JP2007086373A - Permanent pattern forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a permanent pattern forming method by which permanent patterns such as a protective film, an insulating film and a solder resist pattern can be efficiently formed with high definition, by forming a desired drawn pattern with few jags on a surface of a photosensitive layer to be exposed without reducing exposure speed, in a pattern forming method in which exposure is performed for drawing by inclining a light modulating means. <P>SOLUTION: The permanent pattern forming method includes exposing a photosensitive layer, wherein at least one of array pitch (a), tilt angle (b), drawing pitch (c) and phase difference (d) of drawn pixels is set so that at least one of jag pitch and jag amplitude of jags produced by reproduction with drawn pixels formed by imaging sections becomes a predetermined value or less, and the exposure is performed under modulation control of the imaging sections based on pattern information at predetermined timing. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention uses an exposure head that is relatively moved in a predetermined scanning direction along an exposed surface of a photosensitive layer, exposes the photosensitive layer based on pattern information, and includes a printed wiring board including a package substrate, Alternatively, the present invention relates to a permanent pattern forming method for efficiently forming a high-definition permanent pattern (a protective film, an interlayer insulating film, and a solder resist pattern) in the semiconductor field.

Conventionally, as a light modulation means, a spatial light modulation element such as a digital micromirror device (DMD) is used to form a drawing pattern (image) with a light beam modulated in accordance with pattern information (image data). Various exposure apparatuses for performing exposure have been proposed.
The DMD is a mirror device in which a number of micromirrors that change the angle of the reflecting surface in accordance with a control signal are two-dimensionally arranged on a semiconductor substrate such as silicon, and an exposure head equipped with this DMD is placed on an exposed surface. By performing relative movement in the scanning direction along the line, exposure to a desired range is performed.

  In general, the DMD micromirrors are arranged so that the arrangement direction of each row and the arrangement direction of each column are orthogonal to each other. By arranging such a DMD so as to be inclined with respect to the scanning direction, the interval between the scanning lines becomes close and the resolution can be increased.

For example, in Patent Document 1, in an illumination system that guides light to a sub-region (spatial light modulation element: image source) having a plurality of light valves, the sub-region is inclined with respect to the projection on the scanning line. Describes that the resolution can be increased.
According to this method, the resolution in the direction orthogonal to the scanning direction can be increased. Further, since the resolution in the scanning direction is usually determined by the scanning speed and the modulation speed of the spatial light modulation element, the exposure speed (scanning speed) is decreased or the modulation speed of the spatial light modulation element is increased. It is possible to increase the resolution.

By the way, in order to increase the resolution of the formed drawing pattern, when drawing is performed with the light irradiation means (spatial light modulation element) tilted as in the method of Patent Document 1, some drawing patterns cannot be ignored. There is a risk of jaggy.
For example, when forming a linear drawing pattern extending in the scanning direction or a direction orthogonal to the scanning direction, the position between each drawing pixel formed by the spatial light modulator and a desired drawing position of the drawing pattern Misalignment may be recognized as jaggy.
That is, a drawing pattern constituted by a set of a large number of discrete pixels is reproduced by discrete drawing pixels corresponding to the pixel part, and therefore, jagged jaggy is formed at the edge of the reproduced image. There is a risk that such a problem may occur that the line width of the drawing pattern based on the pattern information is reduced. When a resist pattern or the like is formed by exposing the photosensitive layer with such a drawing pattern and then performing development or the like, there is a problem that a high-definition pattern cannot be obtained.

  Therefore, by forming a desired drawing pattern with reduced jaggies on the exposed surface without reducing the exposure speed, a permanent pattern such as a protective film, an insulating film, and a solder resist pattern can be formed with high definition and A permanent pattern forming method that can be formed efficiently has not been provided yet, and the present situation is that further improved development is desired.

Special table 2001-500628 gazette

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, the present invention provides a pattern forming method in which exposure is performed by tilting the light modulation means to perform drawing, and the generation of jaggies on the exposed surface of the photosensitive layer is suppressed without reducing the exposure speed. It is an object of the present invention to provide a permanent pattern forming method capable of forming a permanent pattern such as a protective film, an insulating film, and a solder resist pattern with high definition and efficiency by forming a drawing pattern.

