone D22: 2-benzothiazolyl-p- Methoxy-α-styryl ketone D23: 5-chloro-2-benzothiazolyl-p-methylphenyl ketone D24: 2-benzoxazolyl-p-methoxy-α-styryl ketone
D25: 3,3-dimethyl-3H-indol-2-yl-p-methoxyphenyl ketone D26: 4-cyano-quinolylbenzofuran-2-yl ketone D27: 4,5,6,7-tetrahydro-2-benzothia Zolyl phenyl ketone D28: 4,5-bis (2-furyl) thiazolyl phenyl ketone D29: 2-α-naphthothiazolyl phenyl ketone D30: 4-methyl-2-thiazolyl phenyl ketone D31: γ- Naphth-2-thiazolyl phenyl ketone D32: 4,5-bis (p-methoxyphenyl) thiazolyl phenyl ketone

  Among the compounds of D1 to D32, D1: 2-β-naphthothiazolyl phenyl ketone, D20: 2-benzothiazolyl-2-thienyl ketone, D21: bis (2-benzothiazolyl) ketone, D22: 2-benzothiazolyl-p -Methoxy- [alpha] -styryl ketone, D23: 5-chloro-2-benzothiazolyl-p-methylphenyl ketone, D24: 2-benzoxazolyl-p-methoxy- [alpha] -styryl ketone, D28: 4,5-bis ( 2-furyl) thiazolyl phenyl ketone, D31: γ-naphth-2-thiazolyl phenyl ketone is particularly preferred.

  The neutral heterocyclic ketone compound represented by the general formula (I) can be easily synthesized by using known synthesis methods and related synthesis methods. Specific examples of the synthesis method include a method described in detail in JP-B-6-97339.

The neutral heterocyclic ketone compound can be further subjected to various chemical modifications for improving the properties of the photosensitive layer. For example, the neutral heterocyclic ketone compound and the addition polymerizable compound structure (for example, acryloyl group or methacryloyl group) are bonded by a method such as covalent bond, ionic bond, hydrogen bond, etc. Strengthening and unnecessary precipitation suppression of the dye from the film after exposure can be performed.
In addition, the bond between the neutral heterocyclic ketone compound and the hydrogen donor compound described below can significantly increase the photosensitivity particularly in a state where the concentration of the starting system is low. Furthermore, for the purpose of improving the suitability of processing to an (alkaline) aqueous developer, which is a preferred mode of use of the photosensitive layer, introduction of hydrophilic sites (polar groups such as carboxyl ester, sulfonate ester, ethylene oxide group). Is effective. In particular, ester-type hydrophilic groups have a relatively hydrophobic structure in the photosensitive layer, so that they have excellent compatibility, and in the developer, acid groups are generated by hydrolysis, resulting in increased hydrophilicity. Have
In addition, for example, a substituent can be appropriately introduced in order to improve compatibility in the photosensitive layer and to suppress crystal precipitation. For example, in certain types of photosensitive systems, unsaturated bonds such as aryl groups and allyl groups may be very effective in improving compatibility. By introducing an obstacle, crystal precipitation can be remarkably suppressed. In addition, by introducing an epoxy group, trialkoxysilyl group, or the like, adhesion to an inorganic substance such as a metal or metal oxide can be improved. In addition, depending on the purpose, a method such as polymerization of the heterocyclic ketone compound can be used.

The said neutral heterocyclic ketone compound may be used individually by 1 type, and may use 2 or more types together. By using two or more heterocyclic ketone compounds in combination, compatibility with the photosensitive layer can be increased.
In selecting the neutral heterocyclic ketone compound, the molar extinction coefficient at the emission wavelength of the light source used is an important factor in addition to the photosensitivity. By using a compound having a large molar extinction coefficient, the amount added can be made relatively small, which is economical and advantageous from the viewpoint of film properties of the photosensitive layer. The photosensitivity and resolution of the photosensitive layer and the physical properties of the exposed film are greatly affected by the absorbance at the light source wavelength. For example, the sensitivity decreases in a low region where the absorbance is 0.1 or less. Also, the resolution becomes low due to the influence of halation. However, for the purpose of curing a thick film having a thickness of 5 μm or more, for example, such a low absorbance may increase the degree of curing. Further, in a region where the absorbance is high such as 3 or more, most of the light is absorbed on the surface of the photosensitive layer, and the internal curing is further inhibited. For example, when used as a solder resist, the film strength and the substrate adhesion are poor. It may be insufficient.

  The content of the neutral heterocyclic ketone compound represented by the general formula (I) is not particularly limited, but when used in a relatively thick film thickness, for example, the absorbance of the photosensitive layer is 0.1. It is preferable to set it to be in the range of -1.5, preferably in the range of 0.25-1. As content in the photosensitive composition solid content, 0.1-20 mass% is preferable, 0.3-15 mass% is more preferable, 0.5-10 mass% is especially preferable.

-O-acyloxime compound-
The neutral O-acyloxime compounds of the present invention include those that do not contain basic groups such as amino groups, carboxylic acid groups, and sulfonic acid groups in the molecule, and those that exist. , Neutralized by binding to acidic groups or basic groups in the molecule, or by binding to other acidic molecules or basic molecules, for example, the following general formula (II-1) A compound represented by any one of (II-4) is preferred.
However, the general formula (II-1) in ~ (II-4), R 1 is a phenyl group, an alkyl group, a cycloalkyl group, a halogenated alkyl group, an alkanoyl group, a benzoyl group, an alkoxycarbonyl group, a phenoxycarbonyl group , CONR ¹⁴ R ¹⁵ , CN, NO ₂ , an aryl group, and a diphenylphosphinoyl group. R ² represents any one of an alkanoyl group, an alkenoyl group, a benzoyl group, an alkoxycarbonyl group, and a phenoxycarbonyl group. R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are each independently a hydrogen atom, halogen atom, alkyl group, cyclopentyl group, cyclohexyl group, phenyl group, benzyl group, benzoyl group, alkanoyl group, alkoxycarbonyl Represents any of a group, a phenoxycarbonyl group, OR ¹² , SR ¹³ , SOR ¹³ , and SO ₂ R ¹³ . R ⁸ represents any of an alkoxycarbonyl group, a phenoxycarbonyl group, a cycloalkyl group, CONR ¹⁴ R ¹⁵ , CN, a phenyl group, and an alkyl group. R ⁹ , R ¹⁰ , and R ¹¹ are each independently a hydrogen atom, halogen atom, alkyl group, cyclopentyl group, cyclohexyl group, phenyl group, benzyl group, benzoyl group, alkanoyl group, alkoxycarbonyl group, phenoxycarbonyl group, One of OR ¹² , SR ¹³ , SOR ¹³ , and SO ₂ R ¹³ is represented. R ¹² represents a hydrogen atom, an alkyl group, (CH ₂ CH ₂ O) nH, an alkanoyl group, an alkenyl group, an alkenoyl group having 3 to 6 carbon atoms, and a phenyl group, and n represents an integer of 1 to 20. R ¹³ represents either an alkyl group or a phenyl group. R ¹⁴ and R ¹⁵ each independently represent any of a hydrogen atom, an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkenyl group, a cycloalkyl group, a phenyl group, an alkanoyl group, an alkenoyl group, and a benzoyl group. M represents any one of an alkylene group, a cyclohexylene group, and a phenylene group.

Examples of the phenyl group in R ¹ include an unsubstituted phenyl group, and a group having one or more of a C 1-6 alkyl group, a phenyl group, a halogen atom, OR ¹² , and SR ¹³ as a substituent. Is mentioned.
The alkyl group for R ¹ is an alkyl group having 1 to 20 carbon atoms, interrupted by one or more oxygen atoms, and substituted by one or more hydroxyl groups. An alkyl group having 1 to 6 carbon atoms having 20 alkyl groups, S (O) _m (m represents an integer of 1 or 2, the same shall apply hereinafter), and an alkyl having 1 to 10 carbon atoms having SO ₂ O Groups.
Examples of the cycloalkyl group for R ¹ include cycloalkyl groups having 5 to 8 carbon atoms.
Examples of the haloalkyl group for R ¹ include haloalkyl groups having 1 to 4 carbon atoms.
Examples of the alkanoyl group for R ¹ include cycloalkyl groups having 2 to 20 carbon atoms.
Examples of the benzoyl group in R ¹ include an unsubstituted benzoyl group and a group having one or more of a C 1-6 alkyl group, a phenyl group, OR ¹² , and SR ¹³ as a substituent.
Examples of the alkoxycarbonyl group for R ¹ include an alkoxycarbonyl group having 2 to 12 carbon atoms which may be interrupted by one or more oxygen atoms and / or substituted by one or more hydroxyl groups.
Examples of the phenoxycarbonyl group in R ¹ include an unsubstituted phenoxycarbonyl group, an alkyl group having 1 to 6 carbon atoms, a phenyl group, a halogen atom, and a group having one or more of OR ¹² .
Examples of the aryl group in R ¹ include an unsubstituted aryl group, a C ₁ -C ₁₂ alkyl-substituted S (O) _m -C ₆ -C ₁₂ aryl group, and a SO ₂ O-C ₆ -C ₁₀ aryl group. Can be mentioned.

Examples of the alkanoyl group in R ² include alkanoyl groups having 2 to 12 carbon atoms which may have either a halogen atom or CN.
Examples of the alkenoyl group in R ² include alkenoyl groups having 4 to 6 carbon atoms in which a double bond is not conjugated with a carbonyl group.
Examples of the benzoyl group in R ² include an unsubstituted benzoyl group, an alkyl group having 1 to 6 carbon atoms, a halogen atom, CN, OR ¹² , and a group substituted with one or more of SR ¹³ .
Examples of the alkoxycarbonyl group for R ² include an alkoxycarbonyl group having 2 to 6 carbon atoms.
Examples of the phenoxycarbonyl group in R ² include a phenoxycarbonyl group which may have any of an alkyl group having 1 to 6 carbon atoms and a halogen atom.

Examples of the alkyl group in R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ include an alkyl group having 1 to 12 carbon atoms.
Examples of the phenyl group in R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ include groups having one or more of an unsubstituted phenyl group, OR ¹² , and SR ¹³ .
Examples of the alkanoyl group in R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ include alkanoyl groups having 2 to 12 carbon atoms.
The alkoxycarbonyl group in R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ is a carbon that may be interrupted by one or more oxygen atoms and substituted by one or more hydroxyl groups. Examples thereof include an alkoxycarbonyl group having 2 to 12 atoms.
At least one of R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ represents one of OR ¹² and SR ¹³ , and OR ¹² and SR ¹³ are further substituents on the phenyl ring or phenyl ring A 5-membered ring or a 6-membered ring may be formed through one of the carbon atoms of the group and the groups R ¹² and R ¹³ .

As the alkoxycarbonyl group for R ^8, an alkoxycarbonyl group having 2 to 12 carbon atoms which may be interrupted by one or more unsubstituted oxygen atoms and / or substituted by one or more hydroxyl groups may be used. Can be mentioned.
Examples of the phenoxycarbonyl group in R ⁸ include an unsubstituted phenoxycarbonyl group, an alkyl group having 1 to 6 carbon atoms, a phenyl group, a halogen atom, and a group having one or more of OR ¹² .
Examples of the cycloalkyl group for R ⁸ include cycloalkyl groups having 5 to 8 carbon atoms.
The phenyl group in R ⁸ is substituted by SR ¹³ and is a 5-membered or 6-membered ring via R ¹³ by constructing a bond to the carbon atom of the phenyl ring having R ⁹ , R ¹⁰ , and R ^11. A ring may be formed.
As the alkyl group for R ⁸ , when at least one of R ⁹ , R ¹⁰ , and R ¹¹ is SR ⁹ , a halogen atom, OH, OR ² , a phenyl group, a halogenated phenyl group, and an SR ^13- substituted phenyl And an alkyl group having 2 to 12 carbon atoms which may be substituted by one or more groups and may be interrupted by an oxygen atom or NH (CO).

Examples of the alkyl group for R ¹¹ include alkyl groups having 1 to 12 carbon atoms.
Examples of the phenyl group for R ¹¹ include a phenyl group that may have one of OR ¹² and SR ¹³ .
Examples of the alkanoyl group for R ¹¹ include alkanoyl groups having 2 to 12 carbon atoms.
Examples of the alkoxycarbonyl group in R ¹¹ include an alkoxycarbonyl group having 2 to 12 carbon atoms which may be interrupted by one or more oxygen atoms and / or substituted by one or more hydroxyl groups.
OR ¹² and SR ¹³ in R ¹¹ may form a 5-membered ring or a 6-membered ring with a further substituent of the phenyl ring or one of the carbon atoms of the phenyl ring and the groups R ¹² and R ^13. .
At least one of R ⁹ , R ¹⁰ , and R ¹¹ is either OR ¹² or SR ¹³ .
When R ¹⁰ is a methoxy group, R ⁹ and R ¹¹ are hydrogen atoms, and R ⁸ is CN, R ² is not benzoyl or 4- (C ₁ -C ₁₀ alkyl) benzoyl.

Examples of the substituent of the alkyl group in R ¹² include —OH, —SH, —CN, an alkoxy group having 1 to 4 carbon atoms, an alkeneoxy group having 3 to 6 carbon atoms, —OCH ₂ CH ₂ CN, _{-OCH 2 CH 2 (CO) O} (C 1 -C 4 _{alkyl), - O (CO) -C} 1 -C 4 alkyl, -O (CO) - phenyl, - (CO) OH, and - (CO) O _(C 1 -C ₄ alkyl) and the like.
In addition, the alkyl group in R ¹² may be interrupted by one or more oxygen atoms.
Examples of the alkanoyl group for R ¹² include alkanoyl groups having 2 to 8 carbon atoms.
Examples of the alkenyl group for R ¹² include alkenyl groups having 3 to 12 carbon atoms.
Examples of the alkenoyl group for R ¹² include alkenoyl groups having 3 to 6 carbon atoms.
As the phenyl group for R ¹² , an unsubstituted phenyl group, a halogen atom, an alkyl group having 1 to 12 carbon atoms, and a phenyl group substituted with any of alkoxy groups having 1 to 4 carbon atoms, phenyl- Examples thereof include C ₁ -C ₃ alkyl, Si (C ₁ -C ₈ alkyl) _r (phenyl) _3-r , and groups represented by the following formulae.

Examples of the alkyl group for R ¹³ include groups interrupted by one or more oxygen atoms or sulfur atoms.
Examples of the substituent of the phenyl group in R ¹³ include a halogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, phenyl-C ₁ -C ₃ alkyl, and the following formula: And the group represented.

Examples of the alkyl group in R ¹⁴ and R ¹⁵ include an alkyl group having 1 to 12 carbon atoms and an alkyl group having a phenyl group via 1 to 3 carbon atoms.
Examples of the hydroxyalkyl group in R ¹⁴ and R ¹⁵ include a hydroxyalkyl group having 2 to 4 carbon atoms.
Examples of the alkoxyalkyl group for R ¹⁴ and R ¹⁵ include an alkoxyalkyl group having 2 to 10 carbon atoms.
Examples of the alkenyl group for R ¹⁴ and R ¹⁵ include alkenyl groups having 3 to 5 carbon atoms.
Examples of the cycloalkyl group for R ¹⁴ and R ¹⁵ include cycloalkyl groups having 5 to 12 carbon atoms.
Examples of the alkanoyl group for R ¹⁴ and R ¹⁵ include alkanoyl groups having 2 to 3 carbon atoms.
Examples of the alkenoyl group for R ¹⁴ and R ¹⁵ include alkenoyl groups having 3 to 6 carbon atoms.
R ¹⁴ and R ¹⁵ may be bonded to each other to form an alkylene group which may have a substituent via an oxygen atom.
Examples of the phenyl group in R ¹⁴ and R ¹⁵ include a group substituted with any of an unsubstituted phenyl group, an alkyl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms, Further, R ¹⁴ is as long as hydrogen atom, a group represented by the following formula.

M ¹ , M ² , and M ³ are each independently an alkylene group having 1 to 12 carbon atoms, a cyclohexylene group, a phenylene group, — (CO) O— (C ₂ -C ₁₂ alkylene) —O (CO). -, - (CO) O- ( CH 2 CH 2 O) n - (CO) -, or _{- (CO) - (C 2} -C 12 - alkylene) - (CO) - represents a. M ¹ represents a direct bond or an alkyleneoxy group having 1 to 12 carbon atoms interrupted by at least one of 1 to 5 oxygen atoms and sulfur atoms, and M ² represents a direct bond. Or an alkylene-S- having 1 to 12 carbon atoms interrupted by at least one of 1 to 5 oxygen atoms and sulfur atoms. M ³ is a direct bond, but (i) when R ⁵ is a methoxy group and R ² is a benzoyl group or an acetyl group, R ¹ is not a phenyl group,
(Ii) if R ⁵ is a methoxy group and R ² is an ethoxycarbonyl group, then R ¹ is not a benzoyl group or an ethoxycarbonyl group,
(Iii) If R ⁵ is a methoxy group and R ¹ is a 4-methoxybenzoyl group, R ² is not an ethoxycarbonyl group,
(Iv) If R ⁵ is a methacryloylamino group and R ¹ is a methyl group, then R ² is not a benzoyl group,
(V) R ⁵ and R ⁴ , or R ⁵ and R ⁶ are OR ¹² groups, and these OR ¹² groups form a ring through R ³ , thereby forming —O—CH ₂ —O—. And if R ¹ is a methyl group, R ² is not an acetyl group,
(Vi) if R ⁴ , R ⁵ and R ⁶ are simultaneously a methoxy group and R ¹ is an ethoxycarbonyl group, then R ² is not an acetyl group,
(Vii) If R ⁵ is a methoxy group and at the same time R ⁴ or R ⁶ is an acetoxy group and R ¹ is an ethyl group, then R ² is not an acetyl group,
(Viii) In the general formula (II-3), when R ⁸ is a methyl group, R ¹⁰ is a phenylthio group, and R ⁹ and R ¹⁰ are hydrogen atoms, R ² is not 4-chlorobenzoyl. .

The compound represented by the general formulas (II-1) to (II-4) will be further described. The alkoxy substituent is directly bonded to the phenyl group or benzoyl group bonded to the oxime functional group. , An aryloxy substituent, an alkylthio substituent, or an arylthio substituent.
1-4 substituted phenyl groups are substituted, for example, 1, 2 or 3 is preferable, and 2 is particularly preferable. The phenyl ring substituent is preferably 4-position, 3,4-position, 3,4,5-position, 2,6-position, 2,4-position or 2,4,6-position of the phenyl ring, The 4-position or the 3,4-position is particularly preferred.

Examples of the alkyl group, the alkyl group having 1 to 20 carbon atoms, a linear or branched, for _{example, C 1 -C 18 -, C} 1 -C 14 -, C 1 -C 12 -, C 1 - _{C 8 -, C 1 -C 6} - or _C 1 -C _{4 alkyl,} C 4 _{-C 12 -,} and include _C 4 -C ₈ alkyl.
Specifically, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, 2, 4, Examples include 4-trimethylpentyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, pentadecyl group, hexadecyl group, octadecyl group, and icosyl group.

In addition, the alkyl group having 2 to 20 carbon atoms is interrupted by one or more oxygen atoms, for example, 1-9, 1-5, 1-3, 1, or 2 oxygen atoms, The oxygen atom is separated by at least two methylene groups, that is, ethylene groups, and includes groups that are linear or branched.
Specifically, —CH ₂ —CH ₂ —O—CH ₂ CH ₃ , — [CH ₂ CH ₂ O] _y —CH ₃ (where y = 1 to 9), — (CH ₂ —CH _{2 O) 7 -CH 2 CH 3} , -CH 2 CH (CH 3) -O-CH 2 CH 2 CH 3, and _{-CH 2 CH (CH 3) -O} -CH 2 CH 3 and the like.
In addition, as an alkyl group having 2 to 6 carbon atoms, a group interrupted by one or two oxygen atoms, for example, —CH ₂ —CH ₂ —O—CH ₂ —CH ₂ —O—CH ₂ CH ₃ , and _{-CH 2 -CH 2 -O-CH 2} CH 3 and the like.

Examples of the hydroxyalkyl group include a linear or branched alkyl group having 2 to 4 carbon atoms substituted with 1 or 2 oxygen atoms.
Specifically, for example, 2-hydroxyethyl group, 1-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxybutyl group, 4-hydroxybutyl group, 2 -Hydroxybutyl group, 3-hydroxybutyl group, 2,3-dihydroxypropyl group, and 2,4-dihydroxybutyl group are mentioned.

Examples of the cycloalkyl group include cyclopentyl, cyclohexyl, cyclooctyl, and cyclododecyl. Cyclopentyl and cyclohexyl are preferable, and cyclohexyl is more preferable.
The alkoxy group is linear or branched, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butyloxy group, a sec-butyloxy group, an isobutyloxy group, and a tert-butyloxy group. .

Examples of the alkoxyalkyl group having 2 to 10 carbon atoms include an alkyl group having 2 to 10 carbon atoms interrupted by an oxygen atom.
Specific examples include methoxymethyl group, methoxyethyl group, methoxypropyl group, ethoxymethyl group, ethoxyethyl group, ethoxypropyl group, propoxymethyl group, propoxyethyl group, and propoxypropyl.

