JP2007310027A - Photosensitive composition, photosensitive film, photosensitive laminate, permanent pattern forming method, and printed circuit board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition for efficiently forming a highly permanent pattern by including a dendritic branch compound having a polymerization group as a polymerization compound, having excellent sensitivity, excellent resolution, and excellent hardening characteristics as a permanent protective film, and having small exudation (end face fusion) of the photosensitive composition from a filmed roll, and to provide a photosensitive film, a photosensitive laminate, a permanent forming method using the photosensitive laminate, and a printed circuit board forming a permanent pattern by the permanent forming method. <P>SOLUTION: The photosensitive composition includes an oxime derivative by a photo-initiator by including a binder, the polymerization compound, and the photo-initiator, and including the dendritic branch compound having the polymerization compound. The photosensitive film, and the photosensitive laminate are provided. In addition, the permanent pattern forming method using the photosensitive laminate and the printed circuit board forming the permanent pattern by the permanent pattern forming method are provided. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention is excellent in sensitivity, resolution, and storage stability, and is capable of efficiently forming a high-definition pattern (such as a protective film, an interlayer insulating film, and a solder resist pattern), a photosensitive composition, a photosensitive film, and photosensitivity. The present invention relates to a laminate, a permanent pattern forming method using the photosensitive laminate, and a printed board on which a permanent pattern is formed by the permanent pattern forming method.

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

In the photosensitive composition, a solder resist using a binder containing a dendrimer compound has been proposed for the purpose of improving developability and flexibility after heat curing (see Patent Document 1).
However, in the above proposal, since dipentaerythritol hexaacrylate (DPHA) is used as a polymerizable compound, there is a problem that curing shrinkage after photopolymerization is large and flexibility effect after thermosetting is small.
Moreover, a polymerizable composition containing an alkali-soluble binder and a dendrimer compound as a polymerizable compound has been proposed for the purpose of achieving both high sensitivity and film properties of a cured film (Patent Document 2). reference).
However, in the above proposal, the dendrimer compound, which is one of the dendritic compounds, is included as the polymerizable compound, and basic film properties are separately provided with a binder, so that both high sensitivity and cured film characteristics can be achieved. Although it is intended, the cured product characteristics are not sufficient in the field where it is used as a permanent protective film.

  Therefore, by containing the dendritic compound as the polymerizable compound, the sensitivity, resolution, and cured product properties as a permanent protective film are excellent, and the photosensitive composition oozes out from the roll formed into a film (end face fusion). , A photosensitive composition that can efficiently form a high-definition permanent pattern (such as a protective film, an interlayer insulating film, and a solder resist pattern), a photosensitive film, a pattern forming method using the photosensitive film, and the A printed circuit board on which a permanent pattern is formed by a permanent pattern forming method has not yet been provided, and the present situation is that further improvement and development are desired.

JP 2004-300303 A JP 2005-134893 A

  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 includes a dendritic compound having a polymerizable group as a polymerizable compound, and thus has excellent sensitivity, resolution, and cured product characteristics as a permanent protective film, and a photosensitive composition from a filmed roll. Photosensitive composition, photosensitive film, and photosensitive laminate capable of efficiently forming high-definition permanent patterns (protective films, interlayer insulating films, solder resist patterns, etc.) with little oozing (edge fusion) Another object is to provide a pattern forming method using the photosensitive laminate, and a printed board on which a permanent pattern is formed by the permanent pattern forming method.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive studies, including a binder, a polymerizable compound, and a photopolymerization initiator, wherein the polymerizable compound includes a dendritic compound having a polymerizable group, In addition, the photosensitive composition in which the photopolymerization initiator contains an oxime derivative is excellent in sensitivity, resolution, and cured product characteristics as a permanent protective film, and the photosensitive composition oozes out from the roll formed into a film (end face melting). It has been found that high-definition permanent patterns can be efficiently formed.

The present invention is based on the above findings of the present inventors, and means for solving the above problems are as follows. That is,
<1> including a binder, a polymerizable compound, and a photopolymerization initiator,
The photosensitive composition is characterized in that the polymerizable compound contains a dendritic compound having a polymerizable group, and the photopolymerization initiator contains an oxime derivative.
<2> The photosensitive composition according to <1>, wherein the dendritic compound having a polymerizable group is any of a dendrimer compound and a hyperbranched compound having at least two polymerizable groups.
<3> Either a dendrimer compound or a hyperbranched compound in which a dendritic compound having a polymerizable group is formed by either a polycondensation reaction or a polyaddition reaction of a compound having two kinds of functional groups in one molecule. The photosensitive composition according to any one of <1> to <2>.
<4> The photosensitive composition according to any one of <1> to <3>, wherein the dendritic compound having a polymerizable group has an ester bond.
<5> The photosensitive composition according to any one of <1> to <4>, wherein the oxime derivative has a partial structure represented by any one of the following general formula (I) and the following general formula (II): is there.
In the general formula (I) and (II), Ar represents an aromatic group, or a heterocyclic group, Y ¹ represents any substituent of a hydrogen atom and monovalent, Y ² represents an aliphatic group, an aromatic group, a heterocyclic group, COY ³ , CO ₂ Y ³ , or CONY ⁴ Y ⁵ , and Y ³ , Y ⁴ , and Y ⁵ are an aliphatic group, It represents either an aromatic group or a heterocyclic group, and m represents an integer of 1 or more.
<6> The photosensitive composition according to <5>, wherein Ar in the general formulas (I) and (II) has either a phenyl group or a naphthyl group.
<7> The photosensitive composition according to <6>, wherein Ar in the general formulas (I) and (II) is a naphthyl group.

<8> The photosensitive composition according to any one of <1> to <7>, including a thermal crosslinking agent.
<9> The thermal crosslinking agent according to <8>, 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. Of the photosensitive composition.
<10> The photosensitive composition according to any one of <8> to <9>, wherein the thermal crosslinking agent is alkali-insoluble.
<11> The photosensitive composition according to any one of <1> to <10>, wherein the binder is alkali-soluble.
<12> The photosensitive composition according to any one of <1> to <11>, wherein the binder includes a polymer compound having an acidic group and an ethylenically unsaturated bond in a side chain.
<13> A binder in which a polymerizable compound containing a cyclic ether group is added to part of an acidic group of a polymer compound in the presence of a catalyst, and a part or all of the cyclic ether group of the polymer compound is carboxylated The polymer compound selected from any of those obtained by adding a polymerizable compound containing a group in the presence of a catalyst, wherein the catalyst is selected from either an acidic compound or a neutral compound Of the photosensitive composition.
<14> The binder according to any one of <1> to <13>, wherein the binder includes a polymer compound having an acidic group, an aromatic group that may include a heterocyclic ring, and an ethylenically unsaturated bond in a side chain. It is a photosensitive composition.
<15> The photosensitive composition according to any one of <12> to <14>, wherein the polymer compound contains 0.5 to 3.0 meq / g of an ethylenically unsaturated bond.
<16> Any one of <12> to <15>, wherein the polymer compound has a carboxyl group in a side chain, and the content of the carboxyl group in the polymer compound is 1.0 to 4.0 meq / g. It is a photosensitive composition as described above.
<17> The photosensitive composition according to any one of <12> to <16>, wherein the polymer compound has a mass average molecular weight of 10,000 or more and less than 100,000.
<18> The photosensitive composition according to any one of <12> to <17>, wherein the polymer compound contains 20 mol% or more of a structural unit represented by the following general formula (A-1).
However, in said general formula (A-1), R < ₁ >, R < ₂ > and R < ₃ > represent a hydrogen atom or monovalent organic group. L represents an organic group and may not be present. Ar represents an aromatic group that may contain a heterocycle.
<19> The tourism composition according to any one of <1> to <11>, wherein the binder includes an epoxy acrylate compound.

<20> The photosensitive composition according to any one of <1> to <19>, wherein the photosensitive composition contains a sensitizer.
<21> The photosensitive composition according to <20>, wherein the sensitizer includes a hetero-fused ring compound.
<22> The photosensitive composition according to <21>, wherein the hetero-fused ring compound is a thioxanthone compound.

<23> A photosensitive film comprising a support and a photosensitive layer comprising the photosensitive composition according to any one of <1> to <22> on the support. .
<24> The photosensitive film according to <23>, wherein the support includes a synthetic resin and is transparent.
<25> The photosensitive film according to any one of <23> to <24>, wherein the support has a long shape.
<26> The photosensitive film according to any one of <23> to <25>, which is long and wound in a roll shape.
<27> The photosensitive film according to any one of <23> to <26>, wherein the photosensitive film has a protective film on the photosensitive layer.

<28> A photosensitive laminate comprising a photosensitive layer comprising the photosensitive composition according to any one of <1> to <22> on a substrate.
<29> The photosensitive laminate according to <28>, wherein the photosensitive layer is formed of the photosensitive film according to any one of <23> to <27>.
<30> The photosensitive laminate according to any one of <28> to <29>, wherein the photosensitive layer has a thickness of 1 to 100 μm.

<31> A photosensitive layer in the photosensitive laminate according to any one of <28> to <30>,
A pattern forming apparatus comprising: a light irradiating unit capable of irradiating light; and a light modulating unit configured to modulate light from the light irradiating unit and to expose the photosensitive layer. In the pattern forming apparatus according to <31>, 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.
<32> The light modulation unit further includes a pattern signal generation unit that generates a control signal based on pattern information to be formed, and the control signal generated by the pattern signal generation unit generates light emitted from the light irradiation unit. It is a pattern formation apparatus as described in said <31> modulated according to. In the pattern forming apparatus according to <32>, 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.
<33> The light modulation means has n pixel parts, and forms any less than n pixel parts continuously arranged from the n pixel parts. The pattern forming apparatus according to any one of <31> to <32>, which is controllable according to pattern information. In the pattern forming apparatus according to <33>, any less than n pixel parts arranged continuously among n pixel parts in the light modulation unit are controlled according to pattern information. Thereby, the light from the light irradiation means is modulated at high speed.
<34> The pattern forming apparatus according to any one of <31> to <33>, wherein the light modulation unit is a spatial light modulation element.
<35> The pattern forming apparatus according to <34>, wherein the spatial light modulation element is a digital micromirror device (DMD).
<36> The pattern forming apparatus according to any one of <33> to <35>, wherein the picture element portion is a micromirror.
<37> The pattern forming apparatus according to any one of <31> to <36>, wherein the light irradiation unit can synthesize and irradiate two or more lights. In the pattern forming apparatus according to <37>, the light irradiation unit can synthesize and irradiate two or more lights, whereby 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.
<38> The light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that condenses the laser beams irradiated from the plurality of lasers and couples the laser beams to the multimode optical fiber. <31> to the pattern forming apparatus according to any one of <37>. In the pattern forming apparatus according to <38>, 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.

<39> A method for forming a permanent pattern, comprising exposing the photosensitive layer in the photosensitive laminate according to any one of <28> to <30>.
<40> The method for forming a permanent pattern according to <39>, wherein the exposure is performed using a laser beam having a wavelength of 350 to 415 nm.
<41> The permanent pattern forming method according to any one of <39> to <40>, wherein the exposure is performed imagewise based on pattern information to be formed.

<42> Exposure 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 portion in accordance with pattern information, wherein the column direction of the picture element portion forms a predetermined set inclination angle θ with respect to the scanning direction of the exposure head. Using an exposure head arranged as follows:
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 <39> to <41>, 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 <42>, the exposure head is subjected to N multiple exposures (where N is a natural number of 2 or more) of the usable pixel parts by the used pixel part designating unit. 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.
<43> The exposure is performed by a plurality of exposure heads, and the used drawing element specifying means is related to the exposure of the joint area between the heads which is the overlapping exposure area on the exposed surface formed by the plurality of exposure heads. The permanent pattern forming method according to <42>, wherein among the element parts, the image element part used for realizing N double exposure in the inter-head connection region is designated. In the method for forming a permanent pattern according to <43>, the exposure is performed by a plurality of exposure heads, and the used image element designating unit is an overlapping exposure region on the 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. For example, a high-definition pattern is formed by developing the photosensitive layer thereafter.
<44> 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 <43>, wherein the image element portion used for realizing N double exposure in an area other than the inter-head connection area among the image element parts is designated. In the method for forming a permanent pattern according to <44>, the exposure is performed by a plurality of exposure heads, and the used pixel portion 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. For example, a high-definition pattern is formed by developing the photosensitive layer thereafter.
<45> When the set inclination angle θ is N, the number N of the multiple exposures, the number s of the pixel portions in the column direction, the interval p in the column direction of the pixel portions, 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 <42> to <44>. The method for forming a permanent pattern according to any one of <44>.
<46> The method for forming a permanent pattern according to any one of <42> to <45>, wherein N in N-fold exposure is a natural number of 3 or more. In the permanent pattern forming method according to <46>, multiple drawing is performed when N in N-exposure 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.

<47> Use pixel part designation means,
A light spot position detecting means for detecting a light spot position as a pixel unit that is generated by the picture element unit and constitutes an exposure area on the exposed surface;
<42> to <46>, 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.
<48> The permanent pattern forming method according to any one of <42> to <47>, wherein the used pixel part specifying unit specifies the used pixel part used for realizing N double exposure in units of rows. It is.