Means for solving the problems are as follows. That is,
<1> For the photosensitive layer formed on the surface of the substrate with a photosensitive composition containing at least a binder, a polymerizable compound, a photopolymerization initiation system compound, and a thermal crosslinking agent,
A light irradiating means, and n (where n is a natural number of 2 or more) two-dimensionally arranged picture elements that receive and emit light from the light irradiating means, and according to the pattern information, An exposure head provided with a light modulation means capable of controlling a picture element portion, wherein the exposure head is arranged such that a column direction of the picture element portion forms a predetermined inclination angle with respect to a scanning direction of the exposure head. And performing exposure by moving the exposure head relative to the scanning direction,
In the drawing pattern corresponding to the pattern information, at least one of jaggy pitch and jaggy amplitude generated by being reproduced by the drawing pixel formed by the picture element portion is equal to or less than a predetermined value,
(A) an arrangement pitch of the drawing pixels formed by the adjacent picture element portions;
(B) an inclination angle of the two-dimensional drawing pixel group composed of a plurality of the drawing pixels with respect to the scanning direction;
(C) a drawing pitch of the drawing pixels with respect to the scanning direction, and (d) a phase difference of a drawing position with respect to the scanning direction of the drawing pixels formed adjacent to a direction substantially orthogonal to the scanning direction,
The permanent pattern forming method is characterized in that at least one of the above is set, and the picture element portion is subjected to modulation control at a predetermined timing based on the pattern information, exposed, and developed. In the permanent pattern forming method according to <1>, an exposure head provided with a light modulation unit is relatively moved with respect to the photosensitive layer in a predetermined scanning direction along the exposed surface of the photosensitive layer, Exposure is performed based on the pattern information, and (a) an arrangement pitch, (b) an inclination angle, (c) a drawing pitch, so that at least one of the jaggy pitch and the jaggy amplitude is equal to or less than a predetermined value. And (d) means for setting at least one of the phase differences and performing modulation control on each pixel part at a predetermined timing in accordance with the pattern information, thereby increasing the number of drawing pixels per unit area. It is possible to set an optimal drawing condition and draw a drawing pattern (image) that suppresses the occurrence of jaggies without reducing the exposure speed (drawing speed). As a result, the photosensitive layer is exposed with high definition, and then the photosensitive layer is developed to form a high-definition pattern.
<2> The permanent pattern forming method according to <1>, wherein the light modulation unit is a spatial light modulation element.
<3> The method for forming a permanent pattern according to any one of <1> to <2>, wherein the spatial light modulation element is a digital micromirror device (DMD).

<4> The method for forming a permanent pattern according to any one of <1> to <3>, wherein the formation of the photosensitive layer is performed by applying the photosensitive composition to the surface of the substrate and drying. In the permanent pattern forming method according to <4>, the photosensitive composition is applied to the surface of the substrate and dried. As a result, the photosensitive layer is formed on the substrate.
<5> The formation of the photosensitive layer is carried out by subjecting a photosensitive film having a support and a photosensitive layer formed by laminating the photosensitive composition on the support to the base material under at least one of heating and pressurization. The method for forming a permanent pattern according to any one of <1> to <4>, wherein the method is performed by laminating on a surface. In the method for forming a permanent pattern according to <5>, the photosensitive film having the support and a photosensitive layer obtained by laminating a photosensitive composition on the support is at least either heated or pressurized. It is laminated | stacked on the surface of the said base material under this. As a result, the photosensitive layer is formed by being transferred onto the substrate.
<6> The above <1> to <5>, wherein the binder includes at least one of an epoxy acrylate compound and at least one of a vinyl copolymer having a (meth) acryloyl group and an acidic group in a side chain. The permanent pattern forming method according to any one of the above.
<7> From the above <1> to <5>, wherein the binder is a copolymer obtained by reacting 0.1 to 1.2 equivalents of a primary amine compound with respect to the anhydride group of the maleic anhydride copolymer. The permanent pattern forming method according to any one of the above.
<8> The binder is (a) maleic anhydride, (b) an aromatic vinyl monomer, and (c) a vinyl monomer, and the glass transition temperature (Tg) of the homopolymer of the vinyl monomer <1> to <5 obtained by reacting 0.1 to 1.0 equivalent of a primary amine compound with an anhydride group of a copolymer consisting of a vinyl monomer having a temperature of less than 80 ° C. The permanent pattern forming method according to any one of the above.
<9> From the above <1>, wherein the thermal crosslinking agent is at least one selected from an epoxy compound, an oxetane compound, a polyisocyanate compound, a compound obtained by reacting a polyisocyanate compound with a blocking agent, and a melamine derivative. The permanent pattern forming method according to any one of 8>.
<10> The method for forming a permanent pattern according to <9>, wherein the melamine derivative is an alkylated methylol melamine.
<11> The method for forming a permanent pattern according to any one of <1> to <10>, wherein the polymerizable compound includes a monomer having at least one of a urethane group and an aryl group.
<12> The method for forming a permanent pattern according to any one of <1> to <11>, wherein the polymerizable compound includes a monomer having at least one of an ethylene oxide group and a propylene oxide group.
<13> The method for forming a permanent pattern according to any one of <1> to <12>, wherein the photosensitive composition contains a sensitizer.
<14> The above <13, wherein the sensitizer is at least one selected from a condensed ring compound and an amine compound substituted with at least two aromatic hydrocarbon rings or aromatic heterocyclic rings. > Is a method for forming a permanent pattern.