Examples of the alkanoyl group is a straight-chain or branched, for _{example, C 2 -C 18 -, C} 2 -C 14 -, C 2 -C 12 -, C 2 -C 8 -, C 2 -C 6 -, C ₂ -C ₄ alkanoyl _C 4 _{-C 12} -, and _C 4 -C ₈ alkanoyl and the like.
Specifically, for example, acetyl group, propionyl group, butanoyl group, isobutanoyl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, decanoyl group, dodecanoyl group, tetradecanoyl group, pentadecanoyl group, A hexadecanoyl group, an octadecanoyl group, and an icosanoyl group are mentioned, Among these, an acetyl group is preferable.
The alkanoyloxy group having 2 to 4 carbon atoms is linear or branched and includes, for example, acetyloxy group, propionyloxy group, butanoyloxy group, and isobutanoyloxy group, and among these, acetyloxy Groups are preferred.

The alkoxycarbonyl group having 2 to 12 carbon atoms is linear or branched, interrupted by one or more oxygen atoms, and the two oxygen atoms are at least two methyl groups, that is, ethylene groups. Examples include groups that have been separated.
Examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, n-butyloxyocarbonyl group, isobutyloxycarbonyl group, 1,1-dimethylpropoxycarbonyl group, pentyloxycarbonyl group, and hexyloxy. Examples include carbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, and deosyloxycarbonyl, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, n-butyloxycarbonyl group And isobutyloxycarbonyl are preferable, and a methoxycarbonyl group is more preferable.

The phenoxycarbonyl group is a group represented by the following formula.
The substituted phenoxycarbonyl group is substituted by 1 to 4, for example, preferably 1, 2 or 3, and particularly preferably 2 or 3. The substituent on the phenphenyl ring is preferably 4-position, 3,4-position, 3,4,5-position, 2,6-position, 2,4-position or 2,4,6-position of the phenyl ring, The 4-position or the 3,4-position is particularly preferred.

Examples of the phenyl-C ₁ -C ₃ alkyl include a benzyl group, a phenylethyl group, an α-methylbenzyl group, and an α, α-dimethylbenzyl group, and a benzyl group is particularly preferable.
The alkenyl group having 3 to 12 carbon atoms may be mono- or poly-substituted, for example, allyl group, methallyl group, 1,1-dimethylallyl group, 1-butenyl group, 3-butenyl group, A 2-butenyl group, a 1,3-pentadienyl group, a 5-hexenyl group, a 7-octenyl group, a 7-octenyl group, or a dodecyl group is exemplified, and an allyl group is particularly preferable.
The alkeneoxy group having 3 to 6 carbon atoms may be mono- or poly-substituted, for example, allyloxy group, methallyloxy group, butenyloxy group, penteneoxy group, 1,3-pentadienyloxy group, and 5- A hexenyloxy group is mentioned.
The alkenoyl group having 3 to 6 carbon atoms may be mono- or poly-substituted, for example, propenoyl group, 2-methyl-propenoyl group, butenoyl group, pentenoyl group, 1,3-pentadienoyl group, 5- A hexenoyl group is mentioned.
A methylsulfanyl group is —SCH ₃ . Examples of the halogen atom include fluoro, chloro, bromo and iodo. Fluoro, chloro and bromo are preferred, and fluoro and chloro are more preferred.
Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group, and among these, a phenyl group is preferable.

The substituents OR ¹² and SR ¹³ on the phenyl ring are substituted with another substituent of the phenyl ring or one of the carbon atoms of the phenyl ring and either a 5-membered ring or a 6-membered ring via any of R ¹² and R ¹³ Can be obtained, for example, a structure containing two or four rings (including phenyl ring) represented by the following formula:

R ⁸ is a phenyl group substituted by SR ¹³ and the 5-membered or 6-membered ring builds a bond to the carbon atom of the phenyl ring having R ⁹ , R ¹⁰ , and R ¹¹ to form R ¹³ The structure of the following formula can be formed.

The compound of the general formula (II-3) in which R ¹³ is a phenyl group and R ² is a halogen-substituted benzoyl group is preferably excluded from the above definition.
Suitable compounds include, for example,
i) whether R ¹ is substituted or a phenyl group substituted by C ₁ -C ₆ alkyl, phenyl, halogen, OR ¹² , or SR ¹³ ;
ii) R ¹ is an alkyl group having 1 to 20 carbon atoms optionally interrupted by one or more oxygen atoms and substituted by one or more hydroxy groups;
iii) R ¹ is a haloalkyl group having 1 to 4 carbon atoms, and R ⁸ is substituted by one or more of an alkyl group having 1 to 6 carbon atoms, a halogen atom, a phenyl group, OR ¹² , or SR ¹³ A good phenoxycarbonyl group,
iv) whether R ⁸ is -CONR ¹⁴ R ¹⁵ ;
v) If at least one of R ⁵ , R ¹⁰ and R ¹¹ is —SR ¹³ , then R ⁸ is further substituted with a halogen atom, OH group, OR ¹² group, phenyl group, halogenated phenyl group, or SR ¹³ Or an alkyl group having 1 to 12 carbon atoms which may be substituted by one or more of phenyl groups or interrupted by oxygen atom or -NH (CO)-, and R ² is substituted by a halogen atom. Or an alkanoyl group having 2 to 12 carbon atoms,
vi) R ² is an alkenoyl group having 4 to 6 carbon atoms, and the double bond is not conjugated with a carbonyl group,
vii) R ² is an alkyl group having 1 to 6 carbon atoms or a benzoyl group optionally substituted by a halogen atom,
R ⁵ and R ⁷ are hydrogen, and R ⁴ , R ⁶ , R ¹⁰ , and R ¹¹ are independently of each other a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, OR ¹² , or SR ^13. in and, ^{R 5} and ^{R 6} are ^{oR 12} or ^{SR 13,} any of the compounds of formula (II-1) and (II-3) can be mentioned.
Particularly preferred are those of the general formulas (II-1) and (II-3) in which R ³ , R ⁴ , R ⁵ , R ⁶ or R ⁷ or R ⁹ , R ¹⁰ or R ¹¹ is SR ¹³ A compound.
Other suitable compounds include compounds of general formula (II-1), wherein R ³ and R ⁴ are hydrogen atoms and R ⁴ and R ⁵ are OR ¹² .
In particularly preferred compounds of the general formulas (II-1) and (II-3), R ³ , R ⁴ , and R ³ , or R ⁵ and R ⁶ are hydrogen atoms, and R ¹ and R ⁶ are , SR ¹³ . Particularly preferably, R ¹³ is a phenyl group, that is, R ⁵ or R ¹⁰ is a compound of the following formula:
Also suitable are compounds of formula (II-3), wherein R ⁸ is an alkyl group having 1 to 12 carbon atoms (which is unsubstituted or substituted by halogen or phenyl), Particularly preferred is a compound wherein R ¹¹ is SR ¹³ and the following formula.

Furthermore, as other suitable compounds, R ¹ is a phenyl group or a C ₁ -C ₁₂ -alkyl group, and R ⁸ is a C ₂ -C ₄ alkoxycarbonyl group or a phenyl group (which is represented by SR ¹³ 5- or 6-membered ring, optionally substituted, via R ¹³ by building a bond to the carbon atom of the phenyl ring having R ⁹ , R ¹⁰ , and R ¹¹ via R ¹³ Or at least one of R ⁹ , R ¹⁰ , and R ¹¹ is —SR ¹³ , R ⁸ is further an alkyl group having 1 to 12 carbon atoms (which is R ² is an alkanoyl group having 2 to 4 carbon atoms, or a benzoyl group (which is unsubstituted or carbon), which is unsubstituted or substituted by one or more of fluoro Alkyl group having 1 to 4 atoms R ³ , R ⁵ , and R ⁷ are hydrogen, and R ⁴ and R ⁵ are independently of each other a hydrogen atom, OR ¹² , or SR ¹³ . R ⁹ and R ¹⁰ are each independently a hydrogen atom, OR ¹² , or SR ¹³ ; R ¹¹ is a hydrogen atom; and R ¹² and R ¹³ are alkyl having 1 to 4 carbon atoms. A group, a phenyl group, or a group of any of the following formulas, wherein R ¹⁴ and R ¹⁵ are a methyl group or an ethyl group, or are bonded to each other to form an alkylene group having 2 to 6 carbon atoms (this is represented by — M is C ₁ -C ₁₂ alkylene; and M ² is a direct bond, general formula (II-1), general formula (II-2), The compound of a formula (II-3) or general formula (II-4) is mentioned. Particularly effective compounds include compounds of formula (II-3), wherein R ⁹ and R ¹¹ are hydrogen and R ¹⁰ is SR ¹³ .

R ¹ is preferably phenyl (which is unsubstituted or substituted by one or more alkyl groups of 1 to 6 carbon atoms, phenyl groups, halogen atoms, OR ¹² , or SR ¹³ ) Or an alkyl group having 1 to 20 carbon atoms (which is unsubstituted or substituted by one or more alkyl groups having 1 to 6 carbon atoms, phenyl group, OR ¹² , or SR ¹³ Is).
Particularly preferred is a group in which at least one of R ^{3 to} R ⁷ is SR ¹³ or OR ¹² and particularly at least one of R ^{3 to} R ⁷ is SR ¹³ . R ⁵ is preferably SR ¹³ or OR ¹² , and SR ¹³ is particularly preferable.
Among the compounds represented by the general formulas (II-1) to (II-4), the compounds of the formulas (II-1) and (II-3) are preferable. A compound in which R ³ and R ⁷ are hydrogen atoms is more preferable.
R ¹ is preferably an alkyl group having 1 to 12 carbon atoms. R ² is preferably a benzoyl group, a methylbenzoyl group, a dimethylbenzoyl group, or acetyl. R ⁷ is preferably a hydrogen atom. R ¹⁰ is preferably an alkyl group having 1 to 12 carbon atoms or a 4- (C ₁ -C ₄ alkylthio) phenyl group. R ¹⁰ is preferably an alkylthio group having 1 to 4 carbon atoms or a phenylthio group.

Specific preferred compounds represented by any one of the general formulas (II-1) to (II-4) include, for example, the following OE1 to OE39.
OE1: 1- (4-phenylsulfanylphenyl) -butane-1,2-dione-2-oxime-O-benzoate OE2: 1- (4-methylsulfanylphenyl) -butane-1,2-dione-2- Oxime-O-benzoate OE3: 1- (3,4-dimethoxyphenyl) -butane-1,2-dione-2-oxime-O-acetate OE4: 1- (3,4-dimethoxyphenyl) -butane-1 , 2-Dione-2-oxime-O-benzoate OE5: 1- (4-methylsulfanylphenyl) -3-phenylethane-1,2-dione 2-oxime-O-acetate OE6: 1- (4-methoxy Phenyl) -butane-1,2-dione-2-oxime-O-acetate OE7: 1- (4-methoxyphenyl) -butane-1,2-dione-2- Oxime-O-benzoate OE8: 1- (4-phenylsulfanylphenyl) -butane-1,2-dione-2-oxime-O-acetate OE9: 1- (4-methylsulfanylphenyl) -butane-1,2 -Dione-2-oxime-O-2,4,6-trimethylbenzoate OE10: 1- (4-methylsulfanylphenyl) -propane-1,2-dione-2-oxime-O-benzoate OE11: 1- (4-Methylsulfanylphenyl) -octane-1,2-dione-2-oxime-O-acetate OE12: 1- (4-methylsulfanylphenyl) -octane-1,2-dione-2-oxime-O-benzo Art OE13: 1- (4-phenylsulfanylphenyl) -octane-1,2-dione-2-oxime-O-be Zoate OE14: 1- (4-methylsulfanylphenyl) -4,6,6-trimethylhexane-1,2-dione-2-oxime-O-benzoate OE15: 1- (4-methylsulfanylphenyl) -4, 6,6-Trimethylhexane-1,2-dione 2-oxime-O-acetate OE16: 1- (4-methylsulfanylphenyl) -octane-1,2-dione-2-oxime-Op-methylbenzoate OE17: 1- (4-Methylsulfanylphenyl) -octane-1,2-dione-2-oxime-Op-chlorobenzoate OE18: 1- (4-methylsulfanylphenyl) -octane-1,2-dione -2-oxime-Om-methylbenzoate OE19: 1- (4-methylsulfanylphenyl) -butane 1-one oxime-O-acetate OE20: 1- (4-phenylsulfanylphenyl) -butan-1-one oxime-O-acetate OE21: hydroxyimino- (4-methylsulfanylphenyl) -acetic acid ethyl ester-O-acetate OE22: Hydroxyimino- (4-methylsulfanylphenyl) -acetic acid ethyl ester-O-benzoate OE23: Hydroxyimino- (3,4-dimethoxyphenyl) -acetic acid ethyl ester-O-acetate OE24: Ethyl 2- (3,4- Dimethoxyphenyl) -2-benzoyloxyimino-benzoate OE25: 1- (4-methylsulfanylphenyl) -butan-1-one oxime-O-benzoate OE26: 1- (4-phenylsulfanylphenyl) -octane-1 Onoxime-O-acetate OE27: 1- (4-phenylsulfanylphenyl) -octane-1-oneoxime-O-benzoate OE28: 2,2,2-trifluoro-1- (4-methylsulfanylphenyl) -ethanone Oxime-O-acetate OE29: 1- (4-phenylsulfanylphenyl) -ethanone oxime-O-acetate OE30: 1- (4-phenylsulfanylphenyl) -decan-1-one oxime-O-pentafluorobenzoate OE31: 1- (4-methylsulfanylphenyl) -propan-1-one oxime-O-acetate OE32: 1- (4-methylsulfanylphenyl) -ethanone oxime-O-acetate OE33: 1,9-bis- (4-methyl) Sulfanylphenyl) -nonane- 1,2,8,9-tetraone-2,8-dioximedi (O-acetate)
OE34: 1,9-bis- (4-methylsulfanylphenyl) -nonane-1,9-butanedioxime di (O-acetate)
OE35: 1- {4- [4- (2-acetoxyiminobutyryl) -phenylsulfanyl] -phenyl} -butane-1.2-dione-2-oxime-O-acetate OE36: 1- {4- [4 -(2-Benzoxyiminobutyryl) -phenylsulfanyl] -phenyl} -butane-1.2-dione-2-oxime-O-benzoate OE37: 1- {4- [4- (2-acetoxyiminobutyl) -Phenylsulfanyl] -phenyl} -butan-1-one oxime-O-acetate OE38: 2,4-diethylthioxanthen-9-one oxime-O-benzoate OE39: (2-acetyloxyiminomethyl) -thioxanthene-9 -ON Among OE1 to OE39, OE39: (2-acetyloxyiminomethyl) -thioxan Ten-9-one is particularly preferred.

  Although there is no restriction | limiting in particular in content in the photosensitive composition solid content of the said O-acyl oxime compound, For example, 0.1-20 mass% is preferable, 0.3-15 mass% is more preferable, and 0.1. 5-10 mass% is especially preferable.

  The content ratio between the neutral heterocyclic ketone compound and the neutral O-acyloxime compound is preferably, for example, 1: 6 to 6: 1, and more preferably 1: 3 to 3: 1.

<Hydrogen donor compound>
The photopolymerization initiating compound preferably contains a hydrogen donor compound in addition to the compound represented by the general formula and the O-acyloxime compound. In some cases, the sensitivity can be further increased by adding the hydrogen donor compound.
The hydrogen donor compound is excited by active energy rays and can donate hydrogen (electrons) by interacting with the compound represented by the general formula (I) and the O-acyloxime compound. There are no particular limitations as long as these are neutral compounds, and can be appropriately selected according to the purpose, for example, mercapto compounds, amino acids, phosphorus compounds, active hydrogen-containing hydrocarbon compounds, Borate compounds, and the like.
Examples of the mercapto compound include mercapto compounds represented by the following general formulas (III-1a) and (III-1b), thioether compounds represented by the following general formula (III-2), and the following general formula (III- 3), a compound represented by the following general formula (III-4), and the like.
In the general formulas (III-1a) and formula (III-1b), wherein R ³¹ represents any of an alkyl group and an aryl group, R ³² represents a hydrogen atom or an alkyl group.
The alkyl group for R ³¹ and R ³² is preferably an alkyl group having 1 to 4 carbon atoms. The aryl group of R ³¹ is preferably a phenyl group, a naphthyl group and the like having 6 to 10 carbon atoms, and the substituted aryl group includes the above aryl group, a halogen atom such as a chlorine atom, and a methyl group. And those substituted with an alkoxy group such as a methoxy group or an ethoxy group. R ³¹ and R ³² may be an atomic group necessary for bonding to complete a heterocyclic ring which may have a condensed ring together with a carbon atom or a nitrogen atom. Examples of the condensed ring include a benzene ring.
However, the general formula ^{(III-2), R 33} is an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group and an alkenyl ^{group,, R 34} and ^{R 35} are the same meaning as ^{R 33,} Or represents a group having a positive Hammett σ _p value.
In the general formula ^{(III-3), R 36} represents an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkenyl group, and either ^Y 1 -CS-S- of. Y ¹ represents —OR ³⁹ or —NR ⁴⁰ R ⁴¹ . R ³⁹ , R ⁴⁰ , and R ⁴¹ are each independently a hydrogen atom, alkyl group, hydroxyalkyl group, alkoxyalkyl group, alkenyl group, cycloalkyl group, phenyl group, alkanoyl group, alkenoyl group, or benzoyl group. R ³⁰ and R ³¹ may combine to form a ring.
In the above (III-4), Z represents R ⁴² —SO ₂ —, R ⁴² —O—SO ₂ —, R ⁴² represents the same meaning as R ³⁹ , R ⁴⁰ , and R ⁴¹ , R ³⁷ and R ³⁸ represents the same meaning as R ³³ , R ³⁹ , and Z, or represents a hydrogen atom, a group having a positive Hammett σ _p value, —OR ³³ , or —SR ³³ .

  Examples of the compound represented by the general formula (III-1a) or (III-1b) include thioformamide, thioacetamide, N-methylthioformamide, N-methylthioacetamide, N-phenylthiopropionic acid amide, N- Phenylthiocaproic acid amide, No-chloro-phenylthioacetamide, No-chlorophenylthiocaproic acid amide, Np-tolylthiocaproic acid amide, Nm-methoxyphenylthioacetamide, Nm-methyl Toxiphenylthiopropionic acid amide, Np-ethoxyphenylthioacetamide, Np-ethoxyphenylthiopropionic acid amide, No-methoxyphenylthiocaproic acid amide, 2-mercapto-4,5-dihydro-2- Thiazole, 2-mercapto-4-methyl-4, -Dihydro-2-thiazole, 2-mercapto-5-methyl-4,5-dihydro-2-thiazole, 2-mercapto-4,4-dimethyl-4,5-dihydro-2-thiazole, 2-mercapto-5 , 5-dimethyl-4,5-dihydro-2-thiazole, 2-mercapto-4,5-dihydro-2-oxazole, 2-mercapto-4-methyl-4,5-dihydro-2-oxazole, 2-mercapto -4,4-dimethyl-4,5-dihydro-2-oxazole, 1-methyl-2-mercapto-1,3-imidazole, 2-mercapto-4,5-dihydro-1,3-thiazine, 2-mercapto -6-methyl-4,5-dihydro-1,3-thiazine, 2-mercapto-4,5-dihydro-1,3-oxazine, 2-mercapto-tetrahydro-1 Pyridine, 1- [p- (n-hexylaminocarbonyl) phenyl} -2-mercaptoimidazole, 1- (p-tolyl) -2-mercapto-4,5,6,7-tetrahydro-1,3-benzimidazole 2-mercapto-5-methylthio-1,3,4-oxadiazole, 2-mercapto-3,4,5,6-tetrahydro-1-azepine, 2-mercapto-1,3-benzoxazole, 3- Mercapto-5-chloro-1,2-benzisoxazole, 2-mercapto-1,3-benzimidazole, 2-mercapto-6-methoxy-1,3-benzimidazole, 1-methyl-2-mercapto-1, 3-benzimidazole, 2-mercapto-6-methyl-1,3-benzimidazole, 2-mercapto-5,6-dimethyl-1,3 -Benzimidazole, 2-mercapto-6-methoxy-1,3-benzimidazole, 2-mercapto-5-caproylamino-1,3-benzimidazole, 1- (n-propyl) -2-mercapto-1, 3-benzimidazole, 1-isopropyl-2-mercapto-1,3-benzimidazole, 2-mercapto-6-chloro-1,3-benzimidazole, 1- (n-heptyl) -2-mercapto-1,3 -Benzimidazole, 1- (n-hexyl) -2-mercapto-5-chloro-1,3-benzimidazole, 2-mercapto-6-chloro-1,3-benzimidazole, 1- (n-octyl)- 2-mercapto-5-methoxy-1,3-benzimidazole, 1- (n-hexyl) -2-mercapto-5-ethoxycarbo 1,3-benzimidazole, 1- (2-methoxyethyl) -2-mercapto-1,3-benzimidazole, 3-mercapto-6-methyl-1,2-benzothiazole, 1-phenyl-2- Mercapto-1,3-benzimidazole, 1-phenyl-2-mercapto-5-methylsulfonyl-1,3-benzimidazole, 1- (p-sulfonatomethylphenyl) -2-mercapto-1,3-benzimidazole Sodium salt, 3-mercapto-1,2-benzothiazole, 3-mercapto-6-caproylamino-1,2-benzothiazole, 3-mercapto-6-chloro-1,2-benzothiazole, 3-mercapto -6-methyl-1,2-benzothiazole, 2-mercapto-naphtho [2,1] -1,3-imidazole, (N-butyl) -2-mercapto-naphtho [2,1] -1,3-imidazole, 1- (n-octyl) -2-mercapto-imidazo [4,5-b] pyridine, 1- (n- Octyl) -2-mercapto-imidazo [4,5-b] pyrazine, 1- (n-butyl) -2-mercapto-1,3-imidazo [4,5-b] quinoxaline, 1- (n-hexyl) 2-mercapto-6-chloro-1,3-imidazo [4,5-b] quinoxaline, 1,5-diethyl-3-mercapto-1,2,4-triazole, 4- (n-hexyl) -3 -Mercapto-1,2,4-triazole, 4-phenyl-3-mercapto-1,2,4-triazole, 4-phenyl-3-mercapto-5-methylthio-1,2,4-triazole, 1- ( n-hexyl) -5-me Lucaptotetrazole, 1- (n-octyl) -5-mercaptotetrazole, 1-phenyl-5-mercaptotetrazole, 2- (n-hexyl) -3-mercapto-1,2,4-oxadiazine, 2-phenyl- Examples include 3-mercapto-5-methyl-1,2,4-thiadiazine, 3-phenyl-4-mercapto-6-phenyl-1,2,3,6-tetrahydro-1,3,5-thiadiazine. Among these, 1-phenyl-2-mercapto-1,3-benzimidazole is preferable.