<49> The fact that the light spot position detector detects the row direction of the light spot on the surface to be exposed and the scanning direction of the exposure head when the exposure head is tilted based on the detected at least two light spot positions. 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.
<50> 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 <49>, wherein the permanent pattern forming method is one of a maximum value and a minimum value.
<51> The pixel part selection means derives a natural number T close to t that satisfies the relationship of t tan θ ′ = N (where N represents N of N double exposure numbers) based on the actual inclination angle θ ′, and m <47> to <50>, wherein the pixel elements from the first line to the T-th line are selected as used graphic elements in a line (where m represents a natural number of 2 or more) arranged graphic elements. The permanent pattern forming method according to any one of the above.
<52> The pixel part selection means derives a natural number T close to t satisfying a relationship of t tan 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 in the (T + 1) -th line to the 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 <47> to <51>, wherein the pixel part excluding the element part is selected as a used pixel part.

<53> 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 the above <47>, which is one of means for selecting a pixel part to be used so that an area of an underexposed area is minimized and an overexposed area does not occur with respect to typical N double exposure <52> The permanent pattern forming method according to any one of the above.
<54> In the connection area between the heads, which is an overlapping exposure area 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 <47> to <53>.
<55> The permanent pattern forming method according to <54>, wherein the unused pixel parts are specified in units of rows.

<56> In order to specify the used pixel part in the used pixel part specifying means, among the usable pixel parts, N (n-1) pixel part columns for N multiple exposures The permanent pattern forming method according to any one of <42> to <55>, wherein the reference exposure is performed by using only the image element portion that constitutes. In the permanent pattern forming method according to the above <56>, 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.
<57> In order to specify the used pixel part in the used pixel part specifying means, among the usable pixel parts, for each N-exposure N, a pixel part line is formed every 1 / N lines. The permanent pattern forming method according to any one of <42> to <55>, wherein the reference exposure is performed using only the pixel part. In the permanent pattern forming method according to the above <57>, in order to designate the use pixel part in the use pixel part designating unit, among the usable picture element parts, N is 1 for N double exposure. / Reference exposure is performed using only the pixel part constituting the pixel part column for every N rows, and a simple permanent pattern of substantially single drawing is obtained. As a result, the picture element portion in the head-to-head connection region is easily specified.

<58> From the above <42> to <57>, the used pixel part designation means includes a slit and a photodetector as the light spot position detection means, and an arithmetic unit connected to the photodetector as the pixel part selection means. The permanent pattern forming method according to any one of the above.
<59> The method for forming a permanent pattern according to any one of <42> to <58>, wherein N in N-exposure exposure is a natural number of 3 or more and 7 or less.

<60> The light modulation means further includes a 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. The method for forming a permanent pattern according to any one of <42> to <59>, wherein the modulation is performed according to. In the permanent pattern forming apparatus according to <60>, since the light modulation unit includes the pattern signal generation unit, light emitted from the light irradiation unit is converted into a control signal generated by the pattern signal generation unit. Modulated accordingly.
<61> The method for forming a permanent pattern according to any one of <42> to <60>, wherein the light modulator is a spatial light modulator.
<62> The method for forming a permanent pattern according to <61>, wherein the spatial light modulation element is a digital micromirror device (DMD).
<63> The permanent pattern forming method according to any one of <42> to <62>, wherein the picture element portion is a micromirror.
<64> From the above <42> to <42> having conversion means for converting the pattern information so that the dimension of the predetermined part of the pattern represented by the pattern information matches the dimension of the corresponding part that can be realized by the designated used pixel part 63>. The permanent pattern forming method according to any one of 63>.

<65> The permanent pattern formation method according to any one of <42> to <64>, wherein the light irradiation unit can synthesize and irradiate two or more lights. In the permanent pattern forming method according to <65>, the light irradiation unit can synthesize and irradiate two or more lights, so that exposure is performed with exposure light having a deep focal depth. As a result, the exposure to the photosensitive film is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, a very fine permanent pattern is formed.
<66> 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. The permanent pattern forming method according to any one of <42> to <65>. In the method for forming a permanent pattern according to <66>, the light irradiation unit can collect the laser light respectively irradiated from the plurality of lasers by the collective optical system and be coupled to the multimode optical fiber. As a result, exposure is performed with exposure light having a deep focal depth. As a result, the exposure to the photosensitive film is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.

<67> The method for forming a permanent pattern according to any one of <39> to <66>, wherein the photosensitive layer is developed after the exposure. In the method for forming a permanent pattern according to <67>, a high-definition pattern is formed by developing the photosensitive layer after the exposure.
<68> The method for forming a permanent pattern according to <67>, wherein after the development, the photosensitive layer is cured.
<69> The method for forming a permanent pattern according to <68>, 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.

<70> A permanent pattern formed by the pattern forming method according to any one of <39> to <69>. Since the permanent pattern according to <70> 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 buildup wiring boards.
<71> The pattern according to <70>, which is at least one of a protective film, an interlayer insulating film, and a solder resist pattern. Since the permanent pattern according to the above <71> 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 insulating property, heat resistance, etc. of the film. Protected from.

  <72> A printed circuit board wherein a permanent pattern is formed by the method for forming a permanent pattern according to any one of <39> to <69>.

  According to the present invention, conventional problems can be solved, and by including a dendritic compound having a polymerizable group as a polymerizable compound, it has excellent sensitivity, resolution, and cured product properties as a permanent protective film, and A photosensitive composition, a photosensitive film, which can efficiently form a high-definition permanent pattern (such as a protective film, an interlayer insulating film, and a solder resist pattern) with less bleeding of the photosensitive composition from a filmed roll. A photosensitive laminate, a pattern forming method using the photosensitive laminate, and a printed board on which a permanent 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, and a photopolymerization initiator, and preferably contains a sensitizer and a thermal crosslinking agent. Further, if necessary, a coloring pigment, an extender pigment, It is preferable to contain other components, such as a thermosetting agent (curing accelerator of a thermal crosslinking agent), a thermal polymerization inhibitor, and a surfactant.

<Polymerizable compound>
The polymerizable compound includes a dendritic compound having a polymerizable group. The dendritic compound having a polymerizable group is not particularly limited as long as it is a compound having a polymerizable group and a dendritic branched structure, and can be appropriately selected depending on the purpose. For example, dendrimers Compound, hyperbranched compound and the like. In addition, about the said dendrimer compound, For example, Angew. Chem. , Int. Ed. 38, P884 (1999) and the like, the hyperbranched compound is described in, for example, Polym. Prepr. 29 (1988), etc., respectively.

The dendritic compound having a polymerizable group according to the present invention preferably contains at least two polymerizable groups. The dendritic compound having at least two polymerizable groups has a dendritic multi-branched structure composed of a core site, a branch site, a branch site, and a terminal site. FIG. 23 is a model diagram showing a standard structure of a dendritic compound having at least two polymerizable groups.
The central core part 110 has a plurality of branch parts 112A, the terminal part of the branch part 112A becomes a branch part 114, and a new branch part 112B branches from the branch part 114, and each branch part 112B has a terminal portion 116. The dendritic compound having at least two polymerizable groups has a structure in which at least two of the most terminal sites 116 have a polymerizable group. In this model diagram, the branch site 114 exists only at the end of the branch site 112A generated from the core site 110. However, the present invention is not limited to this, and the end of the branch site 112B continuous to the branch site 114 becomes the branch site. It may take a structure having a plurality of branch sites.
In general, in the case of a dendritic compound having a regularly regular polymerizable group, the size thereof is represented by a concept term of generation. If the dendritic branching compound having at least two polymerizable groups has a branched structure starting from the above-defined core portion, that is, a terminal portion (terminal group) at the tip of the branch portion 112A in FIG. The first part of the first-generation dendritic branching compound is referred to as a first-generation dendritic compound, and has a branched structure branched from the first-generation all terminal part (branch part 114 in FIG. 23), that is, the branched part 112B and the terminal located at the tip thereof The region up to site 116 is referred to as a second generation dendritic compound. This is defined as the generation in the dendritic compound having at least two polymerizable groups. The preferred size of the dendritic compound having at least two polymerizable groups is preferably 2 to 10 generations, more preferably 2 to 8 generations, and particularly preferably 2 to 6 generations.

Hereinafter, preferable structures of the core part, the branched part, the branch part, and the terminal part of the dendritic branched compound having at least two polymerizable groups will be sequentially described.
In the dendritic compound having at least two polymerizable groups, the core part preferably has a structure in which at least three branch parts are bonded.
Below, the typical structure of a core part is shown. Examples of the core portion composed of one atom include the following structural formula (ia) and structural formula (ib), and the center thereof is a trivalent or higher atom, for example, N, C, Etc. As what a core part is comprised with a cyclic compound, what is shown by following Structural formula (ic), Structural formula (id), Structural formula (ie) is mentioned, for example. Thus, the cyclic structure may be an aromatic ring structure, an alicyclic structure, or a heterocyclic structure.
In addition, a structure formed by combining a plurality of atoms around a multivalent atom as represented by the structural formula (if) or the structural formula (ig) or a metal atom can be exemplified as the core portion. The structure shown by the structural formula (if) or the structural formula (ig) exemplified here can be used not only as a core site but also as a branched site described later.
Note that the structures represented by the following structural formulas (i-h) to (ik) are examples of structures corresponding to only the core part, and the core part of this structure may have four or more branches. preferable.

In the structural formulas (ih) to (ik), Rx is an alkylene group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms.

The branch site in the dendritic compound having at least two polymerizable groups is a general term for components that bind one core site or branch site to an adjacent branch site or terminal site, and the structure is particularly limited. Not.
In addition, the total number of branch sites present in one molecule of the dendritic branched compound having a polymerizable group (the total of those linked directly to the core site and those linked to the branch site) is preferably 9 to 160, -130 are more preferable, and 18-100 are especially preferable.

The branching site of the dendritic branching compound having at least two polymerizable groups is composed of a trivalent or higher-valent atom or atomic group, and a bond with an adjacent core site or a connecting site located on the core site side, and a terminal direction There is no particular limitation as long as it has a bond with a plurality of branch sites linked to the above, and those having the same structure as the core site described above can be used, but usually a carbon atom, a nitrogen atom, or Are composed of atomic groups containing these atoms.
The dendritic branching compound having at least two polymerizable groups preferably has at least two polymerizable groups at the ends of the branch sites connected to the branch sites. As described above, the polymerizable group preferably has 6 to 180 in the molecule, more preferably 8 to 140, and particularly preferably 10 to 120 from the viewpoint of the effect.

The polymerizable group in the dendritic compound having at least two polymerizable groups is not particularly limited as long as it is a radical polymerizable group.
Preferred examples include α-substituted methylacrylic groups [—OC (═O) —C (—CH ₂ Z) ═CH ₂ (where Z is a hydrocarbon group starting from a heteroatom)], acrylic groups, and methacrylic groups. , An allyl group, a styryl group, and the like, among which an acryl group and a methacryl group are particularly preferable.
As is clear from the specific examples shown below, the polymerizable group may be present in all of the terminal sites of the dendritic branched compound, or may be present only in a part of the terminal sites.

  The dendritic compound having at least two polymerizable groups can be synthesized using a known method. A specific method is described in Shi W. et. Appl. Polym. Sci. 59, 12, 1945 (1996), Moszner N .; et. al. , Macromol. Chem. Phys. 197, 2, 621 (1996), Qichun W., et al. Scott R.D. et. al. , Pure Appl. Chem. A37 (11), 1301, (2000), Qichun W., et al. Scott R.D. et. al. , Pure Appl. Chem. , A39 (4), 267, (2000), Shikichi Yokoyama, Nobuo Masuko, Collection of Polymers, Vol 59, No. 10, 642 (2002).

  The dendritic compound having a polymerizable group of the present invention is not particularly limited in its structure, but is preferably obtained by polycondensation reaction or polyaddition reaction of compounds having two different functional groups in the molecule. In the compound having two different functional groups in the molecule, the two different functional groups do not undergo intramolecular condensation or intramolecular addition, but can cause a condensation reaction or addition reaction chemically with each other. Functional group. Examples of combinations of these functional groups include hydroxyl groups and carboxylic acid derivatives such as carboxylic acid groups and carboxylic acid alkyl ester groups, amino groups and carboxylic acid groups, halogenated alkyl groups and phenolic hydroxyl groups, acetoxy groups and carboxylic acid groups, and acetyl groups. And a hydroxyl group, an isocyanate group and a hydroxyl group, and the combination of a carboxylic acid group or a derivative thereof and a hydroxyl group or a derivative thereof is preferable from the viewpoint of simplicity of the reaction process and reaction control.