<15> The method for forming a permanent pattern according to any one of <5> to <14>, wherein the support includes a synthetic resin and is transparent.
<16> The method for forming a permanent pattern according to any one of <5> to <15>, wherein the support has a long shape.
<17> The method for forming a permanent pattern according to any one of <5> to <16>, wherein the photosensitive film has a long shape and is wound in a roll shape.
<18> The method for forming a permanent pattern according to any one of <5> to <17>, wherein the photosensitive film has a protective film on the photosensitive layer.
<19> The method for forming a permanent pattern according to any one of <1> to <18>, wherein the photosensitive layer has a thickness of 3 to 100 μm.
<20> The permanent pattern forming method according to any one of <1> to <19>, wherein the base material is a printed wiring board on which wiring has been formed. In the permanent pattern forming method according to <20>, since the base material is a printed wiring board on which wiring has been formed, by using the permanent pattern forming method, a multilayer wiring board or build-up of a semiconductor or a component can be used. High-density mounting on a wiring board or the like is possible.

<21> The exposure is performed using an exposure apparatus including at least one of a drawing pixel group rotating unit, a drawing magnification changing unit, a drawing timing changing unit, a moving speed changing unit, and a phase difference changing unit. To <20>.
<22> The permanent pattern according to any one of <1> to <21>, wherein either the entire exposure head or the light modulation unit is rotated by the drawing pixel group rotating unit to change the tilt angle (b). It is a forming method.
<23> The drawing magnification changing unit changes the drawing magnification of the drawing pixels formed on the exposed surface of the photosensitive layer, and adjusts either the arrangement pitch (a) or the drawing pitch (c). > To <21>. The method for forming a permanent pattern according to any one of <21>.
<24> The method according to any one of <1> to <21>, wherein the drawing timing changing unit changes the drawing timing of the photosensitive layer on the exposed surface of the photosensitive layer by the drawing unit and adjusts the drawing pitch (c). This is a permanent pattern forming method.
<25> The permanent pattern according to any one of <1> to <21>, wherein the moving speed changing unit changes the relative moving speed of the exposure head with respect to the exposed surface of the photosensitive layer to adjust the drawing pitch (c). It is a forming method.
<26> The permanent pattern according to any one of <1> to <21>, wherein the phase difference changing unit changes the phase difference of the modulation control timing of adjacent pixel parts to change the phase difference (d). It is a forming method.