  Examples of the thioether compound represented by the general formula (III-2) include di-n-butyl sulfide, di-n-octyl sulfide, triphenylthiomethane, diphenylthiomethane, phenylmethyl sulfide, and p-methylthiobenzoate. Acid, p-methylthiobenzaldehyde, p-methylthiobenzonitrile, 1-phenylthioethylmethyl ketone, 1-phenylthiopropionitrile, 1-chloromethylphenyl sulfide, 1,3,5-trithiane, 2-methyl-4- Examples include methoxyphenyl methyl sulfide, thiochroman, 4-oxothiochroman and the like.

  Examples of the compound represented by the general formula (III-3) include dithiocarbonate O-isobutyl S-n-butyl, dithiocarbonate O-isobutyl S-benzyl, diethyl dithiocarbamate n-butyl, diethyl dithiocarbamate benzyl, N, N, N ′, N′-tetraethylthiuram disulfide, N, N-diethyl-N ′, N′-di-n-butylthiuram disulfide, 1,2,3-tri (diethyldithiocarbamoylthio) propane, etc. Is mentioned.

  Examples of the compound represented by the general formula (III-4) include di-n-butylsulfone, ethyl p-tolylsulfone, p-tolylmethylthiomethylsulfone, acetylmethyl p-tolylsulfone, and bis (p-toluene). Sulfonyl) methane, cyanomethyl-p-tolylsulfone, n-butyl p-toluenesulfonate, ethyl methanesulfonate, phenyl acetylmethanesulfonate, diphenylmethanedisulfonate, phenylsulfolane 3-sulfolene cyanomethanesulfonate, and the like. .

Examples of the amino acid include N-phenylamino acid derivatives represented by the following general formula (IV).
In the general formula (IV), X ³ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, a nitro group, an amino group, a halogen It represents any of an atom, an acyl group, and a carboxyl group, and n is an integer of 1 to 5. R ⁴³ represents any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group, and an aralkyl group, and R ⁴⁴ represents a hydrogen atom, hydroxy group, Represents any one of a group, a methylthio group, an alkyl group having 1 to 4 carbon atoms which may be substituted with a —COOR ⁴⁵ group, and a benzyl group, and R ⁴³ and R ⁴⁴ together with a nitrogen atom and an adjacent carbon atom A 6-membered ring may be formed. R ⁴⁵ represents any of an alkyl group having 1 to 4 carbon atoms and a benzyl group.

  The N-phenylamino acid derivative represented by the general formula (IV) is not particularly limited. For example, N-phenylglycine, N- (p-acetylphenyl) glycine, N- (m-trifluoromethylphenyl) ) Glycine, N- (m-acetylphenyl) glycine, N- (p-trifluoromethylphenyl) glycine, N-phenylalanine, N-phenylserine, N-phenylthreonine, N-phenylcysteine, N-phenylproline, N -Phenylglutamic acid and the like. The glycine derivative may be a bipolar ion compound containing an amino cation and a carboxylic acid anion in the structure. Among these, N-phenylglycine is particularly preferable.

Examples of the phosphorus compound include a phosphonic acid diester represented by the following general formula (V-1) and a phosphorous acid triester represented by the following general formula (V-2).
However, if in the general formula ^{(V-1), R 46} represents an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a alkenyl ^{group, R 47} represents the same meaning as ^{R 46} , Represents a group having a positive Hammett σ _p value.
In the general formula (V-2), R ⁴⁸ represents any of an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, and an alkenyl group, and R ⁴⁹ and R ⁵⁰ have the same meaning as R ^48. Or a group having a positive Hammett σ _p value.

  Examples of the phosphonic acid diester represented by the general formula (V-1) include dimethyl phosphonate, diethyl phosphonate, di (n-butyl) phosphonate, di (2-ethylhexyl) phosphonate, and ethyl methyl phosphonate. Phosphonate diphenyl, phosphonate ethylphenyl, phosphonate di (p-dimethylaminophenyl), phosphonate di (p-cyanophenyl), phosphonate di (p-acetylphenyl), phosphonate di (p-methoxyphenyl) Phosphonate di (p-tolyl), phosphonate di (o-methoxyphenyl), phosphonate di (o-chlorophenyl), phosphonate di (m-bromophenyl), phosphonate (o-chlorophenyl) (p-methoxy) Phenyl), methylphenyl phosphonate, β-naphthylphenyl phosphonate, phosphonate ester Ren, propylene phosphonic acid di, trimethylene phosphonic acid, phosphonic acid oxydiethylene, and the like.

  Examples of the phosphorous acid triester represented by the general formula (V-2) include diethyl phosphite, di-n-butyl phosphite, di (2-ethylhexyl) phosphite, ethyl methyl phosphite, Triethyl phosphite, triphenyl phosphite, diphenyl phosphite, tri (p-dimethylaminophenyl) phosphite, tri (p-cyanophenyl) phosphite, di (p-cyanophenyl) phosphite, Tri (p-methoxyphenyl) phosphite, di (p-methoxyphenyl) phosphite, tri (o-chlorophenyl) phosphite, di (o-chlorophenyl) phosphite, tri (m-bromophosphite) Phenyl), phenyldimethyl phosphite, diphenylmethyl phosphite, phenylmethyl phosphite, dimethyl phosphite (α-naphthyl), ethylene methyl phosphite, ethylene phosphite Cycloalkenyl, phosphite orthoformate ethylene phosphite, tri ethylene, and the like.

Examples of the active hydrogen-containing hydrocarbon compound include cyclic β-dicarbonyl compounds represented by the following general formula (VI).
In the general formula (VI), R ⁵¹ is a substituted or unsubstituted alkyl group, and represents one of the aralkyl group, G is a divalent organic group, a hetero atom in the chain group It may contain and may have a substituent in at least any one of carbon and a hetero atom.

  Examples of the cyclic β-dicarbonyl compound represented by the general formula (VI) include 2,4-diethyl-1,3-cyclobutanedione, 2-methyl-1,3-cycloheptanedione, 5-methyl- 2-thiobarbituric acid, 3-ethyltetronic acid, 2,4-dimethyl-3-oxo-5-hydroxy-5-methoxypentenoic acid δ-lactone, 1,3,5-trimethylbarbituric acid, 1,3-dimethyl -5-ethylbarbituric acid, 2-methyl-1,3-cyclopentanedione, 5-methylbarbituric acid, 1,5-dimethylbarbituric acid, 2-methyldimedone, 2-methyl-1,3-indandione 1,3-dimethyl-5-benzylbarbituric acid, bis- [5- (1,3-dimethylbarbituryl))-methane, 1,5-diphenyl-3- [2- (phenyl Thio) ethyl] -2,4-pyrrolidinedione, 1-phenyl-3,5-diketo-4-n-butyl-tetrahydropyrazole, and the like.

Examples of the borate compound include an organic boron compound represented by the following general formula (VII).
In the general formula ^{(VII), R 52} represents an aliphatic group. R ⁵³ , R ⁵⁴ , and R ⁵⁵ each independently represent any of an aliphatic group, an aromatic group, a heterocyclic group, and —SiR ⁴⁶ R ⁴⁷ R ⁴⁸ . R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represent either an aliphatic group or an aromatic group. Y ⁺ represents a group that forms a cation.

  Examples of the organic boron compound represented by the general formula (VII) include tetra (n-butyl) ammonium-n-butyltriphenylborate, tetraethylammonium-diphenylmethylsilyltriphenylborate, and tetramethylammonium-diphenyl. Methylsilyltriphenylborate, tetra (n-hexyl) ammonium-n-hexyltriphenylborate, tetra (n-butyl) ammonium-n-butyldi (p-fluorophenyl) phenylborate, tetra (n-butyl) Ammonium-n-butyltri (p-fluorophenyl) borate, tetra (n-butyl) ammonium-n-hexyltri (p-chlorophenyl) borate, tetra (n-butyl) ammonium-n-hexyldi (p-chlorophenyl) phenyl , Tetra (n-butyl) ammonium-di (n-hexyl) di (m-fluorophenyl) borate, tetra (n-butyl) ammonium-n-hexyltri (2-methyl-5-fluorophenyl) borate, tetra ( n-butyl) ammonium-methyldimesitylphenylborate and the like.

  Among these hydrogen donors, 1-phenyl-2-mercapto-1,3-benzimidazole, N-phenylglycine, 4,4′-bis (diethylamino) benzophenone, leucocrystal violet, 2-dimethylamino-2- More preferred are methyl-1- (4-methoxyphenyl) propan-1-one-O-allyloxime and tetra (n-butyl) ammonium-n-butyltriphenylborate, 1-phenyl-2-mercapto-1 , 3-benzimidazole and tetra (n-butyl) ammonium-n-butyltriphenylborate are particularly preferred.

  The blending amount of the hydrogen donor compound in the photopolymerization initiation compound is preferably 0.01 to 15.0% by mass, more preferably 0.05 to 10.0% by mass, and 0.1 to 5.0% by mass. % Is particularly preferred.

<Binder>
The binder in the photosensitive composition is preferably, for example, swellable in an alkaline aqueous solution, and more preferably soluble in an alkaline aqueous solution. Moreover, it is preferable to have crosslinkability.
The alkali-soluble refers to the property that the photosensitive composition containing it is dissolved by an alkaline developer, and specifically, it should be soluble to the extent that the intended development processing is performed. The alkaline developer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alkali metal hydroxides such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, hydroxyethylamine, triethylamine Or an aqueous solution of a quaternary ammonium hydroxide such as tetramethylammonium hydroxide or a mixture thereof with a miscible organic solvent. pH is 8-14 and 0.01-10 mass% aqueous solution of these alkali agents is preferable. Among these alkaline developers, in the printed wiring board industry, 0.2 to 2 mass% sodium carbonate aqueous solution is generally used, and 1 mass% sodium carbonate aqueous solution is the most common.
An example of the development method is as follows. The surface of the copper-clad laminate is prepared by pressure-bonding the photosensitive layer with a laminator while removing the protective film of the photosensitive film on the surface of the dried copper-clad laminate. A laminate comprising a photosensitive layer and a support film is prepared. The pressure bonding conditions are a laminate temperature of 70 ° C., a pressure roll temperature of 105 ° C., a pressure roll pressure of 3 kg / cm ^2, and a pressure bonding speed of 1.2 m / min.
The support film is peeled off from the laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. is sprayed at a pressure of 0.1 MPa over the entire surface of the photosensitive layer on the copper-clad laminate. If the photosensitive layer on the copper clad laminate is removed after spraying for at least 60 seconds, it will be developed.
Such an alkali-soluble resin can be suitably selected from those showing a solubility of 1% by mass or more in a 1% by mass sodium carbonate aqueous solution at 30 ° C., for example.
The crosslinkability refers to the property of changing a linear polymer molecule into a network having a three-dimensional network structure by a photochemical reaction. Specifically, the action of free radicals generated by the photolysis of a photopolymerization initiator. Means a polymer that can be reticulated by polymerization reaction.

The binder (hereinafter also referred to as alkali-soluble crosslinkable resin) is a resin soluble in a 1% aqueous sodium carbonate solution (pH = 10) containing an alkali-soluble group and a crosslinkable group involved in photopolymerization in the molecule. is there.
There is no restriction | limiting in particular as said alkali-soluble crosslinkable resin, According to the objective, it can select suitably, For example, a vinyl polymer type alkali-soluble crosslinkable resin, an epoxy resin ester type alkali-soluble crosslinkable resin etc. are mentioned.

-Vinyl polymer type alkali-soluble crosslinkable resin-
The vinyl polymer type alkali-soluble crosslinkable resin is classified into the following types (A-1), (A-2) and (A-3), and is selected from at least one of the types.
Type (A-1): produced by reaction of (a) a carboxyl group-containing copolymer resin and (b) an epoxy group-containing unsaturated compound.
Type (A-2): (c) An epoxy group-containing copolymer resin and (d) a carboxyl group-containing unsaturated compound are subjected to an addition reaction, and (e) a polybasic acid anhydride is converted into a hydroxyl group of the resulting product. Produced by addition reaction.
Type (A-3): produced by addition reaction of (f) a copolymer resin containing an acid anhydride group and (g) a compound having one hydroxyl group and at least one (meth) acryloyl group in the molecule. The

-Type (A-1)-
The (a) carboxyl group-containing copolymer resin used for the production of the vinyl polymer type alkali-soluble crosslinkable resin of the type (A-1) is one unsaturated group and at least one carboxyl group in one molecule. Alternatively, it is obtained by copolymerizing a compound having an acid anhydride group with at least one of (meth) acrylic acid ester and styrenes.

  The compound (a) having one unsaturated group and at least one carboxyl group or acid anhydride group in one molecule having the carboxyl group-containing copolymer resin as a structural unit is (meth) acrylic acid, Include those containing two or more carboxyl groups in the molecule, such as maleic acid and itaconic acid. Also included are maleic acid, itaconic acid monoesters, or monoamides. Moreover, the half ester compound which is a reaction product of a hydroxyl group containing (meth) acrylate and a saturated or unsaturated dibasic acid anhydride is mentioned. These half ester compounds can be obtained by reacting a hydroxyl group-containing (meth) acrylate with a saturated or unsaturated dibasic acid anhydride in an equimolar ratio.

  Examples of the hydroxyl group-containing acrylate used in the synthesis of the half ester compound include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, and trimethylolpropane. Examples include di (meth) acrylate, pendaerythritol tri (meth) acrylate, diventaerythritol penta (meth) acrylate, and the like.

Examples of the saturated or unsaturated dibasic acid anhydride used in the synthesis of the half ester compound include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyl nadrahydrophthalic anhydride, ethyl tetrahydro Examples thereof include phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride and the like. Of these, (meth) acrylic acid is preferred.
These compounds having one unsaturated group and at least one carboxyl group or acid anhydride group in one molecule may be used alone or in combination of two or more.

  Examples of the (meth) acrylic acid ester that constitutes the structural unit of the carboxyl group-containing copolymer resin include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth). Acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) Acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meta ) Acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monophenyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, Polyethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monoethyl ether (meth) acrylate , Β-phenoxyethoxyethyl acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meta ) Acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, tribromophenyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, and the like.

Examples of the styrenes constituting the structural unit of the carboxyl group-containing copolymer resin (a) include, for example, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, methoxystyrene, Butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethylstyrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc, etc.), methyl vinylbenzoate, α-methyl Examples include styrene.
The (a) carboxyl group-containing copolymer resin comprises a compound having one unsaturated group and at least one carboxyl group or acid anhydride group in one molecule, a (meth) acrylic acid ester monomer, and styrene. It is obtained by copolymerization by a usual copolymerization method with at least one of the above classes, for example, a solution polymerization method.
In addition, (a) maleic acid monoester / styrene copolymers, maleic acid monoamide / styrene copolymers, itaconic acid monoester / styrene copolymers, and itacon included in the carboxyl group-containing copolymer resin. In the case of acid monoamide / styrene copolymers, obtain by polymer reaction of maleic anhydride / styrene copolymers or itaconic anhydride / styrene copolymers with alcohols or primary or secondary amines, respectively. Can do.

Examples of the alcohols used for the polymer reaction with the maleic anhydride include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, pentanol, hexanol, and cyclohexanol. Preferable examples include methoxyethanol, ethoxyethanol, methoxypropanol, ethoxypropanol and the like.
Examples of the primary amines include benzylamine, phenethylamine, 3-phenyl-1-propylamine, 4-phenyl-1-butylamine, 5-phenyl-1-pentylamine, and 6-phenyl-1-hexylamine. , Α-methylbenzylamine, 2-methylbenzylamine, 3-methylbenzylamine, 4-methylbenzylamine, 2- (p-tolyl) ethylamine, β-methylphenethylamine, 1-methyl-3-phenylpropylamine, 2- Chlorobenzylamine, 3-chlorobenzylamine, 4-chlorobenzylamine, 2-fluorobenzylamine, 3-fluorobenzylamine, 4-fluorobenzylamine, 4-bromophenethylamine, 2- (2-chlorophenyl) ethylamine, 2- (3-Chlorophenyl) ethyl Amine, 2- (4-chlorophenyl) ethylamine, 2- (2-fluorophenyl) ethylamine, 2- (3-fluorophenyl) ethylamine, 2- (4-fluorophenyl) ethylamine, 4-fluoro-α, α-dimethyl Phenethylamine, 2-methoxybenzylamine, 3-methoxybenzylamine, 4-methoxybenzylamine, 2-ethoxybenzylamine, 2-methoxyphenethylamine, 3-methoxyphenethylamine, 4-methoxyphenethylamine, methylamine, ethylamine, isopropylamine, n -Propylamine, n-butylamine, tert-butylamine, sec-butylamine, pentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, laurylamine, phenylamine, 1 Naphthylamine, methoxymethylamine, 2-methoxyethylamine, 2-ethoxyethylamine, 3-methoxypropylamine, 2-butoxyethylamine, 2-cyclohexyloxyethylamine, 3-ethoxypropylamine, 3-propoxypropylamine, 3- Preferable examples include isopropoxypropylamine.
Further, examples of the secondary amines preferably include dimethylamine, diethylamine, methylethylamine, methylpropylamine, diethylamine, ethylpropylamine, dipropylamine, dibutylamine, N, N-methylbenzylamine and the like. Can do.

-(B) Epoxy group-containing unsaturated compound-
The (b) epoxy group-containing unsaturated compound used in the production of the vinyl polymer type alkali-soluble crosslinkable resin of the type (A-1) includes one radical polymerizable unsaturated group and epoxy group in one molecule. And compounds represented by the following general formulas (VIII-1) to (VIII-14) can be given.

However, in the general formula (VIII-1) ~ (VIII -14), R 59 is either a hydrogen atom or a methyl ^{group, R 60} is an alkylene group having 1 to 10 carbon ^{atoms, R 61} is 1 to carbon atoms 10 hydrocarbon groups, p represents 0 or the integer of 1-10.
These (b) epoxy group-containing unsaturated compounds may be used alone or in a combination of two or more. Among these, glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate are preferable.

-Type (A-2)-
The epoxy group-containing copolymer resin (c) used for the production of the vinyl polymer type alkali-soluble crosslinkable resin of the type (A-2) is a non-reactive (meth) epoxy group-containing monomer and other epoxy groups. It can be obtained by copolymerization with acrylic esters and / or styrenes.
As the epoxy group-containing monomer, the compounds described above in the description of the vinyl polymer type alkali-soluble crosslinkable resin of type (A-1) are preferably used.
At least one of the (meth) acrylic acid ester and styrenes that are non-reactive with the epoxy group is a carboxyl group, an alcoholic hydroxyl group, among the above-described alkali-soluble crosslinkable resins of the type (A-1), Those containing no phenolic hydroxyl group or amino group are preferably used.
As a production method, it is obtained by copolymerizing an epoxy group-containing monomer, a non-reactive (meth) acrylic acid ester and styrene with a conventional method such as a solution polymerization method.
Here, the molar ratio of the epoxy group-containing monomer and the other epoxy group and non-reactive (meth) acrylic ester and / or styrenes is preferably 60:40 to 20:80. If the amount of the epoxy group-containing monomer is too small and the molar ratio is larger than 20:80, the amount of addition of the next unsaturated carboxylic acid and polybasic acid anhydride to the copolymer is reduced. If the molar ratio is less than 60:40, the softening point tends to be too low.
In addition, in the description of the vinyl polymer type alkali-soluble crosslinkable resin of type (A-1), the carboxyl group-containing unsaturated compound (d) is one unsaturated group and at least one carboxyl group in one molecule, or As the compound having an acid anhydride group, each compound described above can be suitably used.
Further, as the polybasic acid anhydride (e), maleic anhydride, succinic anhydride, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-ethyltetrahydrophthalic acid Saturated or unsaturated aliphatic, alicyclic or aromatic compounds having one acid anhydride group in the molecule, such as anhydride, 4-ethyltetrahydrophthalic anhydride and phthalic anhydride are preferred. Among these, tetrahydrophthalic anhydride is particularly preferable.
The reaction of the epoxy group-containing copolymer, the carboxyl group-containing unsaturated compound and the subsequent polybasic acid anhydride is preferably carried out as follows. After addition reaction of 0.8 to 1.2 mol of unsaturated carboxylic acid per one epoxy group equivalent of the copolymer to the epoxy group-containing monomer copolymer, Polybasic acid anhydride is subjected to addition reaction.