  Specific examples of the compound having two different functional groups in the molecule include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, diphenolic acid, and 5- (2hydroxyethoxy). Isophthalic acid, 5-acetoxyisophthalic acid, 3,5-bis (2-hydroxyethoxy) benzoic acid, 3,5-bis (2-hydroxyethoxy) benzoic acid methyl ester, 4,4- (4′-hydroxyphenyl) Pentanoic acid, 5-hydroxycyclohexane-1,3-dicarboxylic acid, 1,3-dihydroxy-5-carboxycyclohexane, 5- (2-hydroxyethoxy) cyclohexane-1,3-dicarboxylic acid, 1,3- (2- Hydroxyethoxy) -5-carboxycyclohexane, 5- (bromomethyl) -1,3-dihydroxybenzene, 3 5-diaminobenzoic acid, phenol-3,5-diglycidyl ether, one-to-one reaction product of isophorone diisocyanate and diisopropanolamine, one-to-one reaction product of isophorone diisocyanate and diethanolamine, 3,5-bis ( 4-aminophenoxy) benzoic acid and the like. Among these, 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid are preferable from the viewpoint of versatility as a raw material compound and simplicity of the polymerization reaction step.

  The dendritic compound having a polymerizable group used in the present invention is obtained by, for example, condensing a compound having two different functional groups in the molecule in the first step, and a large amount of hydroxyl or carboxylic acid groups at the terminal, or these In the second step, an unsaturated bond group such as an acrylate group or a methacrylate group is added to the functional group at the end of the molecule.

In the first stage reaction, the dendritic branched compound may be reacted alone in the presence of a condensation reaction catalyst, or a polyvalent hydroxy compound, a polyvalent carboxylic acid compound, or a compound having both of them is dendritic. It may be used as a branch point of a branched compound molecule.
Examples of the polyvalent hydroxy compound include various glycol compounds generally used as a polyester resin raw material, and trifunctional or higher functional hydroxyl group-containing compounds such as trimethylolpropane, pentaerythritol, and dipentaerythritol. Examples of the polyvalent carboxylic acid compound also include trifunctional or higher functional carboxylic acid compounds such as various dibasic acids, trimellitic acid, pyromellitic acid, and benzophenone tetracarboxylic acid that are commonly used as polyester resin raw materials. Furthermore, glycolic acid, hydroxypivalic acid, 3-hydroxy-2-methylpropionic acid, lactic acid, glyceric acid, malic acid, citric acid and the like can be given as examples of compounds having both a hydroxyl group and a carboxylic acid group.

  In addition to the above, the compound serving as the branching point of the dendritic compound molecule used in the present invention is a linear polyester oligomer obtained by a condensation reaction of a dibasic acid component and a glycol component, or a polyfunctional compound having three or more functional groups. A branched polyester oligomer obtained by copolymerizing a polyvalent carboxylic acid or a polyvalent hydroxy compound may be used.

As a constituent material of the linear or branched polyester oligomer that can be the branching point, various general dibasic acid compounds and glycol compounds, or tri- or higher functional polycarboxylic acids and polyhydric alcohol compounds can be used. .
Examples of the dibasic acid compound include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanoic acid and other aliphatic dibasic acids, terephthalic acid, isophthalic acid, orthophthalic acid, 1,2-naphthalenecarboxylic acid, 1, Aromatic dibasic acids such as 6-naphthalenedicarboxylic acid, or alicyclic dibasic acids such as 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid Is mentioned.

Examples of the glycol compound include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, and 1,4-butylene glycol. 2-methyl-1,3-propylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,4-diethyl-1, 5-pentanediol, 2-ethyl-1,3-hexanediol, 2,2-dimethyl-3-hydroxypropyl-2 ′, 2′-dimethyl-3-hydroxypropanoate, 2-nbutyl-2-ethyl- 1,3-propanediol, 3-ethyl-1,5-pentanediol, 3-propyl-1,5-penta Aliphatic diols such as diol, 2,2-diethyl-1,3-propanediol, 3-octyl-1,5-pentanediol, 1,3-bis (hydroxymethyl) cyclohexane, 1,4-bis ( Hydroxymethyl) cyclohexane, 1,4-bis (hydroxyethyl) cyclohexane, 1,4-bis (hydroxypropyl) cyclohexane, 1,4-bis (hydroxymethoxy) cyclohexane, 1,4-bis (hydroxyethoxy) cyclohexane, 2 , 2bis (4-hydroxymethoxycyclohexyl) propane, 2,2-bis (4hydroxyethoxycyclohexyl) propane, bis (4-hydroxycyclohexyl) methane, 2,2-bis (4-hydroxycyclohexyl) propane, 3 (4 ), 8 (9) -Tricyclo [5.2 1.0 ^2,6 ] alicyclic glycols such as decanedimethanol, or aromatic glycols such as ethylene oxide and propylene oxide adducts of bisphenol A.

  Furthermore, examples of the trifunctional or higher polyhydric carboxylic acid and polyhydric alcohol compound include trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, glycerin, trimethylolpropane, and pentaerythritol.

  In the first stage reaction, the condensed water produced by the condensation reaction is azeotropically dehydrated with toluene or xylene, or the inert gas is blown into the reaction system and the water or monoalcohol produced by the condensation reaction together with the inert gas. Is carried out by blowing out the reaction system or distilling it off under reduced pressure. As the catalyst used for the reaction, as with a normal polyester resin polymerization catalyst, various metal compounds such as titanium, tin, antimony, zinc and germanium, and strong acid compounds such as p-toluenesulfonic acid and sulfuric acid should be used. Can do.

Next, in the second-stage reaction, an unsaturated bond group such as acrylate or methacrylate is added to the dendritic compound obtained in the first stage and having a large amount of hydroxyl terminal or carboxylic acid terminal. Specific examples of the compound used in the case of a dendritic branched compound having a hydroxyl group at the end include a method by condensation with a monocarboxylic acid such as acrylic acid and methacrylic acid, and a method by addition of maleic anhydride. Alternatively, after converting the hydroxyl group to carboxylic acid with an acid anhydride compound such as succinic anhydride or trimellitic acid, it is also possible to introduce an unsaturated bond by reacting this carboxylic acid group with the glycidyl group of the glycidyl (meth) acrylate compound. It is.
On the other hand, when the terminal is a carboxylic acid group, a method by condensation with a monoalcohol such as 2-hydroxyethyl acrylate or 2-hydroxy methacrylate, or a method by reaction with a glycidyl group of a glycidyl (meth) acrylate compound can be mentioned. . Any method may be used for the synthesis of the dendritic branched compound of the present invention.

  In the reaction in the second stage, unsaturated bond groups may be introduced into all of the terminal functional groups of the dendritic compound obtained in the first stage, or partly introduced. It may be left unreacted.

  Examples of dendritic compounds having at least two polymerizable groups that can be suitably used in the present invention will be shown below [Exemplary compounds (M-1) to (M-24)], but the present invention is limited to these. Is not to be done. In addition, although an exemplary compound shows the example which all the terminal R substituted by the polymeric group, this is partially unreacted and may exist with a hydroxy group, a carboxyl group, an amino group, etc. as it is. In the case of the partial unreaction, it is preferable from the viewpoint of improving the polymerization reactivity that the number of substituted polymerizable groups is larger than the partially unreacted hydroxy group, carboxyl group, and amino group.

The dendritic compound having at least two polymerizable groups is preferably a multi-branched compound having a mass average molecular weight of 1,000 or more and having 6 or more polymerizable groups, and having a mass average molecular weight of 1,500 or more. It is more preferably a multi-branched compound having 8 or more polymerizable groups, and a compound having a mass average molecular weight of 2,000 or more and 10 or more polymerizable groups is particularly preferable.
There is no particular upper limit to the weight average molecular weight of the dendritic compound having at least two polymerizable groups, but from the viewpoint of developability and the like, it is preferably 20,000 or less, more preferably 15,000 or less. Particularly preferably, it is 10,000 or less. Moreover, it is preferable that a polymeric group is located in the terminal of each branched structure.

  As the polymerizable compound, in addition to the dendritic compound having the polymerizable group, a compound having one or more ethylenically unsaturated bonds may be used in combination.

  Examples of the ethylenically unsaturated bond include (meth) acryloyl group, (meth) acrylamide group, styryl group, vinyl group such as vinyl ester and vinyl ether, allyl group such as allyl ether and allyl ester, and the like.

  The compound having one or more ethylenically unsaturated bonds is not particularly limited and may be appropriately selected depending on the intended purpose. For example, at least one selected from monomers having a (meth) acryl group is Preferably mentioned.

  There is no restriction | limiting in particular as a monomer which has the said (meth) acryl group, According to the objective, it can select suitably, For example, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) ) Monofunctional acrylates and monofunctional methacrylates such as acrylates; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentylglycol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin Poly (functional) alcohols such as tri (meth) acrylate, trimethylolpropane, glycerin, bisphenol, etc., which are subjected to addition reaction with ethylene oxide and propylene oxide, and converted to (meth) acrylate, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50- Urethane acrylates described in JP-A-6034, JP-A-51-37193, etc .; JP-A-48-64183, JP-B-49-43191, JP-B-52-30 Polyester acrylates described in each publication of such 90 No.; and epoxy resin and (meth) polyfunctional acrylates or methacrylates such as epoxy acrylates which are reaction products of acrylic acid. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are particularly preferable.

  5-50 mass% is preferable and, as for solid content in the said photosensitive composition solid content of the said polymeric compound, 10-40 mass% is more preferable. If the solid content is less than 5% by mass, problems such as deterioration of developability and reduction in exposure sensitivity may occur, and if it exceeds 50% by mass, the adhesiveness of the photosensitive layer may become too strong. is there.

<Photopolymerization initiator>
The photopolymerization initiator includes an oxime derivative. There is no restriction | limiting in particular as said oxime derivative, Although it can select suitably according to the objective, It is preferable that it is a compound which has an aromatic group at least, and the following general formula (I) and the following general formula (II) It is more preferable that the compound has a partial structure represented by any of them. Two or more oxime derivatives may be used in combination.
In the general formula (I) and (II), Ar represents an aromatic group, or a heterocyclic group, Y ¹ represents any substituent of a hydrogen atom and monovalent, Y ² represents an aliphatic group, an aromatic group, a heterocyclic group, COY ³ , CO ₂ Y ³ , or CONY ⁴ Y ⁵ , and Y ³ , Y ⁴ , and Y ⁵ are an aliphatic group, It represents either an aromatic group or a heterocyclic group, and m represents an integer of 1 or more.

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

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

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

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

The heterocyclic (heterocyclic) group includes a pyrrole ring group, a furan ring group, a thiophene ring group, a benzopyrrole ring group, a benzofuran ring group, a benzothiophene ring group, a pyrazole ring group, an isoxazole ring group, and an isothiazole ring. Group, indazole ring group, benzisoxazole ring group, benzoisothiazole ring group, imidazole ring group, oxazole ring group, thiazole ring group, benzimidazole ring group, benzoxazole ring group, benzothiazole ring group, pyridine ring group, Quinoline ring group, isoquinoline ring group, pyridazine ring group, pyrimidine ring group, pyrazine ring group, phthalazine ring group, quinazoline ring group, quinoxaline ring group, acylidine ring group, phenanthridine ring group, carbazole ring group, purine ring group, Pyran ring group, piperidine ring group, piperazine ring group, morpholine ring group, India Ring group, indolizine ring group, chromene ring group, cinnoline ring group, acridine ring group, phenothiazine ring group, tetrazole ring group, triazine ring group, etc., among which furan ring group, thiophene ring group, imidazole ring group , Thiazole ring group, benzothiazole ring group, pyridine ring group, indole ring group, and acridine ring group are particularly preferable.
Moreover, these heterocyclic groups may have a substituent, and examples of such a substituent include a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom. For example, what was shown as a substituent in the below-mentioned alkyl group, a substituted alkyl group, or a substituted alkyl group can be mentioned.

  Examples of the monovalent substituent include a halogen atom, an amino group which may have a substituent, an alkoxycarbonyl group, a hydroxyl group, an ether group, a thiol group, a thioether group, a silyl group, a nitro group, and a cyano group. An alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group which may have a hydrogen atom is preferred.

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

  Examples of the alkyl group that may have a substituent include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group. , Ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl A group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group, 2-norbornyl group Can do. Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

Examples of the substituent of the alkyl group which may have a substituent include a substituent composed of a monovalent non-metal atom excluding a hydrogen atom. Preferred examples include halogen atoms (—F, —Br, -Cl, -I), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkyl Carbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcal Moyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkyl Ureido group, N′-arylureido group, N ′, N′-diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N -Alkylureido group, N'-alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N-arylureido group, N'-aryl-N -Alkylureido group, N'-aryl-N-arylureido group, N ', N'-diaryl-N-alkylureido group, N', N'-diary Ru-N-arylureido group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, Acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl- N-arylcarbamoyl group, al Killsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N— Alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group _(-PO 3 _{H 2)} and its conjugated base group (a phosphonato And referred), a dialkyl phosphono group _(-PO 3 _{(alkyl) 2)} "alkyl = alkyl group, hereinafter the" diarylphosphono group _(-PO 3 _{(aryl) 2)} "aryl = aryl group, hereinafter the same", An alkylarylphosphono group (—PO ₃ (alkyl) (aryl)), a monoalkylphosphono group (—PO ₃ (alkyl)) and a conjugate base group thereof (referred to as an alkylphosphonate group), a monoarylphosphono group ( -PO ₃ H (aryl)) and its conjugate base group (referred to as arylphosphonate group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (referred to as phosphonatoxy group), dialkylphosphonooxy group (— _{OPO 3 H (alkyl) 2)} , diaryl phosphono group _{(-OPO 3 (aryl) 2)} , alkylaryl Phosphonooxy group _(-OPO 3 (alkyl) (aryl)), monoalkyl phosphono group _(-OPO 3 H (alkyl)) and (referred to as alkylphosphonato group) a conjugate base group thereof, monoarylphosphono group (—OPO ₃ H (aryl)) and its conjugate base group (referred to as arylphosphonatoxy group), cyano group, nitro group, aryl group, alkenyl group, alkynyl group, heterocyclic group, silyl group and the like.