-Type (A-3)-
The acid anhydride group-containing resin (f) used for the production of the vinyl polymer type alkali-soluble crosslinkable resin of type (A-3) is a copolymer of maleic anhydride and styrene or itaconic anhydride and styrene. Is obtained by copolymerization.
As the styrene as the copolymer component, those described above in the description of the alkali-soluble crosslinkable resin of type (A-1) are preferably used. The copolymer composition ratio of maleic anhydride or itaconic anhydride and styrene is preferably 9: 1 to 1: 9, more preferably 8: 2 to 2: 8, and particularly preferably 7: 3 to 3: 7. If it is 9: 1 or more, the developing resistance of the cured part is inferior, and if it is 1: 9 or less, the developability is inferior.
A copolymer having a mass average molecular weight of about 1,000 to 5,000 obtained by copolymerizing styrene at a ratio of 1 mol to 3 mol with respect to 1 mol of maleic anhydride is preferable. For example, ARCO Chemical Company Examples thereof include SMA ranges 1000, 2000, and 3000.

  Examples of the compound (g) having one hydroxyl group and at least one (meth) acryloyl group in the molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl. (Meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polycaprolactone mono (meth) acrylate, pendaerythritol tri (meth) acrylate, trimethylolpropane di (meth) acrylate, neopentyl glycol mono (Meth) acrylate, 1,6-hexanediol mono (meth) acrylate, mono (2- (meth) acryloyloxyethyl) acid phosphate, di (2- (meth) acryloyloxyethyl) ) Acid phosphate, glycerol di (meth) acrylate.

The ring-opening addition reaction of the acid anhydride copolymer and a monomer having one hydroxyl group and at least one (meth) acryloyl group in the molecule is performed in an organic solvent not containing active hydrogen. It can manufacture by the method of. Preferred solvents are ethyl acetate, methoxypropyl acetate, methyl ethyl ketone and the like. In this case, the molar ratio of hydroxyl group in the monomer / acid anhydride group in the copolymer is preferably 0.8 to 1.2.
The above ring-opening addition reaction is usually carried out at 50 to 200 ° C., but is preferably about 80 to 150 ° C. in order to prevent formation of diester and gelation. As reaction accelerators, tertiary amines such as triethylamine, triethanolamine, morpholine, and pentamethyldiethylenetriamine, or quaternary ammonium salts can be used. On the other hand, a known polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, t-butylhydroquinone, t-butylcatechol, benzoquinone, phenothiazine and the like can be added and used in order to prevent the formation of a polymer during the reaction.

As described above, the obtained vinyl polymer type alkali-soluble crosslinkable resin composed of at least one of the types (A-1), (A-2) and (A-3) has an acid value of 50 to 50. It is preferably in the range of 250 mg KOH / g.
The acid value is more preferably from 70 to 200 mgKOH / g, particularly preferably from 90 to 180 mgKOH / g. When the acid value is less than 50 mgKOH / g, it is difficult to remove the unexposed area with a developing solution that is a weak alkaline aqueous solution. There are harmful effects. The vinyl polymer type alkali-soluble crosslinkable polymer (A) preferably has a mass average molecular weight in the range of 5,000 to 200,000. The mass average molecular weight is more preferably 10,000 to 100,000, and particularly preferably 30,000 to 80,000. When the mass average molecular weight is less than 5,000, the dryness to touch is remarkably inferior and the peelability from the support is inferior. On the other hand, a mass average molecular weight exceeding 200,000 is not preferable because problems such as removability of unexposed portions and storage stability due to an alkaline developer are caused.
The solid content of the alkali-soluble crosslinkable resin in the total solid content of the photosensitive composition is preferably 15 to 70% by mass. If it is less than 15% by mass, the toughness of the cured film may be inferior. If it exceeds 70% by mass, the performance balance may be deteriorated, such as a decrease in reliability.
In particular, one mixture from the types (A-1) to (A-3) and one mixture from the epoxy resin ester type alkali-soluble crosslinkable oligomer described later are preferable because they can provide balanced performance. . In this case, the mixing ratio is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2, and particularly preferably 3: 7 to 7: 3 in terms of mass.

-Epoxy resin ester type alkali-soluble crosslinkable resin-
There is no restriction | limiting in particular as said epoxy resin ester type alkali-soluble crosslinking resin, According to the objective, it can select suitably, For example, (h) epoxy resin and (i) one unsaturated group in 1 molecule It is produced by further reacting (j) a polybasic acid anhydride with an esterification reaction product of a compound having at least one carboxyl group or acid anhydride group.
Examples of the epoxy resin (h) include YDCN-701, YDCN-704 manufactured by Toto Kasei Co., Ltd .; N-665, N-680, N-695 manufactured by Dainippon Ink & Chemicals, Inc .; Nippon Kayaku Co., Ltd. EOCN-102, EOCN-104 manufactured by Asahi Kasei Kogyo Co., Ltd. ECN-265, ECN-293, ECN-285, ECN-299 and other cresol novolac type epoxy resins, and Toto Kasei K.K. -602; DEN-431, DEN-438, DEN-439 manufactured by Dow Chemical Japan Co., Ltd .; EPN-1138, EPN-1235, EPN-1299 manufactured by Ciba Specialty Chemicals Co., Ltd .; Phenol novolac type epoxy resins such as N-730 and N-770 manufactured by the same company may be mentioned. In addition, a part of the novolac type epoxy resin is, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, bixylenol type epoxy resin, trishydroxyphenylmethane type epoxy resin, tetra Epoxy resins such as phenylethane type epoxy resins, alicyclic epoxy resins, salicylaldehyde type epoxy resins and the like can also be used advantageously.

Next, the compound (i) having one unsaturated group and at least one carboxyl group or acid anhydride group in one molecule is a vinyl polymer type alkali-soluble crosslinkable resin of the type (A-1). Each compound already described in the description can be preferably used.
Similarly, the polybasic acid anhydride (j) may use the above-mentioned compounds as the component (e) in the description of the vinyl polymer type alkali-soluble crosslinkable resin of the type (A-2).

--Method for producing epoxy resin ester type alkali-soluble crosslinkable resin--
There is no restriction | limiting in particular as a manufacturing method of the said epoxy resin ester type alkali soluble crosslinkable resin, According to the objective, it can select suitably, For example, the epoxy resin (h) in the case of manufacture, and one piece in 1 molecule In the reaction of the compound (i) having at least one carboxyl group or acid anhydride group with one unsaturated group in one molecule per one equivalent of the epoxy group of the epoxy resin (h) It is preferable that the compound (i) having a group and at least one carboxyl group or acid anhydride group is reacted at a ratio of 0.8 to 1.05 equivalent, more preferably 0.9 to 1.0 equivalent.
The epoxy resin (h) and the compound (i) having one unsaturated group and at least one carboxyl group or acid anhydride group in one molecule are dissolved and reacted in an organic solvent. For example, ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl Glycol ethers such as ether, dipropylene glycol diethyl ether and triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate and carbitol acetate, fats such as octane and decane Hydrocarbons, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and petroleum solvents such as solvent naphtha.

Furthermore, it is preferable to use a catalyst to accelerate the reaction. Examples of the catalyst used include triethylamine, benzylmethylamine, methyltriethylammonium chlorite, benzyltrimethylammonium chlorite, benzyltrimethylammonium bromide, benzyltrimethylmethylammonium iodide, triphenylphosphine, and the like. The amount of the catalyst used is preferably 0.1 to 10 parts by mass with respect to a total of 100 parts by mass of the epoxy resin and the vinyl group-containing monocarboxylic acid (b).
Further, it is preferable to use a polymerization inhibitor for preventing polymerization during the reaction. Examples of the polymerization inhibitor include hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, and the amount used is 100 parts by mass in total of the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b). The amount is preferably 0.01 to 1 part by mass. The reaction temperature is preferably 60 to 150 ° C, more preferably 80 to 120 ° C.

  The epoxy resin ester type alkali-soluble crosslinkable resin is obtained by reacting the reaction product thus obtained with a polybasic acid anhydride (j). The reaction temperature between the reaction product and the polybasic acid anhydride (c) is preferably 60 to 120 ° C.

By reacting 0.1 to 1.0 equivalent of polybasic acid anhydride (j) with respect to 1 equivalent of hydroxyl group in the reaction product, the acid value of the epoxy resin ester type alkali-soluble crosslinkable resin is reduced. Can be adjusted. The acid value of the epoxy resin ester type alkali-soluble crosslinkable resin is preferably 30 to 150 mgKOH / g, more preferably 50 to 120 mgKOH / g. When the acid value is less than 30 mgKOH / g, the solubility of the photocurable resin composition in a dilute alkali solution is lowered, and when it exceeds 150 mgKOH / g, the electric characteristics of the cured film tend to be lowered.
The epoxy resin ester type alkali-soluble crosslinkable resin preferably has a mass average molecular weight of 500 to 5,000, more preferably 1,000 to 4,000, and particularly preferably 1,500 to 3,500. If it is 500 or less, the adhesiveness is too high, and it may be difficult to peel off the protective film, and if it exceeds 5,000, it may be difficult to produce the resin.

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

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

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

<Thermal crosslinking agent>
There is no restriction | limiting in particular as said heat-crosslinking agent, According to the objective, it can select suitably, For example, an epoxy resin, a polyfunctional oxetane compound, etc. are mentioned suitably.
The epoxy resin and the polyfunctional oxetane compound are not particularly limited and can be appropriately selected depending on the purpose. For example, the film strength after curing of the photosensitive layer formed using the photosensitive composition is improved. Therefore, an epoxy resin compound having at least two oxirane groups in one molecule, an oxetane compound having at least two oxetanyl groups in one molecule, and the like can be used within a range that does not adversely affect developability.

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

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

  There is no restriction | limiting in particular as solid content in solid content of the said photosensitive composition solution of the said epoxy resin or a polyfunctional oxetane compound, According to the objective, it can select suitably, For example, 2-50 mass% Is preferable, and 3-30 mass% is more preferable. If the solid content is less than 2% by mass, the hygroscopicity of the cured film is increased, resulting in deterioration of insulation, or solder heat resistance and electroless plating resistance may be reduced. If it exceeds mass%, the developability may deteriorate and the exposure sensitivity may decrease, which is not preferable.

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

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

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

<Thermosetting accelerator>
The thermosetting accelerator has a function of promoting thermal crosslinking of the epoxy resin compound or the polyfunctional oxetane compound, and is preferably added to the photosensitive resin.
The thermosetting accelerator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy. Amine compounds such as -N, N-dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; quaternary ammonium salt compounds such as triethylbenzylammonium chloride; blocked isocyanate compounds such as dimethylamine; imidazole and 2-methyl Imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methyl Imidazole Any imidazole derivatives bicyclic amidine compounds and salts thereof; phosphorus compounds such as triphenylphosphine; guanamine compounds such as melamine, guanamine, acetoguanamine, benzoguanamine; 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2 -Vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid S-triazine derivatives such as adducts, boron trifluoride-amine complex, organic hydrazide cumulative, phthalic anhydride, trimellitic anhydride, ethylene glycol bis (anhydro trimellitate), glycerol tris (anhydro trimellitate) , Benzo Aromatic acid anhydrides such as phenonetetracarboxylic anhydride, aliphatic acid anhydrides such as maleic anhydride and tetrahydrophthalic anhydride, polyphenols such as polyvinylphenol, polyvinylphenol bromide, phenol novolac and alkylphenol novolac Etc. can be used. These may be used alone or in combination of two or more. The epoxy resin compound or the polyfunctional oxetane compound is a curing catalyst, or any compound capable of promoting the thermal crosslinking other than the above as long as it can promote the reaction of these with a carboxyl group. May be used.
The solid content in the solid content of the photosensitive composition solution of the epoxy resin, the polyfunctional oxetane compound, and a compound capable of promoting thermal crosslinking between the epoxy resin and the carboxylic acid is usually 0.01 to 20% by mass. It is.

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

<Inorganic filler>
The inorganic filler can improve the surface hardness of the permanent pattern, can keep the coefficient of linear expansion low, and has a function of keeping the dielectric constant and dielectric loss tangent of the cured layer itself low. It can use suitably for a composition.
The inorganic filler 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 process silica, none Examples include regular silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica.

The average particle size of the inorganic filler is preferably less than 3 μm, more preferably 0.1 to 2 μm. When the average particle diameter is 3 μm or more, resolution may be deteriorated due to light scattering.
5-75 mass% is preferable, as for the addition amount of the said inorganic filler, 8-70 mass% is more preferable, and 10-65 mass% is especially preferable. When the addition amount is less than 5% by mass, the linear expansion coefficient may not be sufficiently reduced. When the addition amount exceeds 90% 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.

Further, organic fine particles can be added as necessary. Suitable organic fine particles are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include melamine resin, benzoguanamine resin, and crosslinked polystyrene resin. Further, silica having an average particle diameter of 0.1 to ² 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.

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

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

-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 (C I.26150), Monolite Yellow GT (C.I. Pigment Yellow 12), Permanent Yellow GR (C.I. Pigment Yellow 17), Permanent Yellow HR (C.I. Pigment Yellow 83), C.I. I. Pigment yellow 139, C.I. I. Pigment Yellow 185, Permanent Carmine FBB (C.I. Pigment Red 146), Hoster Balm Red ESB (C.I. Pigment Violet 19), Permanentorby FBH (C.I. Pigment Red 11) Fastel Pink B Supra (C Pigment Red 81) Monastral First Blue (CI Pigment Blue 15), Monolite First Black B (CI Pigment Black 1), Carbon, C.I. 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. And CI Pigment Blue 64. These may be used alone or in combination of two or more.

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

-Solvent-
There is no restriction | limiting in particular as said solvent, According to the objective, it can select suitably, For example, alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, n-hexanol; acetone , Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone; esters such as ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxypropyl acetate Aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene; halogenated carbonization such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, monochlorobenzene Motorui; tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethers such as 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and sulfolane. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.
-Surfactant-
A known surfactant can be added to the photosensitive composition in order to improve the surface unevenness generated when the pattern forming material of the present invention is produced.
The surfactant can be appropriately selected from, for example, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and a fluorine-containing surfactant.

As for content of the said surfactant, 0.001-10 mass% is preferable with respect to solid content of the photosensitive composition for pattern formation materials.
When the content is less than 0.001% by mass, the effect of improving the surface shape may not be obtained, and when it exceeds 10% by mass, the adhesion may be deteriorated.

  As the surfactant, in addition to the above-mentioned surfactant, as a fluorine-based surfactant, it contains 40% by mass or more of fluorine atoms in a carbon chain of 3 to 20, and at least 3 counted from the non-bonding terminal A polymer surfactant having, as a copolymerization component, an acrylate or methacrylate having a fluoroaliphatic group in which a hydrogen atom bonded to a carbon atom is fluorine-substituted is also preferred.

-Adhesion promoter-
The adhesion promoter has a function of improving adhesion between layers, adhesion between the photosensitive layer and the substrate, and electrolytic corrosion.
The adhesion promoter is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include melamine, acetoguanamine, benzoguatemine, melamine-phenol formalin resin, ethyldiamino-S-triazine, 2,4-diamino. And triazine compounds such as -S-triazine and 2,4-diamino-6-xylyl-S-triazine. Commercially available triazine compounds include Shikoku Kasei Kogyo Co., Ltd. shown in the following structural formulas (E) to (G); 2MZ-AZINE (structural formula (E)), 2E4MZ-AZINE (structural formula (F)), CllZ -AZINE (Structural Formula (G)) and the like can be given.
These compounds increase the adhesion to the copper circuit, improve the PCT resistance, and have an effect on electrolytic corrosion. These can be used alone or in combination of two or more. 0.1-40 mass% is preferable with respect to photosensitive composition solid content, and, as for content of an adhesion promoter, 0.1-20 mass% is more preferable.

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

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

(Photosensitive film)
The photosensitive film has at least a support and a photosensitive layer made of the photosensitive composition of the present invention on the support, and other layers appropriately selected such as a cushion layer according to the purpose. Laminated.

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

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

  There is no restriction | limiting in particular in the thickness of the said support body, According to the objective, it can select suitably, For example, 4-300 micrometers is preferable and 5-175 micrometers is more preferable.

  The shape of the support is not particularly limited and can be appropriately selected according to the purpose. For example, the support is wound around a cylindrical core, wound into a long roll, and stored. preferable. 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 on the end face, and it is also preferable to use a material with low moisture permeability for packaging. As the separator, those having moisture resistance and those containing a desiccant are particularly preferable.

<Photosensitive layer>
The photosensitive layer is formed using the photosensitive composition of the present invention. There is no restriction | limiting in particular as a location provided in the said photosensitive film of the said photosensitive layer, According to the objective, it can select suitably, Usually, it laminates | stacks on the said support body.
The photosensitive layer may be a single layer or a plurality of layers.

  There is no restriction | limiting in particular in the thickness of the said photosensitive layer, According to the objective, it can select suitably, For example, 1-100 micrometers is preferable and 5-70 micrometers is more preferable.

<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 blocking 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 less, 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 % 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 easily peeled off, and includes 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.

-Protective film-
The protective film has a function of preventing and protecting the photosensitive layer from being stained and damaged.
There is no restriction | limiting in particular as a location provided in the said photosensitive film of the said protective film, According to the objective, it can select suitably, Usually, it provides on the said photosensitive layer.
Examples of the protective film include those used for the support, silicone paper, polyethylene, paper laminated with polypropylene, polyolefin or polytetrafluoroethylene sheet, etc. Among these, polyethylene film, Polypropylene film is preferred.
There is no restriction | limiting in particular in the thickness of the said protective film, According to the objective, it can select suitably, For example, 5-100 micrometers is preferable and 8-30 micrometers is more preferable.
When the protective film is used, it is preferable that the adhesive force A between the photosensitive layer and the support and the adhesive force B between the photosensitive layer and the protective film satisfy the relationship of adhesive force A> adhesive force B.
Examples of the combination of the support and the protective film (support / protective film) include polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate, and the like. . Moreover, the relationship of the above adhesive forces can be satisfy | filled by surface-treating at least any one of a support body and a protective film. The surface treatment of the support may be performed in order to increase the adhesive force with the photosensitive layer. For example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow treatment Examples thereof include discharge irradiation treatment, active plasma irradiation treatment, and laser beam irradiation treatment.

Moreover, 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.

  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.

[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 resin 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 resin 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.

(Photosensitive laminate)
The photosensitive laminate is formed by laminating at least the photosensitive layer on a 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 member to be transferred onto which at least the photosensitive layer of the photosensitive film of the present invention is transferred. For example, it can be arbitrarily selected from those having high surface smoothness to those having an uneven surface. A plate-like substrate is preferable, and a so-called substrate is used. Specific examples include a known printed wiring board (printed board), a glass plate (soda glass plate, etc.), a synthetic resin film, paper, and a metal plate.

[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.

(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 process, and includes other appropriately selected processes such as a development process and a curing process.
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 said photosensitive layer in the photosensitive laminated body of this invention. Examples of the photosensitive layer in the photosensitive laminate of the present invention include a photosensitive layer formed from the photosensitive composition of the present invention and a photosensitive layer transferred from the photosensitive film.

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

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

  The digital exposure is not particularly limited and can be appropriately selected depending on the purpose.For example, a control signal is generated based on pattern formation information to be formed, and light modulated in accordance with the control signal is generated. For example, the photosensitive layer is arranged in a two-dimensional array of light irradiation means and n pieces (where n is a natural number of 2 or more) that receives and emits light from the light irradiation means. An exposure head comprising a light modulation means capable of controlling the drawing portion in accordance with pattern information, the column direction of the drawing portion relative to the scanning direction of the exposure head Using an exposure head arranged so as to form a predetermined set inclination angle θ, the exposure head is subjected to N-fold exposure (where N is (Natural number of 2 or more) Designation of a grapheme part and control of the pixel part for the exposure head so that only the picturee part designated by the use picture element part designation means is involved in exposure by the picture element part control means It is preferable that the exposure head is moved relative to the photosensitive layer in the scanning direction.

In the present invention, “N double exposure” means that the exposed surface is irradiated with a straight line parallel to the scanning direction of the exposure head in almost all of the exposed region on the exposed surface of the photosensitive layer. This means exposure by setting that intersects N light spot rows (pixel rows). Here, the “light spot array (pixel array)” has a smaller angle with the scanning direction of the exposure head in the array of light spots (pixels) as pixel units generated by the pixel unit. It shall refer to a sequence of directions. Note that the arrangement of the picture element portions is not necessarily a rectangular lattice shape, and may be, for example, an arrangement of parallelograms. Here, “substantially all areas” of the exposure area is described as a straight line parallel to the scanning direction of the exposure head by tilting the pixel part rows at both side edges of each picture element part. Since the number of drawing element rows of the used drawing element parts to be crossed decreases, even if it is used to connect a plurality of exposure heads in such a case, it is parallel to the scanning direction due to errors in the mounting angle and arrangement of the exposure heads. The number of pixel parts in the used pixel part that intersect with a straight line may slightly increase or decrease, and the connection between the pixel parts in each used pixel part is only a fraction of the resolution. However, due to errors such as the mounting angle and the arrangement of the picture element parts, the pitch of the picture element parts along the direction orthogonal to the scanning direction does not exactly match the pitch of the picture element parts of other parts, and is parallel to the scanning direction. The number of used pixel parts that intersect with the straight line may increase or decrease within a range of ± 1. It is an order. In the following description, N multiple exposures where N is a natural number of 2 or more are collectively referred to as “multiple exposure”. Further, in the following description, the pattern forming apparatus (exposure apparatus) or the exposure method of the present invention is implemented as a drawing apparatus or a drawing method, and the terms corresponding to “N double exposure” and “multiple exposure” are “ The terms “N-fold drawing” and “multiple drawing” shall be used.
N in the N-fold exposure is not particularly limited as long as it is a natural number of 2 or more, and can be appropriately selected according to the purpose. However, a natural number of 3 or more is preferable, and a natural number of 3 or more and 7 or less is more preferable. .

<Pattern forming device>
An example of a pattern forming apparatus according to the permanent pattern forming method of the present invention will be described with reference to the drawings.
The pattern forming apparatus is a so-called flatbed type exposure apparatus, and as shown in FIG. 1, a sheet-like photosensitive laminate 12 (hereinafter referred to as a laminate) in which at least the photosensitive layer in the photosensitive film is laminated. , “Photosensitive material 12” or “photosensitive layer 12”) is provided. Two guides 20 extending along the stage moving direction are installed on the upper surface of the thick plate-shaped installation table 18 supported by the four legs 16. The stage 14 is arranged so that the longitudinal direction thereof faces the stage moving direction, and is supported by the guide 20 so as to be reciprocally movable. The pattern forming apparatus 10 is provided with a stage driving device (not shown) that drives the stage 14 along the guide 20.

  A U-shaped gate 22 is provided at the center of the installation base 18 so as to straddle the movement path of the stage 14. Each end of the U-shaped gate 22 is fixed to both side surfaces of the installation base 18. A scanner 24 is provided on one side across the gate 22, and a plurality of (for example, two) sensors 26 that detect the front and rear ends of the photosensitive material 12 are provided on the other side. The scanner 24 and the sensor 26 are respectively attached to the gate 22 and fixedly arranged above the moving path of the stage 14. The scanner 24 and the sensor 26 are connected to a controller (not shown) that controls them.

  Here, for explanation, an X axis and a Y axis orthogonal to each other are defined in a plane parallel to the surface of the stage 14 as shown in FIG.

  A slit formed in a “<” shape that opens in the direction of the X-axis at the upstream edge (hereinafter sometimes simply referred to as “upstream”) along the scanning direction of the stage 14. 10 are formed at equal intervals. Each slit 28 includes a slit 28 a located on the upstream side and a slit 28 b located on the downstream side. The slit 28a and the slit 28b are orthogonal to each other, and the slit 28a has an angle of −45 degrees and the slit 28b has an angle of +45 degrees with respect to the X axis.

  The position of the slit 28 is substantially coincident with the center of the exposure head 30. Further, the size of each slit 28 is set to sufficiently cover the width of the exposure area 32 by the corresponding exposure head 30. Further, the position of the slit 28 may be substantially coincident with the center position of the overlapping portion between the adjacent exposed regions 34. In this case, the size of each slit 28 is set so as to sufficiently cover the width of the overlapping portion between the exposed regions 34.

  In the position below each slit 28 inside the stage 14, single cell type light detection as a light spot position detecting means for detecting a light spot as a pixel unit in a used pixel part designation process described later. A vessel (not shown) is incorporated. In addition, each photodetector is connected to an arithmetic unit (not shown) as a pixel part selection means for selecting the pixel part in the used pixel part specifying process described later.

  The operation form of the pattern forming apparatus at the time of exposure may be a form in which exposure is continuously performed while constantly moving the exposure head, or each movement destination position while the exposure head is moved stepwise. The exposure head may be stationary to perform the exposure operation.

<< Exposure head >>
Each exposure head 30 is connected to the scanner 24 so that each pixel portion (micromirror) row direction of an internal digital micromirror device (DMD) 36 described later forms a predetermined set inclination angle θ with the scanning direction. It is attached. Therefore, the exposure area 32 by each exposure head 30 is a rectangular area inclined with respect to the scanning direction. As the stage 14 moves, a strip-shaped exposed region 34 is formed in the photosensitive layer 12 for each exposure head 30. In the example shown in FIGS. 2 and 3B, the scanner 24 includes ten exposure heads arranged in a substantially matrix of 2 rows and 5 columns.
In the following description, when the individual exposure heads arranged in the mth row and the nth column are indicated, the exposure head 30 _mn is indicated, and exposure by the individual exposure heads arranged in the mth row and the nth column is performed. When an area is indicated, it is expressed as an exposure area 32 _mn .

Further, as shown in FIGS. 3A and 3B, each of the exposure heads 30 in each row arranged in a line so that each of the strip-shaped exposed regions 34 partially overlaps the adjacent exposed region 34 is In the arrangement direction, they are shifted by a predetermined interval (a natural number times the long side of the exposure area, twice in this embodiment). Therefore, can not be exposed portion between the exposure area _{32 11} in the first row and the exposure area _{32 12,} it can be exposed by the second row of the exposure area _{32 21.}

  As shown in FIGS. 4 and 5, each of the exposure heads 30 includes a light modulation unit (spatial light modulation element that modulates each pixel unit) that modulates incident light for each pixel unit according to image data. DMD36 (manufactured by Texas Instruments, USA). The DMD 36 is connected to a controller serving as a pixel part control unit including a data processing unit and a mirror drive control unit. The data processing unit of this controller generates a control signal for driving and controlling each micromirror in the use area on the DMD 36 for each exposure head 30 based on the input image data. The mirror drive control unit controls the angle of the reflection surface of each micromirror of the DMD 36 for each exposure head 30 based on the control signal generated by the image data processing unit.

  As shown in FIG. 4, on the light incident side of the DMD 36, there is provided a laser emission portion in which the emission end portion (light emission point) of the optical fiber is arranged in a line along the direction that coincides with the long side direction of the exposure area 32. The fiber array light source 38, the lens system 40 for correcting the laser light emitted from the fiber array light source 38 and condensing it on the DMD, and the mirror 42 for reflecting the laser light transmitted through the lens system 40 toward the DMD 36 Arranged in order. In FIG. 4, the lens system 40 is schematically shown.

  As shown in detail in FIG. 5, the lens system 40 has a pair of combination lenses 44 that collimate the laser light emitted from the fiber array light source 38, and the light quantity distribution of the collimated laser light becomes uniform. A pair of combination lenses 46 to be corrected in this way, and a condensing lens 48 that condenses the laser light whose light quantity distribution has been corrected on the DMD 36.

  Further, on the light reflection side of the DMD 36, a lens system 50 that images the laser light reflected by the DMD 36 on the exposed surface of the photosensitive layer 12 is disposed. The lens system 50 includes two lenses 52 and 54 arranged so that the DMD 36 and the exposed surface of the photosensitive layer 12 have a conjugate relationship.

  In the present embodiment, the laser light emitted from the fiber array light source 38 is substantially magnified five times, and then the light from each micromirror on the DMD 36 is reduced to about 5 μm by the lens system 50. Is set to

-Light modulation means-
As the light modulation means, there are n (where n is a natural number of 2 or more) two-dimensionally arranged image elements, and the image elements can be controlled according to the pattern information. If it is, there will be no restriction | limiting in particular, According to the objective, it can select suitably, For example, a spatial light modulation element is preferable.

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

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.

Hereinafter, an example of the light modulation means will be described with reference to the drawings.
As shown in FIG. 6, the DMD 36 is a mirror device in which a large number of micromirrors 58 are arranged in a lattice pattern on a SRAM cell (memory cell) 56 as a pixel portion constituting each pixel (pixel). . In the present embodiment, the DMD 36 in which the micromirrors 58 of 1024 columns × 768 rows are arranged is used. Of these, the micromirrors 58 that can be driven by the controller connected to the DMD 36, that is, usable, are 1024 columns × 256 rows. Suppose only. The data processing speed of the DMD 36 is limited, and the modulation speed per line is determined in proportion to the number of micromirrors to be used. Thus, by using only some of the micromirrors in this way, Modulation speed increases. Each micromirror 58 is supported by a support column, and a material having high reflectivity such as aluminum is deposited on the surface thereof. In the present embodiment, the reflectance of each micromirror 58 is 90% or more, and the arrangement pitch thereof is 13.7 μm in both the vertical direction and the horizontal direction. The SRAM cell 56 is of a silicon gate CMOS manufactured on a normal semiconductor memory manufacturing line via a support including a hinge and a yoke, and the entire structure is monolithic (integrated).

  When an image signal representing the density of each point constituting a desired two-dimensional pattern in binary is written in the SRAM cell (memory cell) 56 of the DMD 36, each micromirror 58 supported by the column is centered on the diagonal line. As shown in FIG. 1, the inclination is inclined to ± α degrees (for example, ± 10 degrees) with respect to the substrate side on which the DMD 36 is disposed. FIG. 7A shows a state in which the micromirror 58 is tilted to + α degrees in the on state, and FIG. 7B shows a state in which the micromirror 58 is tilted to −α degrees in the off state. In this way, by controlling the inclination of the micromirror 58 in each pixel of the DMD 36 as shown in FIG. 6 in accordance with the image signal, the laser light B incident on the DMD 36 moves in the inclination direction of each micromirror 58. Reflected.

  FIG. 6 shows an example in which a part of the DMD 36 is enlarged and each micromirror 58 is controlled to + α degrees or α degrees. The on / off control of each micromirror 58 is performed by the controller connected to the DMD 36. Further, a light absorber (not shown) is arranged in the direction in which the laser beam B reflected by the off-state micromirror 58 travels.

-Light irradiation means-
The light irradiation means is not particularly limited and may be appropriately selected depending on the purpose. For example, (ultra) high pressure mercury lamp, xenon lamp, carbon arc lamp, halogen lamp, copier, fluorescent tube, LED, etc. , A known light source such as a semiconductor laser, or means capable of synthesizing and irradiating two or more lights. Among these, means capable of synthesizing and irradiating two or more lights are preferable.
The light irradiated from the light irradiation means, for example, when light irradiation is performed through a support, transmits the support and activates the used photopolymerization initiating compound or sensitizer. Examples include electromagnetic waves, ultraviolet to visible light, electron beams, X-rays, and laser beams. Among these, laser beams are preferable, and a laser that combines two or more lights (hereinafter sometimes referred to as a “combined laser”). Is more preferable. Even when light irradiation is performed after the support is peeled off, similar light can be used.

The wavelength of the ultraviolet to visible light is, for example, preferably 300 to 1,500 nm, more preferably 320 to 800 nm, and particularly preferably 330 to 650 nm.
As a wavelength of the said laser beam, 200-1500 nm is preferable, for example, 300-800 nm is more preferable, 330-500 nm is still more preferable, 400-450 nm is especially preferable.

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

  Examples of means (fiber array light source) capable of irradiating the combined laser include means described in JP-A-2005-258431 [0109] to [0146].

<< Used pixel part designation means >>
The used pixel part specifying means includes a light spot position detecting means for detecting the position of a light spot on a surface to be exposed as a pixel unit, and N-fold exposure based on a detection result by the light spot position detecting means. It is preferable to include at least a pixel part selection unit that selects a pixel part to be used for the realization.
Hereinafter, an example of a method for designating a pixel part used for N-exposure by the used pixel part specifying unit will be described.

(1) Method for Specifying Picture Element Portions Used in Single Exposure Head In the present embodiment (1), the pattern forming apparatus 10 performs double exposure on the photosensitive material 12, and each exposure head 30. A description will be given of a method for designating a used pixel part for reducing the variation in resolution and density unevenness caused by the mounting angle error and realizing ideal double exposure.

The set inclination angle θ in the column direction of the image element (micromirror 58) with respect to the scanning direction of the exposure head 30 can be used as long as there is no mounting angle error of the exposure head 30 or the like. It is assumed that an angle slightly larger than the angle θ _ideal that is exactly double exposure using 256 lines of pixel parts is adopted.
This angle θ _ideal is equal to the number N of N double exposures, the number s of usable micromirrors 58 in the column direction, the interval p of usable micromirrors 58 in the column direction, and the microscopic exposure head 30 in a tilted state. For the pitch δ of the scanning line formed by the mirror,
spsinθ _ideal ≧ Nδ (Formula 1)
Given by. As described above, the DMD 36 according to the present embodiment includes a large number of micromirrors 58 having equal vertical and horizontal arrangement intervals arranged in a rectangular lattice shape.
pcosθ _ideal = δ (Formula 2)
And the above equation 1 is
stanθ _ideal = N (Formula 3)
It becomes. In the present embodiment (1), since s = 256 and N = 2 as described above, the angle θ _ideal is about 0.45 degrees according to Equation 3. Therefore, for example, an angle of about 0.50 degrees may be employed as the set inclination angle θ. It is assumed that the pattern forming apparatus 10 is initially adjusted so that the mounting angle of each exposure head 30, that is, each DMD 36 is close to the set inclination angle θ within an adjustable range.

  FIG. 8 illustrates an example of unevenness that occurs in the pattern on the exposed surface due to the influence of the mounting angle error of one exposure head 30 and pattern distortion in the pattern forming apparatus 10 that is initially adjusted as described above. FIG. In the following drawings and description, the light spot in the m-th row is represented by r (m) with respect to the light spot generated by each pixel part (micromirror) and constituting the exposure area on the exposed surface. ), The light spot in the nth column is denoted as c (n), and the light spot in the mth row and the nth column is denoted as P (m, n).

The upper part of FIG. 8 shows a pattern of light spots from the usable micromirror 58 projected onto the exposed surface of the photosensitive material 12 with the stage 14 being stationary, and the lower part is the upper part. 2 shows the state of the exposure pattern formed on the surface to be exposed when the stage 14 is moved and continuous exposure is performed in the state where the pattern of light spots as shown in FIG.
In FIG. 8, for convenience of explanation, the exposure pattern of the odd-numbered columns of the usable micromirrors 58 and the exposure pattern of the even-numbered columns are shown separately. However, the actual exposure patterns on the exposed surface are shown in FIG. Two exposure patterns are superimposed.

In the example of FIG. 8, as a result of adopting the set inclination angle θ slightly larger than the above angle θ _ideal , and because it is difficult to finely adjust the mounting angle of the exposure head 30, the actual mounting angle and the above As a result of the error in the set inclination angle θ, density unevenness occurs in any region on the exposed surface. Specifically, in both the exposure pattern by the odd-numbered micromirrors and the exposure pattern by the even-numbered micromirrors, it is ideal in the overlapped exposure region on the exposed surface formed by a plurality of pixel part rows. Overexposure occurs with respect to double exposure, resulting in a redundant drawing area and uneven density.

Further, the example of FIG. 8 is an example of pattern distortion appearing on the surface to be exposed, and “angular distortion” occurs in which the inclination angle of each pixel column projected on the surface to be exposed is not uniform. Causes of such angular distortion include various aberrations and alignment deviations of the optical system between the DMD 36 and the exposed surface, distortion of the DMD 36 itself, micromirror placement errors, and the like.
The angular distortion appearing in the example of FIG. 8 is a distortion in which the tilt angle with respect to the scanning direction is smaller in the left column of the figure and larger in the right column of the figure. As a result of this angular distortion, the overexposed area is smaller on the exposed surface shown on the left side of the figure and larger on the exposed surface shown on the right side of the figure.

In order to reduce the density unevenness in the overlapped exposure region on the exposed surface formed by a plurality of pixel part rows as described above, a set of the slit 28 and the photodetector is used as the light spot position detecting means. The actual inclination angle θ ′ is specified for each exposure head 30, and based on the actual inclination angle θ ′, the arithmetic unit connected to the photodetector as the pixel portion selection unit is used for actual exposure. A process of selecting a micromirror to be used is performed.
The actual inclination angle θ ′ is based on at least two light spot positions detected by the light spot position detection means, and the light spot column direction on the surface to be exposed and the scanning direction of the exposure head when the exposure head is tilted. It is specified by the angle formed by.
Hereinafter, the specification of the actual inclination angle θ ′ and the used pixel selection process will be described with reference to FIGS.

-Specification of actual inclination angle θ'-
FIG. 9 is a top view showing the positional relationship between the exposure area 32 by one DMD 36 and the corresponding slit 28. The size of the slit 28 is set to sufficiently cover the width of the exposure area 32.
In the example of the present embodiment (1), the angle formed by the 512th light spot row positioned substantially at the center of the exposure area 32 and the scanning direction of the exposure head 30 is measured as the actual inclination angle θ ′. . Specifically, the micromirror 58 in the first row and the 512th column and the micromirror 58 in the 256th row and the 512th column on the DMD 36 are turned on, and the light spots on the exposure surface corresponding to each of the micromirrors 58 are turned on. The positions of P (1,512) and P (256,512) are detected, and the angle formed by the straight line connecting them and the scanning direction of the exposure head is specified as the actual inclination angle θ ′.

FIG. 10 is a top view illustrating a method for detecting the position of the light spot P (256, 512).
First, in a state where the micromirror 58 in the 256th row and the 512th column is turned on, the stage 14 is slowly moved to relatively move the slit 28 along the Y-axis direction, and the light spot P (256, 512) is changed. The slit 28 is positioned at an arbitrary position so as to be between the upstream slit 28a and the downstream slit 28b. At this time, the coordinates of the intersection of the slit 28a and the slit 28b are (X0, Y0). The value of this coordinate (X0, Y0) is determined and recorded from the movement distance of the stage 14 to the position indicated by the drive signal given to the stage 14 and the known X-direction position of the slit 28. .

  Next, the stage 14 is moved, and the slit 28 is relatively moved along the Y axis to the right in FIG. Then, as indicated by a two-dot chain line in FIG. 10, the stage 14 is stopped when the light at the light spot P (256, 512) passes through the left slit 28b and is detected by the photodetector. The coordinates (X0, Y1) of the intersection of the slit 28a and the slit 28b at this time are recorded as the position of the light spot P (256, 512).

  Next, the stage 14 is moved in the opposite direction, and the slit 28 is relatively moved to the left in FIG. 10 along the Y axis. Then, as indicated by a two-dot chain line in FIG. 10, the stage 14 is stopped when the light at the light spot P (256, 512) passes through the right slit 28a and is detected by the photodetector. The coordinates (X0, Y2) of the intersection of the slit 28a and the slit 28b at this time are recorded as the position of the light spot P (256, 512).

  From the above measurement results, the coordinates (X, Y) indicating the position of the light spot P (256, 512) on the surface to be exposed are X = X0 + (Y1-Y2) / 2, Y = (Y1 + Y2) / 2. Determine by calculation. By the same measurement, coordinates indicating the position of P (1,512) are also determined, an inclination angle formed by a straight line connecting the respective coordinates and the scanning direction of the exposure head 30 is derived, and this is obtained as an actual inclination angle θ ′. As specified.

-Selection of used pixel part-
Using the actual inclination angle θ ′ specified in this way, the arithmetic unit connected to the photodetector is expressed by the following equation 4
ttanθ ′ = N (Formula 4)
The natural number T closest to the value t satisfying the above relationship is derived, and a process of selecting the micromirrors in the first to Tth rows on the DMD 36 as micromirrors that are actually used during the main exposure is performed. As a result, in the exposure region near the 512th column, a micromirror that minimizes the total area of the overexposed region and the underexposed region with respect to the ideal double exposure is actually obtained. It can be selected as a micromirror to be used for.

Here, instead of deriving the natural number closest to the above value t, the minimum natural number greater than or equal to the value t may be derived. In that case, in the exposure region near the 512th column, a micromirror that minimizes the area of the overexposed region and does not produce an underexposed region with respect to ideal double exposure. It can be selected as a micromirror to be actually used.
It is also possible to derive the maximum natural number equal to or less than the value t. In that case, in the exposure region near the 512th column, a micromirror that minimizes the area of the underexposed region and does not produce an overexposed region with respect to ideal double exposure. It can be selected as a micromirror to be actually used.

FIG. 11 shows how the unevenness on the exposed surface shown in FIG. 8 is improved in the exposure performed using only the light spot generated by the micromirror selected as the micromirror actually used as described above. It is explanatory drawing which showed what was done.
In this example, it is assumed that T = 253 is derived as the natural number T and the micromirrors in the first row to the 253rd row are selected. For the micromirrors in the 254th to 256th rows that are not selected, the pixel part control means sends a signal to set the angle of the always-off state, and these micromirrors are substantially Not involved in exposure. As shown in FIG. 11, in the exposure region near the 512th column, overexposure and underexposure are almost completely eliminated, and uniform exposure very close to ideal double exposure is realized.

On the other hand, in the left region of FIG. 11 (near c (1) in the figure), the inclination angle of the light spot sequence on the exposed surface is near the center (near c (512) in the figure) due to the angular distortion. This is smaller than the inclination angle of the light beam row in the region. Therefore, in the exposure using only the micromirror selected based on the actual inclination angle θ ′ measured with c (512) as a reference, the ideal double pattern is used for each of the even-numbered exposure pattern and the odd-numbered exposure pattern. An area that is underexposed with respect to the exposure is slightly generated.
However, in the actual exposure pattern formed by overlaying the exposure pattern of the odd-numbered columns and the exposure pattern of the even-numbered columns shown in the figure, the regions where the exposure amount is insufficient are complemented with each other, and the exposure unevenness due to the angular distortion is double-exposed. The effect of offsetting can be minimized.

Further, in the right region of FIG. 11 (near c (1024) in the figure), the inclination angle of the light beam on the exposed surface is near the center (near c (512) in the figure) due to the angular distortion. It is larger than the inclination angle of the light beam row in the region. Therefore, in the exposure with the micromirror selected based on the actual inclination angle θ ′ measured with c (512) as a reference, as shown in the figure, there is an overexposed region with respect to the ideal double exposure. It will occur slightly.
However, in the actual exposure pattern formed by superimposing the exposure pattern of the odd-numbered columns and the exposure pattern of the even-numbered columns shown in the figure, the overexposed regions are complemented with each other, and the density unevenness due to the angular distortion is caused by the double exposure. The effect of offsetting can be minimized.