  Specific examples of the alkyl group in these substituents include the above-described alkyl groups, and specific examples of the aryl group in the substituent include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, and a mesityl group. , Cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group , Methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylpheny Group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group, phosphate Hona preparative phenyl group.

Examples of the alkenyl group in the substituent include a vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group, and the like. Examples of the alkynyl group in the substituent Examples thereof include an ethynyl group, a 1-propynyl group, a 1-butynyl group, and a trimethylsilylethynyl group.
Examples of the heterocyclic group in the substituent include a pyridyl group and a piperidinyl group.
Examples of the silyl group in the substituent include a trimethylsilyl group.
The substituent may contain an acyl group (R ⁰¹ CO—), and examples of the acyl group include those in which R ⁰¹ is a hydrogen atom, the above alkyl group, or an aryl group.

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

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

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

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

Examples of the alkenyl group, the substituted alkenyl group, the alkynyl group, and the substituted alkynyl group (-C (R ⁰² ) = C (R ⁰³ ) (R ⁰⁴ ) and -C≡C (R ⁰⁵ )) include R ^{A group in which 02} , R ⁰³ , R ⁰⁴ and R ⁰⁵ are monovalent non-metallic atoms can be used.
R ⁰² , R ⁰³ , R ⁰⁴ , and R ⁰⁵ are preferably a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group, and specific examples thereof are shown in the above examples. Things can be mentioned. Among these, a hydrogen atom, a halogen atom, and a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms are more preferable.
Specifically, vinyl group, 1-propenyl group, 1-butenyl group, 1-pentenyl group, 1-hexenyl group, 1-octenyl group, 1-methyl-1-propenyl group, 2-methyl-1-propenyl group 2-methyl-1-butenyl group, 2-phenyl-1-ethenyl group, 2-chloro-1-ethenyl group, ethynyl group, 1-propynyl group, 1-butynyl group, phenylethynyl group and the like.
Examples of the heterocyclic group include the pyridyl group exemplified as the substituent of the substituted alkyl group.

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

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

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

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

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

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

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

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

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

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

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

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

-Other photopolymerization initiators-
As the photopolymerization initiator, other photopolymerization initiators may be appropriately selected from known photopolymerization initiators in addition to the oxime derivative and used in combination. The photopolymerization initiator that may be used in combination is preferably, for example, one having photosensitivity to visible light from the ultraviolet region, and an activator that generates an active radical by generating some action with a photoexcited sensitizer. It may also be an initiator that initiates cationic polymerization depending on the type of monomer.
The photopolymerization initiator that may be used in combination preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a wavelength range of about 300 to 800 nm. The wavelength is more preferably 330 to 500 nm.

  Examples of the photopolymerization initiator that may be used in combination include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton), hexaarylbiimidazoles, organic peroxides, thios. Compounds, ketone compounds (benzylmethyl ketal compounds, α-hydroxyalkylphenone compounds, α-aminoalkylphenone compounds, etc.), aromatic onium salts, metallocenes, and the like. Among these, a phosphine oxide compound, a ketone compound, and a hexaarylbiimidazole compound are preferable from the viewpoints of sensitivity of the photosensitive layer, storage stability, and adhesion between the photosensitive layer and the printed wiring board forming substrate. The photopolymerization initiators that may be used in combination may be used singly or in combination of two or more.

  0.1-25 mass% is preferable, as for content of the photoinitiator in the said photosensitive composition, 0.5-20 mass% is more preferable, 0.5-15 mass% is still more preferable, 1-10 Part by mass is particularly preferred.

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

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

  The sensitizer is not particularly limited and may be appropriately selected from known sensitizers. For example, known polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, , Fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, indocarbocyanine, thiacarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, Methylene blue, toluidine blue), acridines (eg acridine orange, chloroflavin, acriflavine, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane), anthraquinones (eg anthraquinone), squalium (Eg, squalium), acridones (eg, acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone (eg, 2-chloro-10-butylacridone) Etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- ( 2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis (5,7-di-n-propoxycoumarin), 3,3 ′ -Carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxyc Phosphorus, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5 7-dipropoxycoumarin, JP-A-5-19475, JP-A-7-271028, JP-A-2002-363206, JP-A-2002-363207, JP-A-2002-363208, JP-A-2002-363209, etc. And the like, and thioxanthone compounds (thioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propyloxythioxanthone, Quantacure QTX, etc.) and the like. , Aromatic rings and compounds A compound in which an elemental ring is condensed (condensed compound), and an amine compound substituted with at least two aromatic hydrocarbon rings or aromatic heterocyclic rings are preferred.

  Among the condensed ring compounds, hetero-fused ketone compounds (acridone compounds, thioxanthone compounds, coumarin compounds, etc.) and acridine compounds are more preferable. Among the hetero-fused ketone compounds, an acridone compound and a thioxanthone compound are particularly preferable.

  The amine compound substituted with any one of the at least two aromatic hydrocarbon rings and the aromatic heterocyclic ring is preferably a sensitizer having an absorption maximum with respect to light in a wavelength region of 330 to 450 nm, For example, a disubstituted aminobenzophenone compound, a disubstituted amino-benzene compound having a heterocyclic group as a substituent at a carbon atom at the para position relative to an amino group on the benzene ring, Disubstituted amino-benzene compounds having a substituent containing a sulfonylimino group at the carbon atom at the position, disubstituted amino-benzene compounds having a carbostyryl skeleton, and at least two aromatic rings on the nitrogen atom Examples thereof include compounds having a di-substituted amino-benzene as a partial structure, such as a compound having a bonded structure.

The said sensitizer may be used individually by 1 type, and may use 2 or more types together.
The blending amount of the sensitizer is preferably 0.01 to 4% by mass, more preferably 0.02 to 2% by mass, and particularly preferably 0.05 to 1% by mass in the total solid content of the photosensitive composition.
When the content is less than 0.01% by mass, the sensitivity may decrease, and when the content exceeds 4% by mass, the shape of the pattern may be deteriorated.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The aromatic group can be produced by a normal radical polymerization method using at least one radical polymerizable compound containing an aromatic group and, if necessary, at least one other radical polymerizable compound as a copolymerization component. .
Examples of the radical polymerization method generally include a suspension polymerization method and a solution polymerization method.

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

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

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

In the compound represented by the general formula (AI) and the compound represented by the general formula (A-II), the general formula (AI) is preferable from the viewpoint of sensitivity. Among the structural formulas (AI), those having a linking group are preferable from the viewpoint of stability, and the organic group of L is an alkylene group having 1 to 4 carbon atoms in the non-image portion. It is preferable in terms of removability (developability).
The compound represented by the general formula (AI) is a compound containing a structural unit represented by the following general formula (A-1). Moreover, the compound represented by the said general formula (A-II) turns into a compound containing the structural unit of the following general formula (A-2). Among these, the structural unit of the general formula (A-1) is preferable from the viewpoint of storage stability.

However, in said general formula (A-1), R < ₁ >, R < ₂ > and R < ₃ > represent a hydrogen atom or monovalent organic group. L represents an organic group and may not be present. Ar represents an aromatic group that may contain a heterocycle.
However, in said general formula (A-1) and general formula (A-2), R < ₁ >, R < ₂ > and R < ₃ > and Ar are said general formula (AI) and general formula (A-II). Means the same.
In the general formulas (A-1) and (A-2), R ₁ and R ₂ are hydrogen atoms, and R ₃ is a methyl group, from the viewpoint of the removability (developability) of the non-image area. preferable.
In addition, L in the general formula (A-1) is preferably an alkylene group having 1 to 4 carbon atoms in terms of removability (developability) of non-image areas.

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

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

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

-Ethylenically unsaturated bond-
There is no restriction | limiting in particular as said ethylenically unsaturated bond, Although it can select suitably according to the objective, For example, what is represented by the following general formula (A-3)-(A-5) is preferable.

However, in the general formulas (A-3) to (A-5), R _{1 to} R ₁₁ each independently represent a monovalent organic group. X and Y each independently represent an oxygen atom, a sulfur atom, or —N—R ₄ . Z represents an oxygen atom, a sulfur atom, —N—R ₄ , or a phenylene group. R ₄ represents a hydrogen atom or a monovalent organic group.

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

In the general formula (A-4), examples of R _{4 to} R ₈ include a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, and a substituent. An alkyl group that may have a group, an aryl group that may have a substituent, an alkoxy group that may have a substituent, an aryloxy group that may have a substituent, and a substituent An alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, etc. are preferable, a hydrogen atom, a carboxyl group , An alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are more preferable.
As said substituent which can be introduce | transduced, what was quoted in the said general formula (A-3) is illustrated.

In the general formula (A-5), as R ₉ , for example, a hydrogen atom or an alkyl group which may have a substituent is preferable, and a hydrogen atom or a methyl group is more preferable because of high radical reactivity.
R ₁₀ and R ₁₁ each independently have, for example, a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, or a substituent. An alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino which may have a substituent Group, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and the like, preferably a hydrogen atom, a carboxyl group, an alkoxycarbonyl group An alkyl group which may have a substituent and an aryl group which may have a substituent are more preferable because of high radical reactivity.
Here, as the substituent which can be introduced, those exemplified in the general formula (A-3) are exemplified.
Z represents an oxygen atom, a sulfur atom, —NR ₁₃ —, or a phenylene group which may have a substituent. R ₁₃ represents an alkyl group which may have a substituent, and a hydrogen atom, a methyl group, an ethyl group, and an isopropyl group are preferable because of high radical reactivity.

Among the side chain ethylenically unsaturated bonds represented by the general formulas (A-3) to (A-5), those having the general formula (A-3) have high polymerization reactivity and higher sensitivity. preferable.
The content of the ethylenically unsaturated bond in the polymer compound is not particularly limited, but is preferably 0.5 to 3.0 meq / g, more preferably 1.0 to 3.0 meq / g, 1.5 ˜2.8 meq / g is particularly preferred. When the content is less than 0.5 meq / g, the curing reaction amount is small, so the sensitivity may be low. When the content is more than 3.0 meq / g, the storage stability may be deteriorated.
Here, the content (meq / g) can be measured by, for example, iodine value titration.

The method for introducing an ethylenically unsaturated bond represented by the general formula (A-3) into the side chain is not particularly limited, but for example, a polymer compound containing a carboxyl group in the side chain and ethylenically unsaturated It can be obtained by addition reaction of a compound having a bond and an epoxy group.
The polymer compound containing a carboxyl group in the side chain is usually composed of, for example, one or more radical polymerizable compounds containing a carboxyl group and, if necessary, one or more other radical polymerizable compounds as a copolymerization component. The radical polymerization method includes, for example, suspension polymerization method, solution polymerization method and the like.

The compound having an ethylenically unsaturated bond and an epoxy group is not particularly limited as long as it has these, but for example, a compound represented by the following general formula (A-6) and a general formula (A-7) The compounds represented are preferred. In particular, the use of the compound represented by the general formula (A-6) is preferable in terms of increasing sensitivity.
In the general formula (A-6), _{R 1} represents a hydrogen atom or a methyl group. L ₁ represents an organic group.
In the general formula (A-7), _{R 2} represents a hydrogen atom or a methyl group. L ₂ represents an organic group. W represents a 4- to 7-membered aliphatic hydrocarbon group.
Of the compound represented by the general formula (A-6) and the compound represented by the general formula (A-7), the compound represented by the general formula (A-6) is preferable, and the general formula (A- Also in 7), L ₁ is more preferably an alkylene group having 1 to 4 carbon atoms.

The compound represented by the general formula (A-6) or the compound represented by the general formula (A-7) is not particularly limited, and examples thereof include the following exemplified compounds (31) to (40). It is done.

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

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

Although there is no restriction | limiting in particular as a structural unit which has an ethylenically unsaturated bond in the said side chain, For example, the structure represented by the following general formula (A-8), the structure represented by general formula (A-9) And those represented by a mixture thereof are preferred.
However, in said general formula (A-8) and general formula (A-9), Ra-Rc represents a hydrogen atom or monovalent organic group. R ₁ represents a hydrogen atom or a methyl group. L ₁ represents an organic group that may have a linking group.