In the present embodiment (1), as described above, the actual inclination angle θ ′ of the 512th ray array is measured, and based on the T derived from the equation (4) using the actual inclination angle θ ′. The micro-mirror 58 to be used is selected. However, as a method of specifying the actual inclination angle θ ′, a plurality of actual directions formed by the column direction (light spot column) of the plurality of image elements and the scanning direction of the exposure head are used. Each of the tilt angles is measured, and any one of the average value, median value, maximum value, and minimum value is specified as an actual tilt angle θ ′. It is good also as a form to select.
When the average value or the median value is set to the actual inclination angle θ ′, it is possible to realize exposure with a good balance between an overexposed area and an underexposed area with respect to an ideal N-fold exposure. For example, the total area of the overexposed region and the underexposed region is minimized, and the number of pixel units (number of light spots) in the overexposed region and the underexposed region are drawn. It is possible to realize exposure such that the number of prime units (number of light spots) is equal.
Further, if the maximum value is set to the actual inclination angle θ ′, it is possible to realize an exposure that places more importance on eliminating an overexposed region with respect to an ideal N double exposure, for example, an underexposure. It is possible to realize exposure that minimizes the area of the region and does not generate an overexposed region.
Further, if the minimum value is set to the actual inclination angle θ ′, it is possible to realize exposure that places more importance on eliminating underexposed areas with respect to ideal N-fold exposure, for example, overexposure. It is possible to realize exposure that minimizes the area of the region and does not cause a region that is underexposed.

On the other hand, the specification of the actual inclination angle θ ′ is not limited to the method based on the positions of at least two light spots in the same pixel part row (light spot row). For example, the angle obtained from the position of one or more light spots in the same pixel part sequence c (n) and the position of one or more light spots in the row near the c (n), The actual inclination angle θ ′ may be specified.
Specifically, one light spot position in c (n) and one or a plurality of light spot positions included in a light spot row on a straight line and in the vicinity along the scanning direction of the exposure head are detected. The actual inclination angle θ ′ can be obtained from the position information. Further, the angle obtained based on the positions of at least two light spots (for example, two light spots arranged so as to straddle c (n)) in the light spot array in the vicinity of the c (n) line is an actual inclination. The angle θ ′ may be specified.

  As described above, according to the specification method of the used picture element portion of the present embodiment (1) using the pattern forming apparatus 10, resolution variation and density unevenness due to the influence of the mounting angle error of each exposure head and pattern distortion are eliminated. It is possible to reduce and realize an ideal N double exposure.

(2) Method for designating used pixel parts between a plurality of exposure heads <1>
In the present embodiment (2), the pattern forming apparatus 10 performs double exposure on the photosensitive material 12 and is a head that is an overlapped exposure region on the exposed surface formed by the plurality of exposure heads 30. In the intermittent region, the variation in resolution and density unevenness due to the deviation from the ideal state of the relative position of the two exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) in the X-axis direction are reduced; A description will be given of a method for designating a used pixel portion for realizing ideal double exposure.

As the set inclination angle θ of each exposure head 30, that is, each DMD 36, the usable pixel portion micromirror 58 of 1024 columns × 256 rows is used if there is no ideal mounting angle error of the exposure head 30. Then, it is assumed that an angle θ _ideal that is exactly double exposure is adopted.
This angle θ _ideal is obtained from the above equations 1 to 3 in the same manner as in the above embodiment (1). In the present embodiment (2), it is assumed that the pattern forming apparatus 10 is initially adjusted so that the mounting angle of each exposure head 30, that is, each DMD 36 becomes this angle θ _ideal .

FIG. 12 shows the deviation of the relative positions of the two exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) in the X-axis direction from the ideal state in the pattern forming apparatus 10 initially adjusted as described above. It is explanatory drawing which showed the example of the density nonuniformity which arises in the pattern on a to-be-exposed surface by the influence. The displacement of the relative position of each exposure head in the X-axis direction can occur because it is difficult to finely adjust the relative position between the exposure heads.

The upper part of FIG. 12 is a light spot group from the micromirror 58 usable for the DMD 36 of the exposure heads 30 ₁₂ and 30 ₂₁ that is projected onto the exposed surface of the photosensitive material 12 with the stage 14 being stationary. It is the figure which showed these patterns. The lower part of FIG. 12 shows the exposure pattern formed on the exposed surface when the stage 14 is moved and the continuous exposure is performed with the light spot group pattern as shown in the upper part appearing. The state is shown for exposure areas 32 ₁₂ and 32 ₂₁ .
In FIG. 12, for convenience of explanation, every other exposure pattern of the micromirrors 58 that can be used is divided into an exposure pattern based on the pixel column group A and an exposure pattern based on the pixel column group B. The actual exposure pattern on the exposed surface is a superposition of these two exposure patterns.

In the example of FIG. 12, as a result of the deviation of the relative position between the exposure heads 30 ₁₂ and 30 ₂₁ in the X-axis direction from the ideal state, the exposure pattern by the pixel column group A and the pixel column group B In both of the above exposure patterns, a portion where the exposure amount is larger than the ideal double exposure state occurs in the connection area between the heads in the exposure areas 32 ₁₂ and 32 ₂₁ .

In order to reduce density unevenness appearing in the inter-head connecting region formed on the exposed surface by the plurality of exposure heads as described above, in this embodiment (2), a slit is used as the light spot position detecting means. 28 and a set of photodetectors, the positions of some of the light spots constituting the connecting area between the heads formed on the exposed surface among the light spot groups from the exposure heads 30 ₁₂ and 30 _21. Detect (coordinates). Based on the position (coordinates), processing for selecting a micromirror to be used for actual exposure is performed using an arithmetic unit connected to the photodetector as the pixel portion selection means.

-Detection of position (coordinates)-
FIG. 13 is a top view showing the positional relationship between the exposure areas 32 ₁₂ and 32 ₂₁ similar to those in FIG. 12 and the corresponding slits 28. The size of the slit 28 is large enough to cover the width of the overlapping portion between the exposed areas 34 by the exposure heads 30 ₁₂ and 30 ₂₁ , that is, the slit 28 is formed on the exposed surface by the exposure heads 30 ₁₂ and 30 _21. The size is sufficient to cover the connection area between the heads.

Figure 14 is a top view for explaining a detection method of detecting the position of a point P of the exposure area _{32 21} as an example (256, 1024).
First, with the micromirror in the 256th row and the 1024th column turned on, the stage 14 is slowly moved to relatively move the slit 28 along the Y-axis direction, and the light spot P (256, 1024) is upstream. The slit 28 is positioned at an arbitrary position so as to be between the slit 28a on the side and the slit 28b on the downstream side. At this time, the coordinates of the intersection of the slit 28a and the slit 28b are (X0, Y0). The value of this coordinate (X0, Y0) is determined and recorded from the movement distance of the stage 14 to the position indicated by the drive signal given to the stage 14 and the known X-direction position of the slit 28. .

  Next, the stage 14 is moved, and the slit 28 is relatively moved along the Y axis to the right in FIG. Then, as indicated by a two-dot chain line in FIG. 14, the stage 14 is stopped when the light at the light spot P (256, 1024) passes through the left slit 28b and is detected by the photodetector. The coordinates (X0, Y1) of the intersection of the slit 28a and the slit 28b at this time are recorded as the position of the light spot P (256, 1024).

  Next, the stage 14 is moved in the opposite direction, and the slit 28 is relatively moved to the left in FIG. 14 along the Y axis. Then, as indicated by a two-dot chain line in FIG. 14, the stage 14 is stopped when the light at the light spot P (256, 1024) passes through the right slit 28a and is detected by the photodetector. The coordinates (X0, Y2) of the intersection of the slit 28a and the slit 28b at this time are recorded as the light spot P (256, 1024).

  From the above measurement results, the coordinates (X, Y) indicating the position of the light spot P (256, 1024) on the exposed surface are calculated as X = X0 + (Y1−Y2) / 2, Y = (Y1 + Y2) / 2. Determined by

-Identification of unused pixel parts-
In the example of FIG. 12, first, the position of the point P of the exposure area _{32 12} (256,1) is detected by a set of slits 28 and a photodetector as the light spot position detecting unit. Subsequently, the position of each light spot on the 256 line of light spots row r of the exposure area _{32 21 (256), P (} 256,1024), to detect the P (256,1023) ··· and order periodically, where the exposure area _{32 21} of point P indicating the exposure area _{32 12} point P (256,1) larger X coordinate than the (256, n) is detected, and terminates the detecting operation. Then, the micro mirrors corresponding to light spots constituting the c (1024) from the light spot column c of the exposure area 32 ₂₁ (n + 1), specifies as a micro-mirror is not used during the exposure (unused pixel parts).
For example, in FIG. 12, the exposure area _{32 21} point P (256,1020) is shows a larger X coordinate than the point P of the exposure area _{32 12} (256,1) of the exposure area _{32 21} spot If P (256,1020) is that the detection operation at the detected ended, the light spots constituting the first 1024 lines from the 1021 line of exposure area _{32 21,} corresponding to the portion 70 covered with hatched in FIG. 15 The corresponding micromirror is identified as a micromirror that is not used during the main exposure.

Next, the number N of the N multiple exposure, the position of the point P of the exposure area _{32 12} (256, N) is detected. In this embodiment (2), since N = 2, the position of the light spot P (256, 2) is detected.
Then, among the light spot columns of the exposure area 32 _21, except those identified as light spots string corresponding to the micromirrors is not used during the exposure in the above, the position of the light spot constituting the rightmost 1020 column a, P (1,1020) in order from P (1,1020), P (2,1020 ) ··· and continue to detection, greater than the point P of the exposure area _{32 12} (256,2) X When the light spot P (m, 1020) indicating the coordinates is detected, the detection operation is terminated.
Thereafter, the connected operational devices to said light detector, and X-coordinate of the exposure area _{32 12} of the light spot P (256, two), point P of the exposure area _{32 21} (m, 1020) and P (m- and X-coordinate of 1,1020) are compared, if the direction of the X coordinate of the point P of the exposure area _{32 21} (m, 1020) is closer to the X coordinate of the point P in the exposure area _{32 12} (256, 2) a micro mirror corresponding to P (m-1,1020) from point P of the exposure area _{32 21} (1,1020) is identified as a micro-mirror is not used during the exposure.
Also, if the direction of the X coordinate of the point P of the exposure area _{32 21} (m-1,1020) is close to the X-coordinate of the point P in the exposure area _{32 12} (256, 2), the light of the exposure area _{32 21} Micromirrors corresponding to points P (1, 1020) to P (m−2, 1020) are specified as micromirrors that are not used for the main exposure.
Furthermore, the position of the point P of the exposure area _{32 12 (256, N-1} ) That point P (256,1), the position of each point constituting the first 1019 column is the next row of the exposure area _{32 21} The same detection process and identification of micromirrors that are not used are also performed.

  As a result, for example, micromirrors corresponding to the light spots that form the shaded area 72 in FIG. 15 are added as micromirrors that are not used during actual exposure. These micromirrors are always signaled to set the micromirror angle to the off-state angle, and these micromirrors are substantially not used for exposure.

As described above, the micromirrors that are not used at the time of actual exposure are identified, and the micromirrors that are not used at the time of actual exposure are selected as the micromirrors that are used at the time of actual exposure, whereby the exposure areas 32 ₁₂ and 32 ₂₁ In the joint area between the heads, the total area of the overexposed area and the underexposed area with respect to the ideal double exposure can be minimized. As shown in the lower part of FIG. Uniform exposure extremely close to double exposure can be realized.

In the above example, when the light spot of a specific constituting the regions 72 covered with hatched in FIG. 15, the X-coordinate of the exposure area _{32 12} of the light spot P (256, two), the exposure area _{32 21} of the light spot P (m, 1020) and P (m-1,1020) without comparison of the X-coordinate of the immediately, P from point P of the exposure area _{32 21 (1,1020) (m-} 2 , 1020) may be specified as a micromirror that is not used during the main exposure. In that case, in the connecting area between the heads, a micromirror is actually used that minimizes the area of an overexposed area with respect to an ideal double exposure and does not cause an underexposed area. It can be selected as a micromirror.
Further, the micro-mirrors corresponding to P (m-1,1020) from point P of the exposure area _{32 21} (1,1020), it may be specified as micro mirrors not used in this exposure. In that case, in the connecting region between the heads, a micromirror is actually used in which the area of the region that is underexposed with respect to the ideal double exposure is minimized and the region that is not overexposed does not occur. It can be selected as a micromirror.
Further, in the connecting area between the heads, the number of pixel units (the number of light spots) in an area that is overexposed with respect to an ideal double drawing and the number of pixel units (the number of light spots) in an area that is underexposed. It is good also as selecting the micromirror actually used so that it may become equal.

  As described above, according to the specification method of the used pixel part of the present embodiment (2) using the pattern forming apparatus 10, the resolution variation caused by the relative position shift in the X-axis direction of the plurality of exposure heads Density unevenness can be reduced, and ideal N-fold exposure can be realized.

(3) Specification method of used pixel parts between a plurality of exposure heads <2>
In this embodiment (3), the pattern forming apparatus 10 performs double exposure on the photosensitive material 12 and is a head that is an overlapped exposure region on the exposed surface formed by a plurality of exposure heads 30. In the intermittent region, the deviation of the relative positions of the two exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) in the X-axis direction from the ideal state, the mounting angle error of each exposure head, and the two exposure heads A description will be given of a method for designating a used pixel part for reducing the variation in resolution and density unevenness caused by the relative mounting angle error between them and realizing ideal double exposure.

As the set tilt angle of each exposure head 30, that is, each DMD 36, in an ideal state where there is no mounting angle error of the exposure head 30, a usable 1024 column × 256 row pixel element (micromirror 58) is provided. It is assumed that an angle slightly larger than the angle θ _ideal that is used for exactly double exposure is adopted.
This angle θ _ideal is a value obtained in the same manner as the above embodiment (1) using the above equations 1 to 3, and in this embodiment, s = 256 and N = 2 as described above. The angle θ _ideal is about 0.45 degrees. Therefore, for example, an angle of about 0.50 degrees may be employed as the set inclination angle θ. It is assumed that the pattern forming apparatus 10 is initially adjusted so that the mounting angle of each exposure head 30, that is, each DMD 36 is close to the set inclination angle θ within an adjustable range.

FIG. 16 shows a mounting angle error of two exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) in the pattern forming apparatus 10 in which the mounting angles of the exposure heads 30, that is, the DMDs 36 are initially adjusted as described above, the influence of the deviation of the relative mounting angle error and the relative position between the exposure heads 30 ₁₂ and 30 ₂₁ is an explanatory view showing an example of unevenness that occurs in the pattern on the exposed surface.

In the example of FIG. 16, exposure by every other light spot group (pixel column groups A and B) as a result of the relative position shift of the exposure heads 30 ₁₂ and 30 _{21 in} the X-axis direction is the same as the example of FIG. In both exposure patterns 32 ₁₂ and 32 ₂₁ , the exposure amount overlaps on the coordinate axis perpendicular to the scanning direction of the exposure head on the exposed surface of the exposure areas 32 ₁₂ and 32 ₂₁ , which is more than the ideal double exposure state. A region 74 is generated, which causes uneven density.
Further, in the example of FIG. 16, it is difficult to finely adjust the result of setting the tilt angle θ of each exposure head slightly larger than the angle θ _ideal satisfying the formula (1) and the mounting angle of each exposure head. Therefore, as a result of the actual mounting angle deviating from the set inclination angle θ, even in regions other than the exposure region overlapping on the coordinate axis perpendicular to the scanning direction of the exposure head on the exposed surface, In the connection region between the pixel part columns, which is an overlapped exposure region on the exposed surface, formed by a plurality of pixel part columns, both in the exposure pattern by every other light spot group (pixel column group A and B). A region 76 that is overexposed than the ideal double exposure state is generated, and this causes further density unevenness.

In this embodiment (3), first, the use pixel selection process for reducing the uneven density due to the influence of the deviation of the mounting angle error and relative mounting angle of the exposure heads 30 ₁₂ and 30 _21.
Specifically, a set of a slit 28 and a photodetector is used as the light spot position detecting means, and an actual inclination angle θ ′ is specified for each of the exposure heads 30 ₁₂ and 30 ₂₁ , and the actual inclination angle θ ′ is set. Based on this, it is assumed that processing for selecting a micromirror to be used for actual exposure is performed using an arithmetic unit connected to a photodetector as the pixel part selection means.

-Specification of actual inclination angle θ'-
The actual inclination angle θ ′ is specified with respect to the positions of the light spots P (1, 1) and P (256, 1) in the exposure area 32 ₁₂ for the exposure head 30 _{12 and in the} exposure area 32 ₂₁ for the exposure head 30 ₂₁ . The positions of the light spots P (1,1024) and P (256,1024) are detected by the combination of the slit 28 and the photodetector used in the above-described embodiment (2), and the inclination angle of the straight line connecting them. And the angle formed by the scanning direction of the exposure head.

-Identification of unused pixel parts-
The arithmetic device connected to the photodetector using the actual inclination angle θ ′ thus specified is similar to the following equation 4 similar to the arithmetic device in the embodiment (1) described above.
ttanθ ′ = N (Formula 4)
The natural number T closest to the value t satisfying the above relationship is derived for each of the exposure heads 30 ₁₂ and 30 ₂₁ , and the micromirrors in the (T + 1) th to 256th rows on the DMD 36 are not used for the main exposure. Processing to identify as a micromirror is performed.
For example, T = 254 for the exposure head _{30 12,} when T = 255 was derived for the exposure head _3O21, micro mirrors corresponding to light spots constituting the parts 78 and 80 covered with hatched in FIG. 17 These are specified as micromirrors that are not used for the main exposure. As a result, in each of the exposure areas 32 ₁₂ and 32 ₂₁ other than the head-to-head connection area, the total area of the overexposed area and the underexposed area with respect to the ideal double exposure is minimized. be able to.

Here, instead of deriving the natural number closest to the above value t, the minimum natural number greater than or equal to the value t may be derived. In this case, exposure is performed for ideal double exposure in each of the exposure areas 32 ₁₂ and 32 ₂₁ other than the head-to-head connection area, which is an overlapping exposure area on the exposed surface formed by a plurality of exposure heads. It is possible to minimize the area where the amount is excessive and to prevent an area where the exposure amount is insufficient.
Or it is good also as deriving the maximum natural number below value t. In this case, exposure is performed for ideal double exposure in each of the exposure areas 32 ₁₂ and 32 ₂₁ other than the head-to-head connection area, which is an overlapping exposure area on the exposed surface formed by a plurality of exposure heads. It is possible to minimize the area of the insufficient region and prevent the region from being overexposed.
In each area other than the head-to-head connection area, which is an overlapping exposure area on the exposed surface formed by a plurality of exposure heads, the number of pixel units (light It is also possible to identify micromirrors that are not used during the main exposure so that the number of pixel units (the number of light points) in the underexposed region is equal to the number of points.

Thereafter, with respect to the micromirror corresponding to the light spots other than the light spots constituting the regions 78 and 80 covered by the oblique lines in FIG. 17, the same processing as that of the present embodiment (3) described with reference to FIGS. In FIG. 17, the micromirrors corresponding to the light spots constituting the shaded area 82 and the shaded area 84 are identified and added as micromirrors that are not used during the main exposure.
With respect to the micromirrors that are specified not to be used at the time of exposure, a signal for setting the angle of the always-off state is sent by the pixel element control means, and these micromirrors are substantially exposed. Not involved.

  As described above, according to the method for designating the used picture element portion of the present embodiment (3) using the pattern forming apparatus 10, the relative position shift in the X-axis direction of the plurality of exposure heads and the attachment of each exposure head Variations in resolution and density unevenness due to angle errors and relative mounting angle errors between exposure heads can be reduced, and ideal N-fold exposure can be realized.

  As described above, the method for designating the used pixel portion by the pattern forming apparatus 10 has been described in detail. However, the above-described embodiments (1) to (3) are merely examples, and various modifications can be made without departing from the scope of the present invention. It is.

  In the above embodiments (1) to (3), as a means for detecting the position of the light spot on the exposed surface, a set of the slit 28 and the single cell type photodetector is used. The present invention is not limited to this, and any form may be used. For example, a two-dimensional detector may be used.

  Further, in the above embodiments (1) to (3), the actual inclination angle θ ′ is obtained from the position detection result of the light spot on the exposed surface by the combination of the slit 28 and the photodetector, and the actual inclination angle θ ′ is obtained. The micromirrors to be used are selected based on the above, but a usable micromirror may be selected without the derivation of the actual inclination angle θ ′. Furthermore, for example, the reference exposure using all available micromirrors is performed, and the micromirror used by the operator is manually specified by checking the resolution and density unevenness by visual observation of the reference exposure results. It is included in the scope of the invention.

In addition to the angular distortion described in the above example, there are various forms of pattern distortion that can occur on the exposed surface.
As an example, as shown in FIG. 18A, there is a form of magnification distortion in which light rays from each micromirror 58 on the DMD 36 reach the exposure area 32 on the exposure surface at different magnifications.
As another example, as shown in FIG. 18B, there is a form of beam diameter distortion in which the light from each micromirror 58 on the DMD 36 reaches the exposure area 32 on the exposed surface with a different beam diameter. . These magnification distortion and beam diameter distortion are mainly caused by various aberrations and alignment deviation of the optical system between the DMD 36 and the exposed surface.
As yet another example, there is a form of light amount distortion in which light beams from the micromirrors 58 on the DMD 36 reach the exposure area 32 on the exposed surface with different light amounts. In addition to various aberrations and misalignment, this light amount distortion is caused by the positional dependence of the transmittance of the optical element between the DMD 36 and the exposed surface (for example, the lenses 52 and 54 in FIG. 5 which is a single lens) and the light amount by the DMD 36 itself. Caused by unevenness. These forms of pattern distortion also cause unevenness in resolution and density in the pattern formed on the exposed surface.