  The content of the polymer compound having the structure represented by the general formula (A-8) to the structure represented by the general formula (A-9) is preferably 20 mol% or more, more preferably 20 to 50 mol%, 25 -45 mol% is particularly preferred. When the content is less than 20 mol%, the curing reaction amount is small, so that the sensitivity may be low. When the content is more than 50 mol%, the storage stability may be deteriorated.

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

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

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

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

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

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

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

The molecular weight of the polymer compound of the present invention is preferably a mass average molecular weight of 3,000 to 100,000, more preferably 5,000 to 80,000, and particularly preferably 10,000 to 50,000. When the mass average molecular weight is less than 3,000, the cured film strength may be insufficient, and when it exceeds 100,000, the developability tends to decrease.
Further, the polymer compound of the present invention may contain an unreacted monomer. In this case, the content of the monomer in the polymer compound is preferably 15% by mass or less.

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

-Epoxy acrylate compound-
Furthermore, an epoxy acrylate compound can also be used as the binder. The epoxy acrylate compound of the present invention is a compound having a skeleton derived from an epoxy compound and containing an acidic group such as an ethylenically unsaturated double bond and a carboxyl group in the molecule. Such a compound can be obtained, for example, by a method of reacting a polyfunctional epoxy compound with a carboxyl group-containing monomer and further adding a polybasic acid anhydride.

Examples of the polyfunctional epoxy compound include a bixylenol type or bisphenol type epoxy resin (“YX4000; manufactured by Japan Epoxy Resin Co., Ltd.”) or a mixture thereof, a heterocyclic epoxy resin (“TEPIC; NISSAN CHEMICAL INDUSTRY CO., LTD. “ALALDITE PT810; Ciba Specialty Chemicals”, etc.), bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolac Type epoxy resin, cresol novolac type epoxy resin, halogenated phenol novolac type epoxy resin, glycidylamine type epoxy resin (for example, tetraglycidyldiaminodiphenylmethane), hydantoin Epoxy resin, alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A novolac 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 and Chemicals”, etc.), epoxy resins having a dicyclopentadiene skeleton (“HP -7200, HP-7200H; manufactured by Dainippon Ink & Chemicals, Inc.); condensation of phenolic compounds such as phenol, o-cresol, naphthol and the like with aromatic aldehydes having a phenolic hydroxyl group (for example, p-hydroxybenzaldehyde) Anti Reaction product of polyphenol compound and epichlorohydrin obtained by the above; reaction product of polyphenol compound obtained by addition reaction of phenol compound and diolefin compound such as divinylbenzene and dicyclopentadiene and epichlorohydrin; 4-vinylcyclohexene-1- Epoxidized ring-opening polymer of oxide with peracetic acid or the like; epoxy resin having a heterocyclic ring such as triglycidyl isocyanurate; glycidyl methacrylate copolymer epoxy resin (“CP-50S, CP-50M; NOF Corporation) And the like, and a copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate. These may be used individually by 1 type and may use 2 or more types together.
Examples of the carboxyl group-containing monomer include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, α-cyano. Cinnamic acid, acrylic acid dimer; in addition, addition reaction of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate with a cyclic acid anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride A reaction product with a halogen-containing carboxylic acid compound, ω-carboxy-polycaprolactone mono (meth) acrylate, and the like. Furthermore, commercially available products include Aronix M-5300, M-5400, M-5500 and M-5600 manufactured by Toa Synthetic Chemical Industry Co., Ltd., NK Esters CB-1 and CBX- manufactured by Shin-Nakamura Chemical Co., Ltd. 1. Kyoeisha Yushi Chemical Co., Ltd. HOA-MP and HOA-MS, Osaka Organic Chemical Industry Co., Ltd. biscoat # 2100, etc. can be used. These may be used individually by 1 type and may use 2 or more types together.
Examples of the polybasic acid anhydride include succinic anhydride, methyl succinic anhydride, 2,3-dimethyl succinic anhydride, 2,2-dimethyl succinic anhydride, ethyl succinic anhydride, dodecenyl succinic anhydride, and nonenyl succinic anhydride. , Maleic anhydride, methylmaleic anhydride, 2,3-dimethylmaleic anhydride, 2-chloromaleic anhydride, 2,3-dichloromaleic anhydride, bromomaleic anhydride, itaconic anhydride, citraconic anhydride, cisaccot anhydride Acid, phthalic anhydride, tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylene Tetrahydro anhydride Dibasic acid anhydrides such as phosphoric acid, chlorendic anhydride and 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, anhydrous Polybasic acid anhydrides such as pyromellitic acid and 3,3 ′, 4,4′-benzophenonetetracarboxylic acid can also be used. These may be used individually by 1 type and may use 2 or more types together.
Each of them is reacted in order to obtain an epoxy acrylate, and the ratio of reacting them is preferably 0.8 to 1.2 equivalents of carboxyl groups of the carboxyl group-containing monomer with respect to 1 equivalent of epoxy groups of the polyfunctional epoxy compound. Is 0.9-1.1 equivalent, 0.1-1.0 equivalent of polybasic acid anhydride, preferably 0.3-1.0 equivalent.
In addition, compounds obtained by adding the polybasic acid anhydride to an epoxy acrylate having a fluorene skeleton (a compound having no carboxyl group) described in JP-A-5-70528 are also used as the epoxy acrylate of the present invention. Available.
The molecular weight of the epoxy acrylate compound is preferably 3,000 to 100,000, more preferably 5,000 to 50,000 in terms of mass average molecular weight. When the molecular weight is less than 3,000, the tackiness of the surface of the photosensitive layer may become strong, and after curing of the photosensitive layer described later, the film quality may become brittle, or the surface hardness may deteriorate, If it exceeds 100,000, developability may deteriorate. Also, synthesis of the resin becomes difficult.

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

<Thermal crosslinking agent>
The thermal crosslinking agent is not particularly limited and may be appropriately selected depending on the purpose. In order to improve the film strength after curing of the photosensitive layer formed using the photosensitive composition, developability For example, an epoxy compound having at least two oxirane groups in one molecule and an oxetane compound having at least two oxetanyl groups in one molecule can be used. The thermal crosslinking agent is preferably insoluble in alkali from the viewpoint of gold plating resistance.

  Examples of the epoxy compound having at least two oxirane groups in one molecule include, for example, a bixylenol type or biphenol type epoxy resin (“YX4000 Japan Epoxy Resin” etc.) or a mixture thereof, a complex having an isocyanurate skeleton, etc. Cyclic epoxy resin (“TEPIC; manufactured by Nissan Chemical Industries, Ltd.”, “Araldite PT810; manufactured by Ciba Specialty Chemicals”, etc.), bisphenol A type epoxy resin, novolac type epoxy resin, bisphenol F type epoxy resin, water Bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, halogenated epoxy resin (for example, low brominated epoxy resin, high halogenated epoxy resin) Brominated phenol novolac type epoxy resin, etc.), allyl group-containing bisphenol A type epoxy resin, trisphenolmethane type epoxy resin, diphenyldimethanol type epoxy resin, phenol biphenylene type epoxy resin, dicyclopentadiene type epoxy resin ("HP-7200") , HP-7200H; manufactured by Dainippon Ink and Chemicals, Inc.), glycidylamine type epoxy resins (diaminodiphenylmethane type epoxy resins, diglycidylaniline, triglycidylaminophenol, etc.), glycidyl ester type epoxy resins (phthalic acid) Diglycidyl ester, adipic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer acid diglycidyl ester, etc.) Hydantoin type epoxy resin, alicyclic epoxy resin ( , 4-Epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, dicyclopentadiene diepoxide, “GT-300, GT-400, ZEHPE3150; Daicel Chemical Industries , Imide type alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A novolac type epoxy resin, tetraphenylolethane type epoxy resin, glycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene Group-containing epoxy resin (naphthol aralkyl type epoxy resin, naphthol novolac type epoxy resin, tetrafunctional naphthalene type epoxy resin, commercially available products such as “ESN-190, ESN-360; Gaku Co., Ltd. "," HP-4032, EXA-4750, EXA-4700; Dainippon Ink and Chemicals Co., Ltd. "), phenol compounds and diolefin compounds such as divinylbenzene and dicyclopentadiene Reaction product of polyphenol compound obtained by reaction and epichlorohydrin, ring-opening polymer of 4-vinylcyclohexene-1-oxide epoxidized with peracetic acid, epoxy resin having linear phosphorus-containing structure, cyclic phosphorus-containing Epoxy resin having structure, α-methylstilbene type liquid crystal epoxy resin, dibenzoyloxybenzene type liquid crystal epoxy resin, azophenyl type liquid crystal epoxy resin, azomethine phenyl type liquid crystal epoxy resin, binaphthyl type liquid crystal epoxy resin, azine type epoxy resin, glycidyl meta Acrylate copolymer epoxy Si resin (“CP-50S, CP-50M; manufactured by NOF Corporation”, etc.), copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, bis (glycidyloxyphenyl) fluorene type epoxy resin, bis (glycidyloxy) Phenyl) adamantane type epoxy resin and the like can be mentioned, but not limited thereto. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.

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

  The β-alkyl-substituted glycidyl group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include β-methylglycidyl group, β-ethylglycidyl group, β-propylglycidyl group, β-butylglycidyl group. Among these, a β-methylglycidyl group is preferred from the viewpoint of improving the storage stability of the photosensitive resin composition and the ease of synthesis.

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

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

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

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

  Examples of the oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl -3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate, oligomers or copolymers thereof, and compounds having an oxetane group , Novolac resin, poly (p-hydroxystyrene), potassium Bisphenols, calixarenes, calixresorcinarenes, ether compounds such as silsesquioxane and other hydroxyl-containing resins, etc. In addition, unsaturated monomers having an oxetane ring and alkyl (meth) acrylates And a copolymer thereof.

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

  Further, as the thermal crosslinking agent, a polyisocyanate compound described in JP-A-5-9407 can be used, and the polyisocyanate compound is aliphatic, cycloaliphatic or aromatic containing at least two isocyanate groups. It may be derived from a group-substituted aliphatic compound. Specifically, bifunctional isocyanate (for example, a mixture of 1,3-phenylene diisocyanate and 1,4-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate, 1,3- and 1,4-xylylene). Diisocyanate, bis (4-isocyanate-phenyl) methane, bis (4-isocyanatocyclohexyl) methane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, etc.), the bifunctional isocyanate, trimethylolpropane, pentalithol tol Polyfunctional alcohols such as glycerin; alkylene oxide adducts of the polyfunctional alcohols and adducts of the bifunctional isocyanates; hexamethylene diisocyanate, hexamethylene-1,6-di Isocyanate and cyclic trimers thereof derivatives; and the like.

Furthermore, for the purpose of improving the storage stability of the photosensitive composition of the present invention, a compound obtained by reacting a blocking agent with the isocyanate group of the polyisocyanate and its derivative may be used.
Examples of the isocyanate group blocking agent include alcohols (eg, isopropanol, tert-butanol, etc.), lactams (eg, ε-caprolactam, etc.), phenols (eg, phenol, cresol, p-tert-butylphenol, p-sec). -Butylphenol, p-sec-amylphenol, p-octylphenol, p-nonylphenol, etc.), heterocyclic hydroxyl compounds (eg, 3-hydroxypyridine, 8-hydroxyquinoline, etc.), active methylene compounds (eg, dialkyl malonate, Methyl ethyl ketoxime, acetylacetone, alkyl acetoacetate oxime, acetoxime, cyclohexanone oxime, etc.). In addition to these, compounds having at least one polymerizable double bond and at least one blocked isocyanate group in the molecule described in JP-A-6-295060 can be used.

  Moreover, a melamine derivative can be used as the thermal crosslinking agent. Examples of the melamine derivative include methylol melamine, alkylated methylol melamine (a compound obtained by etherifying a methylol group with methyl, ethyl, butyl, or the like). These may be used individually by 1 type and may use 2 or more types together. Among these, alkylated methylol melamine is preferable and hexamethylated methylol melamine is particularly preferable in that it has good storage stability and is effective in improving the surface hardness of the photosensitive layer or the film strength itself of the cured film.

In order to accelerate the thermal curing of the thermal crosslinking agent, for example, an amine compound (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N- Dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (eg, dimethylamine, etc.), imidazole derivative bicyclic amidines Compounds and salts thereof (for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- ( 2-sia Ethyl) -2-ethyl-4-methylimidazole, etc.), phosphorus compounds (eg triphenylphosphine etc.), guanamine compounds (eg melamine, guanamine, acetoguanamine, benzoguanamine etc.), S-triazine derivatives (eg 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 adduct, etc.) can be used. These may be used alone or in combination of two or more. In addition, there is no restriction | limiting in particular if the curing catalyst of the said thermal crosslinking agent or the reaction of these and a carboxyl group can be accelerated | stimulated, You may use the compound which can accelerate | stimulate thermosetting other than the above.
The solid content in the photosensitive composition of the thermal crosslinking agent and the compound capable of accelerating thermal curing between these and a carboxylic acid is preferably 0.01 to 15% by mass.

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

<Other ingredients>
Examples of the other components include thermal polymerization inhibitors, plasticizers, colorants (color pigments or dyes), extender pigments, and the like, and adhesion promoters to the substrate surface and other auxiliary agents (for example, , Conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, perfumes, surface tension modifiers, chain transfer agents, etc.) may be used in combination. By appropriately containing these components, properties such as stability, photographic properties, film physical properties, etc. of the intended photosensitive composition or the photosensitive film described later can be adjusted.

-Thermal polymerization inhibitor-
The thermal polymerization inhibitor may be added to prevent thermal polymerization or temporal polymerization of the polymerizable compound.
Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine. , Chloranil, naphthylamine, β-naphthol, 2,6-di-tert-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid 4-toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.

  The content of the thermal polymerization inhibitor is preferably 0.001 to 5% 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.

-Color pigment-
There is no restriction | limiting in particular as said coloring pigment, According to the objective, it can select suitably, For example, Victoria pure blue BO (CI. 42595), auramine (CI. 41000), fat black HB (CI. 26150), Monolite Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow HR). Yellow 83), C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 154, C.I. I. Pigment Yellow 185, Permanent Carmine FBB (CI Pigment Red 146), Hoster Balm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11) Fastel・ Pink B Supra (CI Pigment Red 81) Monastral First Blue (CI Pigment Blue 15), Monolite First Black B (CI Pigment Black 1), Carbon, C. I. Pigment red 97, C.I. I. Pigment red 122, C.I. I. Pigment red 149, C.I. I. Pigment red 168, C.I. I. Pigment red 177, C.I. I. Pigment red 180, C.I. I. Pigment red 192, C.I. I. Pigment red 215, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 22, C.I. I. Pigment blue 60, C.I. I. Pigment blue 64 and the like. These may be used alone or in combination of two or more. Moreover, the dye suitably selected from well-known dye can be used as needed.

  The solid content in the photosensitive composition solid content of the color pigment can be determined in consideration of the exposure sensitivity, resolution, etc. of the photosensitive layer at the time of permanent pattern formation, depending on the type of the color pigment. Generally, 0.05 to 10% by mass is preferable, and 0.1 to 5% by mass is more preferable.

-Extender pigment-
If necessary, the photosensitive composition may be inorganic for the purpose of improving the surface hardness of the permanent pattern or keeping the linear expansion coefficient low, or keeping the dielectric constant or dielectric loss tangent of the cured film low. Pigments and organic fine particles can be added.
The inorganic pigment is not particularly limited and may be appropriately selected from known ones. For example, kaolin, barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, vapor phase method silica, amorphous Examples thereof include silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica.
The average particle diameter of the inorganic pigment is preferably less than 10 μm, and more preferably 3 μm or less. When the average particle size is 10 μm or more, resolution may be deteriorated due to light scattering.
There is no restriction | limiting in particular as said organic fine particle, According to the objective, it can select suitably, For example, a melamine resin, a benzoguanamine resin, a crosslinked polystyrene resin etc. are mentioned. Further, silica having an average particle diameter of 1 to 5 μm and an oil absorption of about 100 to 200 m ² / g, spherical porous fine particles made of a crosslinked resin, and the like can be used.

  The amount of the extender is preferably 5 to 60% by mass. When the addition amount is less than 5% by mass, the linear expansion coefficient may not be sufficiently reduced. When the addition amount exceeds 60% by mass, when the cured film is formed on the photosensitive layer surface, 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.

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

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

  0.001 mass%-20 mass% are preferable with respect to all the components in the said photosensitive composition, as for content of the said adhesion promoter, 0.01-10 mass% is more preferable, 0.1 mass%- 5% by mass is particularly preferred.

(Photosensitive film)
The photosensitive film has at least a support and a photosensitive layer, preferably a protective film, and, if necessary, other layers such as a cushion layer and an oxygen barrier layer (PC layer). Having a layer.
The form of the photosensitive film is not particularly limited and can be appropriately selected according to the purpose. For example, the photosensitive layer and the protective film are provided in this order on the support, A form in which the PC layer, the photosensitive layer, and the protective film are provided in this order on the support, and the cushion layer, the PC layer, the photosensitive layer, and the protective film are provided in this order on the support. And the like. The photosensitive layer may be a single layer or a plurality of layers.

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

The support is preferably made of a synthetic resin and transparent, for example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester, poly ( (Meth) acrylic acid ester copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoro Various plastic films such as ethylene, 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, Although it can select suitably according to the objective, For example, 4-300 micrometers is preferable and 5-175 micrometers is more preferable.

  There is no restriction | limiting in particular in the shape of the said support body, Although it can select suitably according to the objective, A long shape is preferable. There is no restriction | limiting in particular in the length of the said elongate support body, For example, the thing of 10-20,000m length is mentioned.

<Photosensitive layer>
The photosensitive layer is formed using the photosensitive composition of the present invention.
In the case where the photosensitive layer is exposed and developed, the minimum energy of light used for the exposure that does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development is 0.1 to 500 mJ / cm ² . Preferably, it is 0.2 to 200 mJ / cm ² , more preferably 0.5 to 100 mJ / cm ² , and particularly preferably 1 to 50 mJ / cm ² .
The minimum energy is less than 0.1 mJ / cm ^2, may fogging in process step occurs, it exceeds 500 mJ / cm ^2, increases the time necessary for exposure, processing speed is slow Sometimes.

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

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

<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 in the location provided in the said photosensitive film of the said protective film, Although it can select suitably according to the objective, Usually, it is provided on the said photosensitive layer.
Examples of the protective film include those used for the support, silicone paper, polyethylene, paper laminated with polypropylene, polyolefin or polytetrafluoroethylene sheet, etc. Among these, polyethylene film, Polypropylene film is preferred.
There is no restriction | limiting in particular in the thickness of the said protective film, Although it can select suitably according to the objective, For example, 5-100 micrometers is preferable and 8-30 micrometers is more preferable.
When the protective film is used, it is preferable that the adhesive force A between the photosensitive layer and the support and the adhesive force B between the photosensitive layer and the protective film satisfy the relationship of adhesive force A> adhesive force B.
Examples of the combination of the support and the protective film (support / protective film) include polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate, and the like. . Moreover, the 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 photosensitive film is preferably stored, for example, wound around a cylindrical core, wound in a long roll shape. There is no restriction | limiting in particular in the length of the said elongate photosensitive film, For example, it can select suitably from the range of 10-20,000m. Further, slitting may be performed so that the user can easily use, and a long body in the range of 100 to 1,000 m may be formed into a roll. In this case, it is preferable that the support is wound up so as to be the outermost side. Moreover, you may slit the said roll-shaped photosensitive film in a sheet form. When storing, from the viewpoint of protecting the end face and preventing edge fusion, it is preferable to install a separator (particularly moisture-proof and containing a desiccant) on the end face, and use a low moisture-permeable material for packaging. Is preferred.

The protective film may be surface-treated in order to adjust the adhesion between the protective film and the photosensitive layer. In the surface treatment, for example, an undercoat layer made of a polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, or polyvinyl alcohol is formed on the surface of the protective film. The undercoat layer can be formed by applying the polymer coating solution to the surface of the protective film and then drying at 30 to 150 ° C. for 1 to 30 minutes. The drying temperature is particularly preferably 50 to 120 ° C.
In addition to the photosensitive layer, the support, and the protective film, a cushion layer, an oxygen blocking layer (PC layer), a release layer, an adhesive layer, a light absorption layer, a surface protective layer, and the like may be included. .
The cushion layer is a layer that has no tackiness at room temperature and melts and flows when laminated under vacuum and heating conditions.
The PC layer is usually a coating of about 0.5 to 5 μm formed mainly of polyvinyl alcohol.

[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.

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

(Photosensitive laminate)
The photosensitive laminate of the present invention is formed by laminating at least a photosensitive layer made of the photosensitive composition of the present invention 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 according to 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 pressure of the said pressurization, 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.

By using the photosensitive composition of the present invention, the photosensitive film and photosensitive laminate of the present invention are excellent in sensitivity, resolution, and cured product properties as a permanent protective film, and are photosensitive from a filmed roll. Since there is little oozing of the composition (end face fusion) and a high-definition permanent pattern can be efficiently formed, it is used for forming various patterns such as a protective film, an interlayer insulating film, a permanent pattern such as a solder resist pattern, It can be suitably used for the production of liquid crystal structural members such as color filters, pillars, ribs, spacers, partition walls, etc., and for pattern formation of holograms, micromachines, proofs, etc., especially for the formation of permanent patterns on printed circuit boards. It can be used suitably.
In particular, since the photosensitive film of the present invention has a uniform thickness, even when the permanent pattern (protective film, interlayer insulating film, solder resist, etc.) is thinned during the formation of the permanent pattern, a high acceleration test is performed. In (HAST), there is no occurrence of ion migration, and a high-definition permanent pattern excellent in heat resistance and moisture resistance can be obtained.

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

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

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

  The exposure target is not particularly limited as long as it is the photosensitive layer in the photosensitive composition, and can be appropriately selected according to the purpose. For example, as described above, the photosensitive composition is formed on the substrate. It is preferably performed on a laminate formed by laminating while performing at least one of heating and pressurization.

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

  The analog exposure is not particularly limited and may be appropriately selected depending on the purpose.For example, a method of performing exposure with a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, or the like through a negative mask having a predetermined pattern. Can be mentioned.

  The digital exposure is not particularly limited and can be appropriately selected depending on the purpose. For example, a control signal is generated based on pattern formation information to be formed, and light modulated in accordance with the control signal is used. For example, the photosensitive layer is arranged in a two-dimensional array of n (where n is a natural number of 2 or more) that receives and emits light from the light irradiation means and the light irradiation means. An exposure head provided with a light modulation unit capable of controlling the drawing unit according to pattern information, wherein the column direction of the drawing unit is relative to the scanning direction of the exposure head. An exposure head arranged so as to form a predetermined set inclination angle θ is used, and the exposure head is subjected to N double exposure (where N is 2) among the usable pixel parts by the use pixel part specifying means. The natural number above) Designate the element part, and control the element part for the exposure head so that only the element part specified by the element part for specifying the used element part is involved in the exposure by the element part controlling unit. A method is preferred in which 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)” is a direction in which the angle formed with the scanning direction of the exposure head is smaller in the array of light spots (pixels) as pixel units generated by the pixel unit. Refers to a sequence of 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, “N multiple drawing” and “multiple exposure” are used as terms corresponding to “N double exposure” and “multiple exposure” for an embodiment in which the exposure apparatus or exposure method of the present invention is implemented as a drawing apparatus or drawing method. The term “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. In addition, 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. For this reason, 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. As a DMD 36 (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 emitting portion in which the emission end portion (light emitting 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. A fiber array light source 38, a lens system 40 for correcting the laser light emitted from the fiber array light source 38 and condensing it on the DMD, and a 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-
The light modulating means has n (where n is a natural number of 2 or more) two-dimensionally arranged image elements, and can control the image elements 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 this embodiment, a DMD 36 in which 1024 columns × 768 rows of micromirrors 58 are arranged is used. Among these, the micromirrors 58 that can be driven by a controller connected to the DMD 36, that is, usable micromirrors 58 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 in a normal semiconductor memory manufacturing line via a support including a hinge and a yoke, and the whole is configured monolithically (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 a means capable of synthesizing and irradiating two or more lights. Among these, a means capable of synthesizing and irradiating two or more lights is preferable.
The light 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, the same light can be used.

The wavelength of ultraviolet to visible light is preferably, for example, 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 designation 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 and the like. It is assumed that an angle slightly larger than the angle θ _ideal, which is a 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 ′ thus specified, 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 the first to T-th row micromirrors on the DMD 36 are selected as micromirrors that are actually used during the main exposure. In this way, 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 includes the positional dependency of the transmittance of the optical element between the DMD 36 and the exposed surface (for example, the lenses 52 and 54 in FIG. 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 development is performed by removing an unexposed portion of the photosensitive layer.
There is no restriction | limiting in particular as the removal method of the said unhardened area | region, According to the objective, it can select suitably, For example, the method etc. which remove using a developing solution are mentioned.

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

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

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

[Curing process]
The curing treatment step is a step of performing a curing treatment on the photosensitive layer in the formed pattern after the development step is performed.
There is no restriction | limiting in particular as said hardening process, Although it can select suitably according to the objective, For example, a whole surface exposure process, a whole surface heat processing, etc. are mentioned suitably.

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

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

-Method for forming protective film, interlayer insulating film, solder resist permanent pattern-
When the pattern forming method is a permanent pattern forming method for forming at least one of a protective film, an interlayer insulating film, and a solder resist pattern, the permanent pattern is formed on the printed circuit board by the permanent pattern forming method. Furthermore, 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 wiring board. Gold plating is performed on the portion of the metal layer exposed on the surface of the printed wiring board, and then soldering is performed. Then, a semiconductor or a component is mounted on the soldered portion. At this time, the permanent pattern of the hardened layer functions 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 or a build-up wiring board.