  According to the above embodiments (1) to (3), the residual elements of pattern distortion in these forms after selecting the micromirrors actually used for the main exposure are the same as the residual elements of angular distortion described above. It is possible to level out by the effect of filling by multiple exposure, and the unevenness of resolution and density can be reduced over the entire exposure area of each exposure head.

<< Reference exposure >>
As a modified example of the above embodiments (1) to (3), among available micromirrors, it corresponds to (N-1) every micromirror column or 1 / N rows of all light spot rows. A reference exposure is performed using only a group of micromirrors constituting an adjacent row, and among the micromirrors used for the reference exposure, micromirrors that are not used at the time of actual exposure are specified so that uniform exposure can be realized. It is good as well.
The result of the reference exposure by the reference exposure means is output as a sample, and the output reference exposure result is analyzed to confirm resolution variation and density unevenness and to estimate the actual inclination angle. The analysis of the result of the reference exposure may be a visual analysis by an operator.

FIG. 19 is an explanatory diagram showing an example of a form in which reference exposure is performed using only a single (N-1) row of micromirrors using a single exposure head.
In this example, it is assumed that double exposure is performed during the main exposure, and therefore N = 2. First, reference exposure is performed using only the micromirrors corresponding to the odd-numbered light spot rows indicated by the solid lines in FIG. 19A, and the reference exposure results are output as samples. Based on the reference exposure result outputted from the sample, it is possible to specify a micromirror to be used in the main exposure by confirming variations in resolution and density unevenness, or estimating an actual inclination angle.
For example, a micromirror other than the micromirror corresponding to the light spot array shown by hatching in FIG. 19B is designated as actually used in the main exposure among the micromirrors constituting the odd light spot array. . For even-numbered light spot arrays, reference exposure may be performed separately in the same manner, and the micromirror used during the main exposure may be designated, or the same pattern as that for the odd-numbered light spot arrays may be applied. Good.
By specifying the micromirrors used in the main exposure as described above, in the main exposure using both the odd-numbered and even-numbered micromirrors, a state close to ideal double exposure can be realized.

FIG. 20 is an explanatory diagram showing an example of a form in which reference exposure is performed using only a plurality of (N-1) rows of micromirrors using a plurality of exposure heads.
In this example, it is assumed that double exposure is performed during the main exposure, and therefore N = 2. First, reference is made using only micromirrors corresponding to odd-numbered light spot rows of two exposure heads adjacent to each other in the X-axis direction (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) shown by a solid line in FIG. Exposure is performed, and a reference exposure result is output as a sample. Based on the output reference exposure result, the variation in resolution and density unevenness in the area other than the joint area between the heads formed on the exposed surface by the two exposure heads are confirmed, or the actual inclination angle is estimated. Thus, the micromirror to be used at the time of the main exposure can be designated.
For example, the micromirrors other than the micromirrors corresponding to the light spot rows in the area 86 shown by hatching in FIG. 20 and the shaded area 88 are among the micromirrors constituting the odd-numbered light spots during the main exposure. Specified as actually used. For even-numbered light spot arrays, reference exposure may be performed separately in the same manner, and a micromirror used in the main exposure may be designated, or the same pattern as that for the odd-numbered pixel columns may be applied. Good.
In this way, in the main exposure using both the odd-numbered and even-numbered micromirrors by designating the micromirrors that are actually used during the main exposure, the two exposure heads form the surface to be exposed. A state close to ideal double exposure can be realized in a region other than the head-to-head connection region.

FIG. 21 is an explanatory diagram showing an example of a form in which reference exposure is performed using a single exposure head and using only micromirror groups constituting adjacent rows corresponding to 1 / N rows of the total number of light spots. It is.
In this example, it is assumed that double exposure is performed during the main exposure, and therefore N = 2. First, reference exposure is performed using only micromirrors corresponding to the light spots in the first to 128 (= 256/2) rows indicated by the solid line in FIG. 21A, and the reference exposure results are output as samples. Based on the reference exposure result outputted from the sample, a micromirror to be used in the main exposure can be designated.
For example, a micromirror other than the micromirror corresponding to the light spot group indicated by hatching in FIG. 21B is designated as actually used in the main exposure among the micromirrors in the first to 128th rows. Can be done. For the micromirrors in the 129th to 256th rows, reference exposure may be separately performed in the same manner, and the micromirrors used in the main exposure may be designated, or the micromirrors in the first to 128th rows may be designated. The same pattern as that for the mirror may be applied.
By designating the micromirror to be used at the time of the main exposure in this way, a state close to an ideal double exposure can be realized in the main exposure using the entire micromirror.

In FIG. 22, a plurality of exposure heads are used, and two adjacent exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) adjacent to each other in the X-axis direction are adjacent to each other corresponding to 1 / N rows of the total number of light spot rows. It is explanatory drawing which showed an example of the form which performs reference exposure using only the micromirror group which comprises a line.
In this example, it is assumed that double exposure is performed during the main exposure, and therefore N = 2. First, reference exposure is performed using only micromirrors corresponding to the light spots in the first to 128th (= 256/2) rows shown by the solid line in FIG. 22, and the reference exposure results are output as samples. . Based on the reference exposure result outputted from the sample, it is possible to realize the main exposure in which the variation in resolution and the density unevenness in the region other than the joint region between the heads formed on the exposed surface by the two exposure heads are minimized. In addition, it is possible to designate a micromirror to be used during the main exposure.
For example, micromirrors other than the micromirrors corresponding to the light spot arrays in the region 90 shown by hatching in FIG. 22 and the region 92 shown by shading are included in the micromirrors in the first to 128th rows. Designated as actually used at the time of exposure. For the micromirrors in the 129th to 256th rows, reference exposure may be separately performed in the same manner, and the micromirrors used for the main exposure may be designated, or the micromirrors in the first to 128th rows may be designated. The same pattern as that for the mirror may be applied.
In this way, by specifying the micromirror to be used during the main exposure, a state close to ideal double exposure is realized in an area other than the inter-head connecting area formed on the exposed surface by two exposure heads. it can.

  In the above embodiments (1) to (3) and the modified examples, the case where the main exposure is the double exposure has been described. However, the present invention is not limited to this, and any multiple exposure more than the double exposure may be used. . In particular, by setting the exposure to about 3 to 7 exposures, high resolution can be secured, and exposure with reduced variations in resolution and density unevenness can be realized.

  Further, in the exposure apparatus according to the embodiment and the modified example, the dimension of the predetermined part of the two-dimensional pattern represented by the image data is matched with the dimension of the corresponding part that can be realized by the selected use pixel. A mechanism for converting image data is preferably provided. By converting the image data in this way, a high-definition pattern according to a desired two-dimensional pattern can be formed on the exposed surface.

[Development process]
The developing step is a step of forming a pattern by exposing the photosensitive layer in the photosensitive film by the exposing step, curing the exposed region of the photosensitive layer, and developing by removing the uncured region. is there.
The developing step can be preferably performed by, for example, developing means.
The developing means is not particularly limited as long as it can be developed using a developer, and can be appropriately selected according to the purpose. For example, means for spraying the developer, means for applying the developer And means for immersing in the developer. These may be used alone or in combination of two or more.
In addition, the developing unit may include a developer replacing unit that replaces the developer, a developer supplying unit that supplies the developer, and the like.

  There is no restriction | limiting in particular as said developing solution, According to the objective, it can select suitably, For example, an alkaline 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 liquid 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.

The pH of the weak alkaline aqueous solution is, for example, 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.

[Curing process]
The curing treatment step is a step of performing a curing treatment on the formed pattern after the developing step is performed on the photosensitive layer.

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

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

Examples of the entire surface heat treatment method include a method of heating the entire surface of the photosensitive laminate on which the permanent pattern is formed after the developing step. By heating the entire surface, the film strength of the surface of the permanent pattern is increased.
As heating temperature in the said whole surface heating, 120-250 degreeC is preferable and 120-200 degreeC is more preferable. 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.
As heating time in the said whole surface heating, 10 to 120 minutes are preferable and 15 to 60 minutes are more preferable.
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.

-Protective film, interlayer insulating film, solder resist pattern formation method-
When the permanent pattern forming method forms at least one of a protective film, an interlayer insulating film, and a solder resist pattern, a permanent pattern is formed on the printed wiring board by the permanent pattern forming method. Soldering can be performed as follows.
That is, by the development, a hardened layer that is the permanent pattern is formed, and the metal layer is exposed on the surface of the printed board. Gold plating is performed on the portion of the metal layer exposed on the surface of the printed circuit board, and then soldering is performed. Then, a semiconductor or a component is mounted on the soldered portion. At this time, the permanent pattern by the hardened layer exhibits a function as a protective film, an insulating film (interlayer insulating film), or a solder resist, and prevents external impact and conduction between adjacent electrodes.

  In the pattern forming apparatus and the permanent pattern forming method, when the permanent pattern formed by the permanent pattern forming method is the protective film or the interlayer insulating film, the wiring can be protected from external impact or bending. In particular, the interlayer insulating film is useful for high-density mounting of semiconductors and components on, for example, a multilayer wiring board and a build-up wiring board.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.
(Example 1)
-Preparation of pigment dispersion-
The following components were prepared by dispersing for 3 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 1.0 mm using a mill type disperser (manufactured by Eiger, Motor Mill M-200).
Color pigment (CI Pigment Green 7) 0.23 parts by mass Inorganic filler (barium sulfate (manufactured by Sakai Chemical Co., Ltd., B30) dispersion) 30.0 parts by mass Dicyandiamide ... 0.92 parts by mass. 2MA-OK (trade name, 2,4-diamino-6- {2'-methylimidazole- (1 ')}-ethyl-s-triazine isocyanuric acid, manufactured by Shikoku Kasei Kogyo Co., Ltd.) Adduct) ... 0.56 parts by mass / PR300P-CP (trade name: Showa High Polymer Co., Ltd., trade name: cresol novolak type epoxy resin after ring opening addition of acrylic acid, tetrahydrophthalic anhydride is added to the resulting hydroxy group 67.3% propylene glycol monomethyl ether acetate solution of the resin obtained in this manner) ... 10.0 parts by mass / propyl acetate: 36.6 parts by mass

-Preparation of photosensitive composition coating solution-
The following components were mixed to prepare a photosensitive composition solution.
[Composition of photosensitive composition coating solution]
-Pigment dispersion liquid-82.9 parts by mass-Cyclomer P-ACA200 (trade name, manufactured by Daicel): methyl methacrylate / methacrylic acid / 2-hydroxy-4-acryloyloxymethylcyclohexyl methacrylate copolymer, molar composition ratio = 30/35/35, bromine number _{= 36gBr} 2 / 100g, acid value = 118MgKOH / g, weight average molecular weight = 15,000 solid concentration = 45% by weight of propylene glycol monomethyl ether solution) ... 53.9 weight Parts / Epicoat 1004 (trade name: Bisphenol A type epoxy resin manufactured by Japan Epoxy Resin Co., Ltd.) ... 14.3 parts by mass / DPHA (trade name manufactured by Nippon Kayaku: Dipentaerythritol hexaacrylate) ... 18.9 mass 2-β-naphthothiazolyl phenyl ketone (hereinafter referred to as “D1 ): Neutral heterocyclic ketone compound: 1.4 parts by mass. CGI325 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd .: (2-acetyloxyiminomethyl) -thioxanthen-9-one, (Referred to as “OE39”): Neutral O-acyloxime compound: 1.5 parts by mass. F780F (trade name: Fluorosurfactant, 30% by mass methyl ethyl ketone solution, manufactured by DIC) 0.57 Parts by mass, hydroquinone monomethyl ether 0.04 parts by mass

-Production of photosensitive film-
A 25 μm thick polyethylene terephthalate film (Lumirror 16FB50, manufactured by Toray Industries, Inc.) was used as a support, and the photosensitive composition coating solution was dried on the support by a bar coater, so that the thickness of the photosensitive layer after drying was about 30 μm. And then dried in a hot air circulating drier for 30 minutes at 80 ° C., and then a polypropylene film having a thickness of 12 μm was laminated as a protective film on the photosensitive layer to produce a photosensitive film. .

-Solder resist pattern formation-
--- Preparation of photosensitive laminate--
As the substrate, a surface of a copper-clad laminate (printed wiring board having no through hole and a copper thickness of 12 μm) on which wiring was formed as a printed board was prepared by subjecting it to chemical polishing treatment. A vacuum laminator (manufactured by Nichigo Morton Co., Ltd., VP130) 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. A photosensitive laminate was prepared in which the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) were laminated in this order.
The pressure bonding conditions were a 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.

--Exposure process--
For the photosensitive layer in the prepared photosensitive laminate, from the polyethylene terephthalate film (support) side, a pattern forming apparatus (INPREX-IP3500, manufactured by Fuji Photo Film Co., Ltd.) by blue-violet laser exposure having a predetermined pattern is used. , A laser beam of 405 nm was irradiated with an energy amount of 40 mJ / cm ² so as to obtain a predetermined pattern, and was exposed to cure a part of the photosensitive layer.

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

-Curing process-
The entire surface of the photosensitive laminate on which the solder resist pattern was formed was heated at 150 ° C. for 1 hour to cure the surface of the solder resist pattern and increase the film strength.

[Evaluation]
The sensitivity film, the resolution, the shortest development time, the storage stability, and the edge roughness were evaluated for the photosensitive film and the photosensitive laminate under the following conditions. The results are shown in Table 2.
The solder resist pattern was evaluated for pencil hardness, adhesion, solvent resistance, acid resistance, alkali resistance, solder heat resistance, insulation resistance, gold plating resistance, and thermal shock resistance under the following conditions. The results are shown in Table 3.

<Minimum development time>
The polyethylene terephthalate film (support) is peeled off from the photosensitive laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. is sprayed at a pressure of 0.15 MPa over the entire surface of the photosensitive layer on the copper clad laminate. The time required from the start of spraying of the aqueous sodium solution until the photosensitive layer on the copper clad laminate was dissolved and removed was measured, and this was taken as the shortest development time.

<Sensitivity>
Wherein the photosensitive layer in the photosensitive laminate from the polyethylene terephthalate film (support) side, a patterning device having a 405nm laser light source as the light irradiation unit, 0.1 mJ / cm ² from 2 ¹ A portion of the photosensitive layer was cured by irradiating with light having different light energy amounts up to 100 mJ / cm < ² > at intervals of ^{/ 2} . After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) is peeled off from the photosensitive laminate, and an aqueous sodium carbonate solution (30 ° C., 1% by mass) is formed on the entire surface of the photosensitive layer on the copper clad laminate. Was sprayed at a spray pressure of 0.15 MPa for twice the minimum development time to dissolve and remove the uncured region, and the thickness of the remaining cured region 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 thus obtained, the amount of light energy when the thickness of the cured region was the same as that before exposure was defined as the amount of light energy (sensitivity) necessary for curing the photosensitive layer.
The pattern forming apparatus has a light modulation unit made of the DMD.

<Resolution>
The photosensitive laminate was allowed to stand for 10 minutes at room temperature (23 ° C., 55% RH). From the obtained polyethylene terephthalate film (support) of the photosensitive laminate, exposure of each line width is performed in increments of 1 μm from 5 μm to 20 μm with a line / space = 1/1 by using the pattern forming apparatus. Each line width was exposed in increments of 5 μm from a line width of 20 μm to 50 μm. The exposure amount at this time is the amount of light energy required to cure the photosensitive layer determined by the sensitivity measurement. After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) was peeled off from the photosensitive laminate. Spray the entire surface of the photosensitive layer on the copper-clad laminate with a sodium carbonate aqueous solution (30 ° C., 1% by mass) as the developer at a spray pressure of 0.15 MPa for twice the shortest development time determined by the above method. Then, the uncured region was dissolved and removed. Observe the surface of the copper-clad laminate with a solder resist pattern as a permanent pattern obtained in this way with an optical microscope, and measure the minimum line width without any abnormalities such as tsumari and twist on the solder resist pattern line, This was the resolution. The smaller the numerical value, the better the resolution.

<Storage stability>
The obtained sheet of photosensitive film was put in a light-proof moisture-proof bag (BF3X manufactured by Tokai Aluminum Foil Co., Ltd.) made of black vinyl and an aluminum foil laminated structure, and stored in a dry oven at 40 ° C. for 3 days. Thereafter, the film sheet was removed, subjected to the shortest development time test described above after laminated on a substrate, and measured the shortest developing time (t _3).
The time required for development was compared with the shortest development time (t ₀ ) on the photosensitive film production day. Specifically, the t ₃ / t ₀ ratio value obtained was evaluated according to the following criteria.
-Evaluation criteria-
○: 1.0 to 1.3
Δ: 1.3-1.8
X: 1.8 or more

<Evaluation of edge roughness>
The photosensitive laminate was exposed using the pattern forming apparatus, and a pattern was formed on a part of the photosensitive layer in the same manner as in the resolution measurement. Among the obtained patterns, arbitrary five points of a line having a line width of 50 μm were observed using a laser microscope (VK-9500, manufactured by Keyence Corporation; objective lens 50 ×), and among the edge positions in the field of view Then, the difference between the most swollen portion (mountain peak portion) and the most constricted portion (valley bottom portion) was obtained as an absolute value, and an average value of five observed positions was calculated, and this was defined as edge roughness. The edge roughness is preferably as the value is small because it exhibits good performance.

<Pencil hardness>
The above-mentioned photosensitive film was vacuum laminated on a copper-clad laminate without a circuit pattern after peeling off the protective film. After this was cooled to room temperature, it was exposed under the conditions of an exposure amount of 500 mJ / cm ² , and cured at 150 ° C. for 60 minutes in a hot air circulating drying furnace, and then cooled to room temperature to obtain an evaluation sample.

  In accordance with the test method of JIS K-5400, a pencil hardness tester was used to determine the highest hardness at which the film was not scratched when a load of 1 kg was applied to the evaluation sample.

<Adhesion>
According to JIS K5400, 100 1 mm grids were produced in the permanent pattern after curing, and a peel test was performed using a cellophane tape. The peeled state of the grid was observed and evaluated according to the following criteria.
-Evaluation criteria-
○: No peeling at 90/100 or more Δ: No peeling at 50/100 or more to less than 90/100 ×: No peeling at 0/100 to less than 50/100

<Solvent resistance>
The cured permanent pattern was immersed in isopropyl alcohol for 30 minutes at room temperature, and after confirming that there was no abnormality in appearance, a peel test was performed using a cellophane tape.
-Evaluation criteria-
○: No abnormality in the appearance of the coating film and no peeling.
X: The appearance of the coating film is abnormal or peels off.

<Acid resistance>
The cured permanent pattern was immersed in a 10% by mass aqueous hydrochloric acid solution at room temperature for 30 minutes, and after confirming that there was no abnormality in the appearance, a peel test was performed using a cellophane tape.
-Evaluation criteria-
○: No abnormality in the appearance of the coating film and no peeling.
X: The appearance of the coating film is abnormal or peels off.

<Alkali resistance>
The cured permanent pattern was immersed in a 5% by mass aqueous sodium hydroxide solution at room temperature for 30 minutes, and after confirming that there was no abnormality in appearance, a peel test was performed using a cellophane tape.
-Evaluation criteria-
○: No abnormality in the appearance of the coating film and no peeling.
X: The appearance of the coating film is abnormal or peels off.

<Solder heat resistance>
A rosin-based flux or a water-soluble flux was applied to the permanent pattern after curing, and was immersed in a solder bath at 260 ° C. for 10 seconds. This was defined as one cycle, and after repeating 6 cycles, the appearance of the coating film was visually observed.
-Evaluation criteria-
○: There is no abnormality (peeling or swelling) in the appearance of the coating film, and there is no solder dent.
X: The appearance of the coating film is abnormal (peeling or swelling) or has a solder dent.

<Insulation resistance>
Using IPC-B-25 comb-shaped test pattern B, applying a photomask for pattern B, exposing the entire surface at 40 mJ / cm ² with the laser device, and 30% at 60 ° C. with 1% by mass aqueous sodium carbonate solution Development, washing and drying were carried out, and a test substrate was prepared by post-heating treatment at 150 ° C. for 1 hour. According to the test method of IPC-SM-840B, the insulation resistance in the normal state was measured and evaluated according to the following criteria.
-Evaluation criteria-
○: Insulation resistance value is 10 ¹⁰ Ω or more ×: Insulation resistance value is less than 10 ¹⁰ Ω

<Gold resistance>
The cured permanent pattern was immersed in an acidic degreasing solution (manufactured by Nihon McDermitt, 20 vol% aqueous solution of Metex L-5B) for 3 minutes, and then washed with water.
Next, after immersing in a 14.4% by volume aqueous ammonium persulfate solution at room temperature for 3 minutes, it was washed with water, and further immersed in a 10% by volume sulfuric acid aqueous solution at room temperature for 1 minute, followed by washing with water.
Next, this test substrate is immersed in a 30 ° C. catalyst solution (Meltex, 10 volume% aqueous solution of Melplate Activator 350) for 7 minutes, washed with water, and 85 ° C. nickel plating solution (Meltex, Melplate). Ni-865M 10 volume% sulfuric acid aqueous solution) was immersed for 1 minute at room temperature and then washed with water.
Next, the test substrate was immersed in a gold plating solution at 95 ° C. (Meltex, 15% by volume of Aurolectroles UP and 3% by volume of potassium gold cyanide, pH 6) for 10 minutes, followed by electroless gold plating. This was washed with water, further immersed in warm water at 60 ° C. for 3 minutes, washed with water and dried. The obtained electroless gold plating evaluation board was observed and evaluated according to the following criteria.
-Evaluation criteria-
○: No abnormality at all.
X: Bad plating adhesion or dent due to plating was observed.

<Heat shock resistance>
As a reliability test item, the appearance and the resistance value change rate of the permanent pattern after curing were evaluated by a temperature cycle test (TCT). TCT was performed using a vapor-phase cooling / heating tester, and the electronic component module was left in a vapor phase at temperatures of −55 ° C. and 125 ° C. for 30 minutes, and this was performed under the conditions of 1,000 cycles.
-Evaluation criteria-
○: No crack occurred △: Shallow crack occurred ×: Deep crack occurred

(Examples 2-8, Example 13, and Example 14)
In Example 1, except that the type and content of the neutral heterocyclic ketone compound were changed as shown in Table 1, sensitivity, resolution, shortest development time, storage stability, edge were the same as in Example 1. Roughness, pencil hardness, adhesion, solvent resistance, acid resistance, alkali resistance, solder heat resistance, insulation resistance, gold plating resistance, and thermal shock resistance were evaluated. The results are shown in Tables 2 and 3.

Example 9
In Example 1, except that the type and content of the neutral O-acyloxime compound were changed as shown in Table 1, sensitivity, resolution, shortest development time, storage stability, Edge roughness, pencil hardness, adhesion, solvent resistance, acid resistance, alkali resistance, solder heat resistance, insulation resistance, gold plating resistance, and thermal shock resistance were evaluated. The results are shown in Tables 2 and 3.

(Example 10, Example 11, and Examples 19-22)
In Example 1, except that the hydrogen donor compound shown in Table 1 was added, sensitivity, resolution, shortest development time, storage stability, edge roughness, pencil hardness, adhesion, solvent resistance were the same as in Example 1. Evaluation of heat resistance, acid resistance, alkali resistance, solder heat resistance, insulation resistance, gold plating resistance, and thermal shock resistance. The results are shown in Tables 2 and 3.

(Example 12)
In Example 1, except that double exposure was performed instead of the pattern forming apparatus described below, sensitivity, resolution, shortest development time, storage stability, edge roughness, The pencil hardness, adhesion, solvent resistance, acid resistance, alkali resistance, solder heat resistance, insulation resistance, gold plating resistance, and thermal shock resistance were evaluated. The results are shown in Tables 2 and 3.

<< Pattern Forming Apparatus >>
A combined laser light source described in JP-A-2005-258431 as the light irradiating means, and a micromirror array in which 1024 micromirrors 58 are arranged in the main scanning direction schematically shown in FIG. 6 as the light modulating means. , DMD 36 controlled to drive only 1024 × 256 rows out of 768 sets arranged in the sub-scanning direction, and an optical system for imaging the light shown in FIG. 5A or FIG. 5B on the pattern forming material, The pattern forming apparatus 10 including the exposure head 30 having the above is used.

As the set inclination angle of each exposure head 30, that is, each DMD 36, an angle slightly larger than the angle θ _{ideal at} which double exposure is performed using a usable 1024 column × 256 row micromirror 58 was adopted. This angle θ _ideal is equal to the number N of N double exposures, the number s of usable micromirrors 58 in the column direction, the interval p of usable micromirrors 58 in the column direction, and the microscopic exposure head 30 in a tilted state. For the pitch δ of the scanning line formed by the mirror,
spsinθ _ideal ≧ Nδ (Formula 1)
Given by. As described above, the DMD 36 according to the present embodiment includes a large number of micromirrors 58 having equal vertical and horizontal arrangement intervals arranged in a rectangular lattice shape.
pcosθ _ideal = δ (Formula 2)
And the above equation 1 is
stanθ _ideal = N (Formula 3)
Since s = 256 and N = 2, the angle θ _ideal is about 0.45 degrees. Therefore, for example, 0.50 degrees is adopted as the set inclination angle θ.

First, the state of the exposure pattern on the exposed surface was examined in order to correct the variation in resolution and uneven exposure in double exposure. The results are shown in FIG. In FIG. 16, the pattern of light spots from the micromirror 58 that can be used by the DMD 36 of the exposure heads 30 ₁₂ and 30 ₂₁ projected onto the exposed surface of the stacked body 12 with the stage 14 being stationary. showed that. The state of the exposure pattern formed on the exposed surface when the stage 14 is moved and the continuous exposure is performed with the light spot group pattern as shown in the upper part appearing in the lower part. Are shown for exposure areas 32 ₁₂ and 32 ₂₁ . In FIG. 16, for convenience of explanation, every other column exposure pattern of the micromirror 58 that can be used is divided into an exposure pattern by the pixel column group A and an exposure pattern by the pixel column group B. The actual exposure pattern on the exposed surface is a superposition of these two exposure patterns.

As shown in FIG. 16, as a result of the deviation of the relative position between the exposure heads 30 ₁₂ and 30 ₂₁ from the ideal state, both the exposure pattern by the pixel column group A and the exposure pattern by the pixel column group B are both. Thus, it can be seen that, in the exposure areas overlapping on the coordinate axes orthogonal to the scanning direction of the exposure head in the exposure areas 32 ₁₂ and 32 ₂₁ , an overexposed area is generated as compared with the ideal double exposure state.

The use of a set of slits 28 and a photodetector as a light spot position detection means, the position of the point P of the exposure head _{30 12} For the exposure area _{32 12} (1,1) and P (256,1), the exposure head For 30 ₂₁ , the positions of the light spots P (1,1024) and P (256, 1024) in the exposure area 32 ₂₁ are detected, and the angle formed by the inclination angle of the straight line connecting them and the scanning direction of the exposure head is determined. It was measured.

Using the actual inclination angle θ ′, the following equation 4
ttanθ ′ = N (Formula 4)
The natural number T closest to the value t satisfying the relationship is derived for each of the exposure heads 30 ₁₂ and 30 ₂₁ . T = 254 for the exposure head _{30 12,} the exposure head _{30 21} T = 255 was derived respectively. As a result, the micromirrors constituting the portions 78 and 80 covered with diagonal lines in FIG. 17 were identified as micromirrors that are not used during the main exposure.

Thereafter, the micromirrors corresponding to the light spots other than the light spots constituting the regions 78 and 80 covered with the oblique lines in FIG. 17 were similarly covered with the shaded areas 82 and the shaded areas in FIG. Micromirrors corresponding to the light spots constituting the region 84 were identified and added as micromirrors that are not used during the main exposure.
With respect to the micromirrors that are specified not to be used at the time of exposure, a signal for setting the angle of the always-off state is sent by the pixel element control means, and these micromirrors are substantially exposed. It was controlled not to be involved.
As a result, in each of the exposure areas 32 ₁₂ and 32 ₂₁ , an ideal double exposure is performed in each area other than the inter-head connection area, which is an overlapping exposure area on the exposed surface formed by the plurality of exposure heads. Thus, the total area of the overexposed region and the underexposed region can be minimized.

(Examples 15 to 18)
In Example 1, except that the content of the neutral heterocyclic ketone compound was changed as shown in Table 1, in the same manner as in Example 1, sensitivity, resolution, shortest development time, storage stability, edge roughness, The pencil hardness, adhesion, solvent resistance, acid resistance, alkali resistance, solder heat resistance, insulation resistance, gold plating resistance, and thermal shock resistance were evaluated. The results are shown in Tables 2 and 3.

(Comparative Example 1 and Comparative Example 2)
In Example 1, the sensitivity, resolution, shortest development time, and storage stability were the same as in Example 1 except that the components shown in Table 1 were added as a radical generator instead of the neutral O-acyloxime compound. Property, edge roughness, pencil hardness, adhesion, solvent resistance, acid resistance, alkali resistance, solder heat resistance, insulation resistance, gold plating resistance, and thermal shock resistance were evaluated. The results are shown in Tables 2 and 3.

(Comparative Example 3)
In Example 9, the sensitivity, resolution, shortest development time, and storage stability were the same as in Example 1 except that the components shown in Table 1 were added as the sensitizing dye instead of the neutral heterocyclic ketone compound. , Edge roughness, pencil hardness, adhesion, solvent resistance, acid resistance, alkali resistance, solder heat resistance, insulation resistance, gold plating resistance, and thermal shock resistance were evaluated. The results are shown in Tables 2 and 3.

(Comparative Example 4)
In Example 1, as a sensitizing dye and a radical generator, the components shown in Table 1 were added in place of the neutral heterocyclic ketone compound and the neutral O-acyloxime compound, respectively, and the hydrogen donor compound was used. Except for the addition, sensitivity, resolution, shortest development time, storage stability, edge roughness, pencil hardness, adhesion, solvent resistance, acid resistance, alkali resistance, solder heat resistance, insulation resistance are the same as in Example 1. Evaluation of gold plating resistance and thermal shock resistance was performed. The results are shown in Tables 2 and 3.

(Comparative Example 5)
In Example 1, except that the neutral heterocyclic ketone compound was not added, the sensitivity, resolution, shortest development time, storage stability, edge roughness, pencil hardness, adhesion, resistance, and the like were the same as in Example 1. Solvent resistance, acid resistance, alkali resistance, solder heat resistance, insulation resistance, gold plating resistance, and thermal shock resistance were evaluated. The results are shown in Tables 2 and 3.

(Comparative Example 6)
In Example 1, except that the neutral O-acyloxime compound was not added, the sensitivity, resolution, shortest development time, storage stability, edge roughness, pencil hardness, adhesion, Solvent resistance, acid resistance, alkali resistance, solder heat resistance, insulation resistance, gold plating resistance, and thermal shock resistance were evaluated. The results are shown in Tables 2 and 3.

(Comparative Example 7)
In Example 1, instead of a neutral heterocyclic ketone compound, an acidic heterocyclic ketone compound (2-β-naphthothiazolyl 4-carboxyphenyl ketone, hereinafter referred to as “D33”) was added. As in 1, sensitivity, resolution, shortest development time, storage stability, edge roughness, pencil hardness, adhesion, solvent resistance, acid resistance, alkali resistance, solder heat resistance, insulation resistance, gold plating resistance, and heat resistance The impact property was evaluated. The results are shown in Tables 2 and 3.

(Comparative Example 8)
In Example 1, a basic heterocyclic ketone compound (2-β-naphthothiazolyl 4-dimethylaminophenyl ketone, hereinafter referred to as “D34”) was added in place of the neutral heterocyclic ketone compound. In the same manner as in Example 1, sensitivity, resolution, minimum development time, storage stability, edge roughness, pencil hardness, adhesion, solvent resistance, acid resistance, alkali resistance, solder heat resistance, insulation resistance, gold plating resistance, The thermal shock resistance was evaluated. The results are shown in Tables 2 and 3.

(Comparative Example 9)
In Example 1, a basic O-acyloxime compound (p-dimethylaminoacetophenone-O-acetyloxime, hereinafter referred to as “OE40”) was added in place of the neutral O-acyloxime compound. In the same manner as in Example 1, sensitivity, resolution, shortest development time, storage stability, edge roughness, pencil hardness, adhesion, solvent resistance, acid resistance, alkali resistance, solder heat resistance, insulation resistance, gold plating resistance And thermal shock resistance were evaluated. The results are shown in Tables 2 and 3.

The formal names of the components indicated by abbreviations in Table 1 are as follows.
D1: 2-β-naphthothiazolyl phenyl ketone D10: 2-benzothiazolyl-p-methoxyphenyl ketone D11: 2-benzothiazolyl-p-chlorophenyl ketone D20: 2-benzothiazolyl-2-thienyl ketone D21: bis (2-benzothiazolyl) ) Ketone D22: 2-benzothiazolyl-p-methoxy-α-styryl ketone D23: 5-chloro-2-benzothiazolyl-p-methylphenylketone D24: 2-benzoxazolyl-p-methoxy-α-styryl ketone D28: 4,5-bis (2-furyl) thiazolyl phenyl ketone D31: γ-naphth-2-thiazolyl phenyl ketone D33: 2-β-naphthothiazolyl 4-carboxyphenyl ketone (acidic heterocyclic ketone compound)
D34: 2-β-naphthothiazolyl 4-dimethylaminophenyl ketone (basic heterocyclic ketone compound)
OE1: 1- (4-Phenylsulfanylphenyl) -butane-1,2-dione 2-oxime-O-benzoate OE39: (2-acetyloxyiminomethyl) -thioxanthen-9-one OE40: p-dimethylamino Acetophenone-O-acetyloxime (basic O-acyloxime compound)
EAB: 4,4′-bis (N, N-diethylamino) benzophenone Irgacure 819: bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide Irgacure 369: 1- (4-morpholinophenyl) -2-benzyl-2-dimethyl Aminobutan-1-one H1: N-phenylglycine H2: 4-benzoyl-4′-methyldiphenyl sulfide H3: 1-phenyl-2-mercapto-1,3-benzimidazole H4: tetra (n-butyl) ammonium n -Butyltriphenylborate H5: Dimedone H6: N-ethyl-N, N-dihydroxyethylamine

From the results of Table 2 and Table 3, Examples 1-22 using a photosensitive composition in which the photopolymerization initiation system compound includes a neutral heterocyclic ketone compound and a neutral O-acyloxime compound are highly sensitive. In addition, it has been found that a high-definition permanent pattern can be formed with high resolution, good storage stability, good properties required for a solder resist.
Further, it was found that the pattern of Example 12 in which the variation in resolution and the exposure unevenness in the double exposure were corrected also had small edge roughness.

The photosensitive composition and photosensitive film of the present invention have high sensitivity and high resolution, good storage stability, and have good properties required to form a high-definition permanent pattern. For this reason, it can be particularly suitably used for forming a permanent pattern such as a solder resist on a printed circuit board.
Since the permanent pattern forming method of the present invention includes the photosensitive film of the present invention, it can be suitably used particularly for forming a high-definition solder resist pattern on a printed board.

FIG. 1 is a perspective view showing an appearance of an example of a pattern forming apparatus. FIG. 2 is a perspective view showing an example of the configuration of the scanner of the pattern forming apparatus. FIG. 3A is a plan view showing an exposed region formed on the exposed surface of the photosensitive layer. FIG. 3B is a plan view showing an arrangement of exposure areas by each exposure head. FIG. 4 is a perspective view showing an example of a schematic configuration of the exposure head. FIG. 5A is a top view showing an example of a detailed configuration of the exposure head. FIG. 5B is a side view showing an example of a detailed configuration of the exposure head. FIG. 6 is a partially enlarged view showing an example of the DMD of the pattern forming apparatus of FIG. FIG. 7A is a perspective view for explaining the operation of the DMD. FIG. 7B is a perspective view for explaining the operation of the DMD. FIG. 8 is an explanatory diagram showing an example of unevenness that occurs in the pattern on the exposed surface when there is an exposure head mounting angle error and pattern distortion. FIG. 9 is a top view showing a positional relationship between an exposure area by one DMD and a corresponding slit. FIG. 10 is a top view for explaining a method of measuring the position of the light spot on the exposed surface using a slit. FIG. 11 is an explanatory diagram showing a state in which unevenness generated in a pattern on an exposed surface is improved as a result of using only selected micromirrors for exposure. FIG. 12 is an explanatory diagram showing an example of unevenness that occurs in the pattern on the exposed surface when there is a relative position shift between adjacent exposure heads. FIG. 13 is a top view showing a positional relationship between an exposure area by two adjacent exposure heads and a corresponding slit. FIG. 14 is a top view for explaining a method of measuring the position of the light spot on the exposed surface using a slit. FIG. 15 is an explanatory diagram showing a state in which only the used pixels selected in the example of FIG. 12 are actually moved and the unevenness in the pattern on the exposed surface is improved. FIG. 16 is an explanatory diagram showing an example of unevenness that occurs in the pattern on the exposed surface when there is a relative position shift and a mounting angle error between adjacent exposure heads. FIG. 17 is an explanatory diagram showing exposure using only the used pixel portion selected in the example of FIG. FIG. 18A is an explanatory diagram showing an example of magnification distortion. FIG. 18B is an explanatory diagram showing an example of beam diameter distortion. FIG. 19A is an explanatory diagram showing a first example of reference exposure using a single exposure head. FIG. 19B is an explanatory diagram showing a first example of reference exposure using a single exposure head. FIG. 20 is an explanatory diagram showing a first example of reference exposure using a plurality of exposure heads. FIG. 21A is an explanatory diagram showing a second example of reference exposure using a single exposure head. FIG. 21B is an explanatory diagram showing a second example of reference exposure using a single exposure head. FIG. 22 is an explanatory view showing a second example of reference exposure using a plurality of exposure heads.

Explanation of symbols

10 pattern forming device 12 photosensitive laminate (photosensitive layer, photosensitive material)
DESCRIPTION OF SYMBOLS 14 Moving stage 18 Installation stand 20 Guide 22 Gate 24 Scanner 26 Sensor 28 Slit 30 Exposure head 32 Exposure area 36 Digital micromirror device (DMD)
38 Fiber array light source 58 Micro mirror (picture element)
111 Multicavity laser 113 Rod lens 114 Lens array 140 Laser array

Claims (10)

  A photosensitive material comprising a binder, a polymerizable compound, a photopolymerization initiation system compound, and a thermal crosslinking agent, wherein the photopolymerization initiation system compound comprises a neutral heterocyclic ketone compound and a neutral O-acyloxime compound. Sex composition. The neutral heterocyclic ketone compound is represented by the following general formula (I), and the neutral O-acyloxime compound is represented by the following general formulas (II-1) to (II-4). Photosensitive composition.
However, in said general formula (I), X < ₁ > and X < ₂ > represent either the alkyl group, the aryl group, and heteroaryl group which may have a substituent each independently, X < ₁ > and X < ₂ >. And may combine with each other to form a 5- to 7-membered ring. X represents a monovalent nonmetallic atomic group. Y represents either an oxygen atom or a sulfur atom.
However, the general formula (II-1) in ~ (II-4), R 1 is a phenyl group, an alkyl group, a cycloalkyl group, a halogenated alkyl group, an alkanoyl group, a benzoyl group, an alkoxycarbonyl group, a phenoxycarbonyl group , CONR ¹⁴ R ¹⁵ , CN, NO ₂ , an aryl group, and a diphenylphosphinoyl group. R ² represents any one of an alkanoyl group, an alkenoyl group, a benzoyl group, an alkoxycarbonyl group, and a phenoxycarbonyl group. R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are each independently a hydrogen atom, halogen atom, alkyl group, cyclopentyl group, cyclohexyl group, phenyl group, benzyl group, benzoyl group, alkanoyl group, alkoxycarbonyl Represents any of a group, a phenoxycarbonyl group, OR ¹² , SR ¹³ , SOR ¹³ , and SO ₂ R ¹³ . R ⁸ represents any of an alkoxycarbonyl group, a phenoxycarbonyl group, a cycloalkyl group, CONR ¹⁴ R ¹⁵ , CN, a phenyl group, and an alkyl group. R ⁹ , R ¹⁰ , and R ¹¹ are each independently a hydrogen atom, halogen atom, alkyl group, cyclopentyl group, cyclohexyl group, phenyl group, benzyl group, benzoyl group, alkanoyl group, alkoxycarbonyl group, phenoxycarbonyl group, One of OR ¹² , SR ¹³ , SOR ¹³ , and SO ₂ R ¹³ is represented. R ¹² represents a hydrogen atom, an alkyl group, (CH ₂ CH ₂ O) nH, an alkanoyl group, an alkenyl group, an alkenoyl group having 3 to 6 carbon atoms, and a phenyl group, and n represents an integer of 1 to 20. R ¹³ represents either an alkyl group or a phenyl group. R ¹⁴ and R ¹⁵ each independently represents any of a hydrogen atom, an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkenyl group, a cycloalkyl group, a phenyl group, an alkanoyl group, an alkenoyl group, and a benzoyl group. M represents any one of an alkylene group, a cyclohexylene group, and a phenylene group.   Neutral heterocyclic ketone compounds are 2-β-naphthothiazolyl phenyl ketone, 2-benzothiazolyl-2-thienyl ketone, bis (2-benzothiazolyl) ketone, 2-benzothiazolyl-p-methoxy-α-styryl ketone, 5-chloro-2-benzothiazolyl-p-methylphenylketone, 2-benzoxazolyl-p-methoxy-α-styrylketone, 4,5-bis (2-furyl) thiazolylphenylketone, and γ-naphtho The photosensitive composition according to claim 1, which is any one of 2-thiazolyl phenyl ketone.   The photosensitive composition according to any one of claims 1 to 3, wherein the neutral O-acyloxime compound is (2-acetyloxyiminomethyl) -thioxanthen-9-one.   The photosensitive composition according to claim 1, wherein the photopolymerization initiating compound contains a hydrogen donor compound.   6. The photosensitive composition according to claim 5, wherein the hydrogen donor compound is any one of 1-phenyl-2-mercapto-1,3-benzimidazole and tetra (n-butyl) ammonium-n-butyltriphenylborate. object.   The photosensitive composition according to claim 1, wherein the content ratio of the neutral heterocyclic ketone compound to the neutral O-acyloxime compound is 1: 6 to 6: 1.   A photosensitive film comprising a support and a photosensitive layer comprising the photosensitive composition according to claim 1 on the 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 method for forming a permanent pattern according to claim 9.