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

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

(Synthesis Example 1)
-Synthesis of Dendritic Branched Compound 1 Having Polymerizable Group (Exemplary Compound (M-1))-
While adding 13.6 parts by mass of pentaerythritol, 163 parts by mass of 2,2-bishydroxymethylpropionic acid, and 0.5 parts by mass of p-toluenesulfonic acid to a three-necked flask equipped with a condenser and a stirrer, flowing nitrogen The mixture was reacted in an oil bath at 145 ° C. for 2 hours to obtain a homogeneous solution. Then, it was made to react at 145 degreeC under pressure reduction (50 mmHg or less) for 2 hours, and the following compound (K-1) which is a precursor of M-1 was obtained. This compound was identified by NMR and IR.

  Thereafter, 20 parts by mass of toluene, 112 parts by mass of methacrylic acid, 0.03 parts by mass of phenothiazine and 0.07 parts by mass of hydroquinone as stabilizers were added to the obtained compound (K-1) at 130 ° C. While the toluene is returned for 3 hours, the generated water is distilled out of the system by azeotropic distillation to form a dendritic compound 1 having a polymerizable group (exemplary compound (M-1), hereinafter “dendritic branched compound 1”). ").

(Synthesis Example 2)
-Synthesis of dendritic compound 2 having a polymerizable group-
To the compound (K-1) obtained in the same manner as in Synthesis Example 1, 20 parts by mass of toluene, 80 parts by mass of acrylic acid, 0.03 parts by mass of phenothiazine and 0.07 parts by mass of hydroquinone were added as stabilizers. Except for the above, a dendritic compound 2 having a polymerizable group in the same manner as in Synthesis Example 1 (in the exemplified compound M-3, a part of OR is a hydroxy group, hereinafter referred to as “dendritic compound 2”). Obtained.

(Synthesis Example 3)
-Synthesis of dendritic compound 3 having a polymerizable group-
A three-necked flask equipped with a condenser, a thermometer, and a stirring rod was charged with 13.6 parts by mass of pentaerythritol, 222 parts by mass of 2,2-dimethylolbutanoic acid, and 2 parts by mass of paratoluenesulfonic acid as a catalyst, and 100 ° C. The mixture was stirred downward to obtain a uniform liquid mixed melt. Subsequently, 20 parts by mass of toluene was injected, the temperature was raised to 140 ° C., and water generated while the toluene was distilled off was distilled out of the system by azeotropic distillation. The reaction was terminated after 5 hours under the same conditions to obtain a dendritic compound.
Thereafter, 85 parts by mass of acrylic acid, 0.03 parts by mass of phenothiazine and 0.07 parts by mass of hydroquinone as stabilizers were additionally added to the three-necked flask, and a dendritic compound having a polymerizable group in the same manner as in Synthesis Example 1. 3 (hereinafter referred to as “dendritic branched compound 3”) was obtained.

(Synthesis Example 4)
-Synthesis of binder 1-
In a 1,000 mL three-necked flask, 159 g of 1-methoxy-2-propanol was placed and heated to 85 ° C. under a nitrogen stream. To this, 63.4 g of benzyl methacrylate, 72.3 g of methacrylic acid, and 4.15 g of 1-methoxy-2-propanol 159 g solution of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued by heating for 5 hours. Subsequently, the heating was stopped to obtain a copolymer of benzyl methacrylate / methacrylic acid (ratio of 30/70 mol%).
Next, 120.0 g of the copolymer solution was transferred to a 300 mL three-necked flask, and 16.6 g of glycidyl methacrylate and 0.16 g of p-methoxyphenol were added and stirred to dissolve. After dissolution, 2.4 g of triphenylphosphine was added and heated to 100 ° C. to carry out an addition reaction. The disappearance of glycidyl methacrylate was confirmed by gas chromatography, and heating was stopped. 1-methoxy-2-propanol was added to prepare a binder 1 solution represented by the following structural formula having a solid content of 30% by mass.
It was 15,000 as a result of measuring the mass mean molecular weight (Mw) of the obtained binder 1 by the gel permeation chromatography method (GPC) which used the polystyrene as a reference material.
Moreover, the acid value per solid content was 2.2 meq / g from the titration using sodium hydroxide.
Furthermore, the content of ethylenically unsaturated bonds per solid (C = C value) determined by iodine value titration was 2.1 meq / g.
* 1 represents a mixture of a structure represented by the following structural formula (a) and a structure represented by the following structural formula (b).

(Synthesis Example 5)
-Synthesis of binder 2-
In a 1,000 mL three-necked flask, 159 g of 1-methoxy-2-propanol was added and heated to 85 ° C. under a nitrogen stream. To this, 36 g of methyl methacrylate, 72.3 g of methacrylic acid, and 4.15 g of 1-methoxy-2-propanol 159 g of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) were added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued by heating for 5 hours. Subsequently, the heating was stopped to obtain a copolymer of methyl methacrylate / methacrylic acid (ratio of 30/70 mol%).
Next, 120.0 g of the copolymer solution was transferred to a 300 mL three-necked flask, and 16.6 g of glycidyl methacrylate and 0.16 g of p-methoxyphenol were added and stirred to dissolve. After dissolution, 2.4 g of triphenylphosphine was added and heated to 100 ° C. to carry out an addition reaction. The disappearance of glycidyl methacrylate was confirmed by gas chromatography, and heating was stopped. 1-Methoxy-2-propanol was added to prepare a binder 2 solution represented by the following structural formula having a solid content of 30% by mass.
It was 15,000 as a result of measuring the mass mean molecular weight (Mw) of the obtained binder 2 by the gel permeation chromatography method (GPC) which used the polystyrene as a reference material.
Moreover, the acid value per solid content was 2.3 meq / g from the titration using sodium hydroxide.
Furthermore, the content (C = C value) of ethylenically unsaturated bonds per solid content determined by iodine value titration was 2.6 meq / g.

(Synthesis Example 6)
-Synthesis of binder 3-
110 parts by mass of phenol novolac type epoxy resin (manufactured by Toto Kasei Co., Ltd., YDPN-702) was dissolved in 150 parts by mass of propylene glycol monomethyl ether acetate, and then 34 parts by mass of acrylic acid and 0.8 parts by mass of benzyldimethylamine were dissolved. In addition, after continuing the reaction at 100 to 120 ° C. for 8 hours, 35 parts by mass of tetrahydrophthalic anhydride was added and reacted at 100 ° C. for 8 hours to obtain an epoxy acrylate compound having an acid value of 70 mgKOH / g.

Example 1
-Preparation of photosensitive composition-
Each component was mix | blended with the following quantity, and the photosensitive composition solution was prepared.
[Each component amount of photosensitive composition solution]
-Binder 1 obtained in Synthesis Example 4 (solid content 30% by mass in the 1-methoxy-2-propanol solution) ... 87.4 parts by mass-Dendritic branched compound 1 obtained in Synthesis Example 1 ... 12 parts by mass-Photopolymerization initiator (oxime derivative) represented by the following formula I-1 ... 6 parts by mass-Sensitizer (thioxanthone compound) represented by the following formula S-1 0.6 parts by mass Fluorosurfactant (Megafac F-176, manufactured by Dainippon Ink & Chemicals, Inc., 30% by weight 2-butanone solution) 0.2 parts by mass Barium sulfate dispersion (Manufactured by Sakai Chemical Industry Co., Ltd., B-30) ... 40 parts by mass / methyl ethyl ketone ... 15 parts by mass The barium sulfate dispersion is barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., B30) 30. Parts by mass, binder 1 (said 1-methoxy-2-propylene 29.2 parts by weight of a solution of C.N. I. Pigment Blue 15: 3 0.2 parts by mass, C.I. I. After mixing 0.05 parts by mass of Pigment Yellow 185 and 40.55 parts by mass of methyl ethyl ketone in advance, a motor mill M-200 (manufactured by Eiger) was used to use zirconia beads having a diameter of 1.0 mm and a peripheral speed of 9 m / s. For 3.5 hours.

-Preparation of photosensitive laminate-
Next, the substrate was prepared by subjecting the surface of a printed board, that is, a copper-clad laminate (without through holes, copper thickness: 12 μm) on which a wiring had been formed, to a chemical polishing treatment. On the copper-clad laminate, the photosensitive composition was applied by a screen printing method using a 120 mesh Tetron screen so that the thickness after drying was 30 μm, and a hot air circulating dryer at 80 ° C. for 15 minutes. Was dried to form a photosensitive layer, and a photosensitive laminate in which the copper-clad laminate and the photosensitive layer were laminated in this order was prepared.

  About the said photosensitive laminated body, evaluation of the shortest image development time, a sensitivity, the resolution, pencil hardness, and the crack property at the time of bending was performed with the following method, respectively. The results other than the shortest development time are shown in Table 2.

<Evaluation of the shortest development time>
A 1 mass% sodium carbonate aqueous solution at 30 ° C. is sprayed on the entire surface of the photosensitive layer on the copper clad laminate at a pressure of 0.15 MPa, and the photosensitive layer on the copper clad laminate is dissolved from the start of spraying of the sodium carbonate aqueous solution. The time required for removal was measured and this was taken as the shortest development time. The shortest development time was 14 seconds.

<Evaluation of sensitivity>
The photosensitive layer in the photosensitive laminate prepared above by using a pattern forming apparatus described below, the light energy different light from 0.1 mJ / cm ² to 100 mJ / cm ² at ^{2 1/2} times the interval Were exposed twice to cure a part of the photosensitive layer. After standing at room temperature for 10 minutes, a 1 mass% sodium carbonate aqueous solution at 30 ° C. is sprayed over the entire surface of the photosensitive layer on the copper clad laminate at a spray pressure of 0.15 MPa for twice the shortest development time. The uncured area was dissolved and removed, and the thickness of the remaining cured area was measured. Subsequently, the relationship between the light irradiation amount and the thickness of the cured layer was plotted to obtain a sensitivity curve. From the sensitivity curve, the amount of light energy when the thickness of the cured region was the same 30 μm as that of the photosensitive layer before exposure was determined as the amount of light energy necessary for curing the photosensitive layer.

<< 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. However, among the 768 sets arranged in the sub-scanning direction, DMD 36 controlled to drive only 1024 × 256 rows, and an optical system for imaging the light shown in FIGS. 5A and 5B on the photosensitive film, 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 columns × 256 rows micromirror 58 is adopted. This angle θ _ideal corresponds to the number N of N double exposures, the number s of usable micromirrors 58 in the column direction, the interval p in the column direction of the usable micromirrors 58, and the microscopic state when the exposure head 30 is tilted. For the pitch δ of the scanning line formed by the mirror,
spsin θ _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.
pcos θ _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. 18, the light spot group from the usable micromirror 58 of the DMD 36 of the exposure heads 30 ₁₂ and 30 ₂₁ projected onto the exposed surface of the photosensitive film 12 with the stage 14 being stationary. Showed the pattern. 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. 18, 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.

As shown in FIG. 18, 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
t tan θ ′ = 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. 19 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 by the oblique lines in FIG. 19 were similarly covered by 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.

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

<Evaluation of pencil hardness>
About the said photosensitive laminated body, the whole surface exposure of the 5 cm x 5 cm range by the said laser exposure, after image development, the whole surface exposure (post-exposure) is carried out at 100 mJ / cm < ² > with an ultrahigh pressure mercury lamp, and the heat processing (150 degreeC for 60 minutes ( Post bake treatment) was performed. With respect to the pattern, pencil hardness was measured based on JIS K-5400.

<Evaluation of cracking properties during bending>
About the said photosensitive laminated body, the whole surface exposure of the 5 cm x 5 cm range by the said laser exposure is performed, after a development, the whole surface exposure (post exposure) is performed at 100 mJ / cm < ² > with an ultrahigh pressure mercury lamp, and also the heat processing for 150 degreeC60 minutes (Post-bake treatment) was performed. With respect to the obtained pattern, the presence or absence of cracks in the photosensitive layer when it was bent at 90 degrees was observed and evaluated according to the following criteria.
〔Evaluation criteria〕
○: No cracking of the photosensitive layer when bent.
Δ: Some cracks occur in the photosensitive layer when bent.
X: The crack of a photosensitive layer enters large at the time of bending.

(Example 2)
-Production of photosensitive film-
The photosensitive composition solution obtained in Example 1 was applied onto a PET (polyethylene terephthalate) film having a thickness of 16 μm (Toray Industries, 16FB50), a width of 300 mm, and a length of 200 m as the support by a bar coater. And dried in an 80 ° C. hot air circulation dryer to form a photosensitive layer having a thickness of 30 μm. Next, a polypropylene film (E-200, manufactured by Oji Paper Co., Ltd.) having a thickness of 20 μm, a width of 310 mm, and a length of 210 m was laminated as a protective film on the photosensitive layer by lamination to produce the photosensitive film.

-Preparation of photosensitive laminate-
Next, on the same copper clad laminate as that of Example 1 as the substrate, the photosensitive film of the photosensitive film was in contact with the copper clad laminate, and the protective film on the photosensitive film was peeled off, and a vacuum laminator ( Nitgo Morton Co., Ltd., VP130) was used to prepare a photosensitive laminate in which the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) were laminated in this order. .
The pressure bonding conditions were a 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.

  About the said photosensitive laminated body, the sensitivity, the resolution, the pencil hardness, the crack property at the time of bending, and the end surface fusion were evaluated. In addition, about the resolution, pencil hardness, and the crack property at the time of bending, it evaluated similarly to Example 1. FIG. The results are shown in Table 2.

<Evaluation of sensitivity>
For the photosensitive layer of the photosensitive film in the prepared photosensitive laminate, a part of the photosensitive layer is cured from the support side in the same manner as in Example 1 by the pattern forming apparatus described in Example 1. It was. After leaving still at room temperature for 10 minutes, the said support body was peeled off from the said photosensitive laminated body, and it carried out similarly to Example 1, and measured the amount of light energy required in order to harden a photosensitive layer.

<With or without end face fusion>
The said photosensitive film was wound up with the winder, and the photosensitive film original fabric roll was manufactured.
The obtained photosensitive film original roll was slit with a coaxial slitter, and wound on an ABS resin cylindrical core having a length of 300 mm and an inner diameter of 76 mm, and wound up to 150 m in a width of 250 mm to prepare a photosensitive film roll.
The photosensitive film roll thus obtained was wrapped in a black polyethylene cylindrical bag (film thickness: 80 μm, water vapor transmission rate: 25 g / m ² · 24 hr or less), and a polypropylene bush was pushed into both ends of the core. .
A roll-shaped sample whose both ends were closed with the bush was stored at 25 ° C. and 55% RH for 30 days, and then the presence or absence of end face fusion was observed and evaluated according to the following criteria.
〔Evaluation criteria〕
○: End face fusion is not confirmed, and the laminate can be used satisfactorily.
(Triangle | delta): The state in which a part of end surface is glossy and a slight amount of end surface fusion has occurred (use limit).
X: A state in which the entire end surface is glossy and a large amount of end surface fusion occurs.

(Example 3)
In Example 2, except that the dendritic compound 1 obtained in Synthesis Example 1 was replaced with the dendritic compound 2 obtained in Synthetic Example 2 as shown in Table 1, it was the same as Example 2. Thus, the sensitivity, resolution, pencil hardness, cracking property at the time of bending, and presence / absence of end face fusion were evaluated. The results are shown in Table 2.

Example 4
In Example 2, the dendritic compound 1 obtained in Synthesis Example 1 was replaced with the dendritic compound 3 obtained in Synthetic Example 3 as shown in Table 1. Thus, the sensitivity, resolution, pencil hardness, cracking property at the time of bending, and presence / absence of end face fusion were evaluated. The results are shown in Table 2.

(Example 5)
In Example 2, the photopolymerization initiator was replaced with a compound represented by the following formula I-2 as shown in Table 1, in the same manner as in Example 1, sensitivity, resolution, pencil hardness, bending The crack property at the time and the presence / absence of end face fusion were evaluated. The results are shown in Table 2.

(Example 6)
In Example 2, the photopolymerization initiator was changed to a compound represented by the following formula I-3 as shown in Table 1, and the sensitivity, resolution, pencil hardness, bending were performed in the same manner as in Example 1. The crack property at the time and the presence / absence of end face fusion were evaluated. The results are shown in Table 2.

(Example 7)
In Example 2, the photopolymerization initiator was changed to a compound represented by the following formula I-4 as shown in Table 1, except that the sensitivity, resolution, pencil hardness, and bending were the same as in Example 1. The crack property at the time and the presence / absence of end face fusion were evaluated. The results are shown in Table 2.

(Example 8)
In Example 2, the photopolymerization initiator was changed to a compound represented by the following formula I-5 as shown in Table 1, and the sensitivity, resolution, pencil hardness, bending were performed in the same manner as in Example 1. The crack property at the time and the presence / absence of end face fusion were evaluated. The results are shown in Table 2.

Example 9
In Example 2, the photopolymerization initiator was changed to a compound represented by the following formula I-6 as shown in Table 1, and the sensitivity, resolution, pencil hardness, bending were performed in the same manner as in Example 1. The crack property at the time and the presence / absence of end face fusion were evaluated. The results are shown in Table 2.

(Example 10)
In Example 2, except that the binder 1 obtained in Synthesis Example 4 was replaced with the binder 2 obtained in Synthesis Example 5 (solid content of 30% by mass in 1-methoxy-2-propanol solution). In the same manner as in Example 2, the sensitivity, resolution, pencil hardness, cracking property during bending, and presence / absence of end face fusion were evaluated. The results are shown in Table 2.

(Example 11)
In Example 2, except that the binder 1 obtained in Synthesis Example 4 was replaced with 49 parts by mass of the binder 3 obtained in Synthesis Example 6 (solid content of 54% by mass in propylene glycol monomethyl ether acetate solution), In the same manner as in Example 2, the sensitivity, resolution, pencil hardness, cracking property during bending, and presence / absence of end face fusion were evaluated. The results are shown in Table 2.

(Example 12)
In Example 1, instead of the pattern forming apparatus, a glass negative mask having the same pattern as this was separately prepared, and this negative mask was brought into contact with the photosensitive laminate, and exposure was performed at 40 mJ / cm ² with an ultrahigh pressure mercury lamp. Exposed in quantity. Then, it developed by the method similar to Example 1, and except having measured the resolution, it carried out similarly to Example 1, and evaluated the resolution, pencil hardness, and the crack property at the time of bending. The results are shown in Table 2.

(Example 13)
In Example 2, instead of the pattern forming apparatus, a glass negative mask having a pattern similar to the above was prepared separately, and this negative mask was brought into contact with the photosensitive laminate, and exposure was performed at 20 mJ / cm ² with an ultrahigh pressure mercury lamp. Exposed in quantity. Then, it developed by the method similar to Example 1, and except having measured the resolution, it carried out similarly to Example 1, and evaluated the resolution, pencil hardness, and the crack property at the time of bending. The results are shown in Table 2.

(Example 14)
In Example 2, the photopolymerization initiator was changed to a compound represented by the following formula I-7 as shown in Table 1, and the sensitivity, resolution, pencil hardness, bending were performed in the same manner as in Example 1. The crack property at the time and the presence / absence of end face fusion were evaluated. The results are shown in Table 2.

(Example 15)
In Example 2, the photopolymerization initiator was changed to a compound represented by the following formula I-8 as shown in Table 1, and the sensitivity, resolution, pencil hardness, bending were performed in the same manner as in Example 1. The crack property at the time and the presence / absence of end face fusion were evaluated. The results are shown in Table 2.

(Example 16)
In Example 2, the photopolymerization initiator was changed to a compound represented by the following formula I-9 as shown in Table 1, and the sensitivity, resolution, pencil hardness, bending were performed in the same manner as in Example 1. The crack property at the time and the presence / absence of end face fusion were evaluated. The results are shown in Table 2.

(Example 17)
In Example 2, except that 1 part by mass of the photopolymerization initiator was replaced with 1 part by mass of the compound represented by the following formula I-10 as shown in Table 1, in the same manner as in Example 2, Sensitivity, resolution, pencil hardness, cracking property during bending, and presence / absence of end face fusion were evaluated. The results are shown in Table 2.

(Example 18)
In Example 2, the sensitizer was changed to 0.6 part by mass of N-methylacridone and 0.2 part by mass of 4,4 ′-(N, N-diethylamino) benzophenone. Similarly, the sensitivity, resolution, pencil hardness, cracking property at the time of bending, and presence / absence of end face fusion were evaluated. The results are shown in Table 2.

Example 19
In Example 2, except that the following components were further added to the photosensitive composition, the sensitivity, resolution, pencil hardness, cracking property at the time of bending, and presence / absence of end face fusion were evaluated in the same manner as in Example 2. It was. The results are shown in Table 2.
-Mixture of bisphenol A type epoxy compound and bisphenol F type epoxy compound (manufactured by Toto Kasei Co., Ltd., Epototo ZX-1059, epoxy equivalent 165 g / eq. (Alkali insoluble thermal crosslinking agent)) ... 5 parts by mass Curing accelerator (dicyandiamide): 0.50 parts by mass

(Comparative Example 1)
In Example 2, except that the dendritic branched compound 1 obtained in Synthesis Example 1 was replaced with dipentaerythritol hexaacrylate (DPHA) as shown in Table 1, the sensitivity, The resolution, pencil hardness, cracking property during bending, and presence / absence of end face fusion were evaluated. The results are shown in Table 2.

(Comparative Example 2)
In Example 2, as shown in Table 1, sensitivity, resolution, and The pencil hardness, the cracking property at the time of bending, and the presence / absence of end face fusion were evaluated. The results are shown in Table 2.

From the result of Table 2, in Examples 1-19, since a polymeric compound uses the photosensitive composition containing the dendritic compound which has a polymeric group, there is no generation | occurrence | production of a crack at the time of bending, and there is also little end surface fusion | melting. I found out. In particular, in Examples 2 to 11 and Examples 14 to 19 in which photosensitive films were prepared and subjected to laser exposure, it was found that sensitivity and resolution were also high. Moreover, it turned out that end surface fusion does not generate | occur | produce in Examples 2-9 and Examples 14-19 in which a binder contains the high molecular compound which has an acidic group and an ethylenically unsaturated bond in a side chain. Furthermore, in Example 19 containing a thermal crosslinking agent, it turned out that pencil hardness is also high.

The photosensitive composition, the photosensitive film, and the photosensitive laminate of the present invention contain a dendritic compound having a polymerizable group as a polymerizable compound, so that sensitivity, resolution, and cured product characteristics as a permanent protective film are obtained. High-definition and high-definition patterns can be efficiently formed with less exudation (end-face fusion) of the photosensitive composition from the roll made into a film, so that protective films, interlayer insulating films, solder resist patterns, etc. Can be suitably used for the formation of various patterns such as permanent patterns, color filters, pillar materials, rib materials, spacers, production of liquid crystal structural members such as spacers, partition walls, holograms, micromachines, and proofs. Can be suitably used for forming a permanent pattern.
Since the permanent pattern forming method of the present invention uses the photosensitive laminate of the present invention, it is used for forming various patterns such as a protective film, an interlayer insulating film, a permanent pattern such as a solder resist pattern, a color filter, a column material, It can be suitably used for the production of liquid crystal structural members such as ribs, spacers and partition walls, the production of holograms, micromachines, and proofs, and can be particularly suitably used for the formation of permanent patterns on printed boards.

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. FIG. 23 is a model diagram showing a standard structure of a dendritic branched compound having at least two polymerizable groups.

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)

Claims (17)

Including a binder, a polymerizable compound, and a photopolymerization initiator,
A photosensitive composition, wherein the polymerizable compound includes a dendritic compound having a polymerizable group, and the photopolymerization initiator includes an oxime derivative.   The photosensitive composition according to claim 1, wherein the dendritic compound having a polymerizable group is either a dendrimer compound or a hyperbranched compound having at least two polymerizable groups.   The dendritic compound having a polymerizable group is either a dendrimer compound or a hyperbranched compound formed by either a polycondensation reaction or a polyaddition reaction of a compound having two kinds of functional groups in one molecule. The photosensitive composition in any one of Claim 1 to 2.   The photosensitive composition according to any one of claims 1 to 3, wherein the dendritic compound having a polymerizable group has an ester bond. 5. The photosensitive composition according to claim 1, wherein the oxime derivative has a partial structure represented by any one of the following general formula (I) and the following general formula (II).
In the general formula (I) and (II), Ar represents an aromatic group, or a heterocyclic group, Y ¹ represents any substituent of a hydrogen atom and monovalent, Y ² represents an aliphatic group, an aromatic group, a heterocyclic group, COY ³ , CO ₂ Y ³ , or CONY ⁴ Y ⁵ , and Y ³ , Y ⁴ , and Y ⁵ are an aliphatic group, It represents either an aromatic group or a heterocyclic group, and m represents an integer of 1 or more.   A thermal crosslinking agent is included, and 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. The photosensitive composition in any one of 1-5.   The photosensitive composition according to any one of claims 1 to 6, wherein the binder is alkali-soluble.   The photosensitive composition in any one of Claim 1 to 7 in which a binder contains the high molecular compound which has an acidic group and an ethylenically unsaturated bond in a side chain.   The photosensitive composition in any one of Claim 1 to 8 in which a binder contains the high molecular compound which has an acidic group, the aromatic group which may contain a heterocyclic ring, and an ethylenically unsaturated bond in a side chain.   The photosensitive composition in any one of Claim 1 to 7 in which a binder contains an epoxy acrylate compound.   A photosensitive film comprising a support and a photosensitive layer made of the photosensitive composition according to claim 1 on the support.   The photosensitive film according to claim 11, which is long and wound in a roll.   A photosensitive laminate comprising a photosensitive layer comprising the photosensitive composition according to claim 1 on a substrate.   The photosensitive laminated body of Claim 13 in which the photosensitive layer was formed with the photosensitive film in any one of Claims 11-12.   The permanent pattern formation method characterized by including exposing with respect to the photosensitive layer in the photosensitive laminated body in any one of Claim 13 to 14.   The permanent pattern formation method according to claim 15, wherein the exposure is performed using a laser beam having a wavelength of 350 to 415 nm. A printed circuit board, wherein a permanent pattern is formed by the method for forming a permanent pattern according to claim 15.