<27> The permanent pattern forming method according to any one of <1> to <26>, wherein the predetermined values of the jaggy pitch and the jaggy amplitude are a dot diameter of a drawing pixel formed on the exposed surface of the photosensitive layer. .
<28> A plurality of drawing pixel groups each having a plurality of picture element portions, and in each of the picture element portion groups, an arrangement pitch (a), an inclination angle (b), a drawing pitch (c), and a phase difference (d) The method for forming a permanent pattern according to any one of <1> to <27>, wherein at least one of the above is individually set.
<29> An arrangement pitch (a) having a plurality of drawing pixel groups each including a plurality of picture element portions, and an average value of any one of the jaggy pitch and the jaggy amplitude generated in each of the picture element portions is equal to or less than a predetermined value. The permanent pattern forming method according to any one of <1> to <27>, wherein at least one of tilt angle (b), drawing pitch (c), and phase difference (d) is set.
<30> Any one of <1> to <29> in which at least one of the arrangement pitch (a), the inclination angle (b), the drawing pitch (c), and the phase difference (d) is set according to the drawing pattern This is a method for forming a permanent pattern as described above.
<31> According to the inclination angle of the drawing pattern with respect to the scanning direction, at least one of the arrangement pitch (a), the inclination angle (b), the drawing pitch (c), and the phase difference (d) is set <1>. To <30>.
<32> The arrangement pitch (a), the inclination angle (b), and the drawing so that any one of the jaggy pitch and the jaggy amplitude generated in the drawing pattern orthogonal or substantially orthogonal to the scanning direction is equal to or less than a predetermined value. The permanent pattern forming method according to any one of <1> to <31>, wherein at least one of pitch (c) and phase difference (d) is set.

<33> Adjustment of arrangement pitch (a), inclination angle (b), drawing pitch (c), and phase difference (d)
(E) the pitch of the control point sequence along the substantially scanning direction of the control point, the control point defined as the center point of the drawing pixel formed on the exposed surface of the photosensitive layer by the picture element unit,
(F) the arrangement direction of the control point sequence;
(G) a pitch of the control points with respect to the scanning direction, and (h) a phase difference of the control points adjacent to the direction substantially orthogonal to the scanning direction with respect to the scanning direction,
The method for forming a permanent pattern according to any one of <1> to <32>, wherein the method is performed by controlling at least one of the method so that jaggy of a drawing pattern is reduced.
<34> At least one of the pitch (e) of the control point sequence, the arrangement direction (f), the pitch (g) of the control point with respect to the scanning direction, and the phase difference (h), and at least one of the jaggy pitch and the jaggy amplitude Find the correlation with the shape of the jaggy defined by
The permanent pattern forming method according to <33>, wherein any one of (e) to (h) is set or changed based on the correlation.
<35> At least one of the pitch (e) of the control point sequence in which the jaggy shape falls within the allowable range, the arrangement direction (f), the pitch (g) of the control point with respect to the scanning direction, and the phase difference (h) The permanent pattern forming method according to any one of <33> to <34>, wherein the condition is defined as a selection condition.
<36> At least one of the pitch (e) of the control point sequence where the jaggy shape is outside the allowable range, the arrangement direction (f), the pitch (g) of the control point with respect to the scanning direction, and the phase difference (h) The method for forming a permanent pattern according to any one of <33> to <34>, wherein the condition is defined as a prohibition condition.
<37> Corresponding to the direction of the drawing pattern, at least one of the pitch (e) of the control point sequence, the arrangement direction (f), the pitch (g) of the control points with respect to the scanning direction, and the phase difference (h) The permanent pattern forming method according to any one of <33> to <35>, wherein a correlation with a jaggy shape defined by at least one of a jaggy pitch and a jaggy amplitude is obtained.
<38> The method for forming a permanent pattern according to <37>, wherein the direction of the drawing pattern is a representative direction of the drawing pattern included in a predetermined region of the drawing pattern.
<39> The permanent pattern forming method according to <38>, wherein a representative direction of the drawing pattern is included in a predetermined region of the drawing pattern and is a direction orthogonal or substantially orthogonal to the scanning direction.
<40> At least one of the pitch (e) of the control point sequence, the arrangement direction (f), the pitch (g) of the control points with respect to the scanning direction, and the phase difference (h) for each drawing pattern in the predetermined region. The permanent pattern forming method according to any one of <34> to <35>, wherein the correlation between the shape and the shape of the jaggy defined by at least one of the jaggy pitch and the jaggy amplitude is obtained.
<41> At least one of the pitch (e) of the control point sequence, the arrangement direction (f), the pitch (g) of the control points with respect to the scanning direction, and the phase difference (h) for each drawing pattern in the predetermined region. It is a permanent pattern formation method as described in said <40> which sets or changes these.

<42> At least one of the pitch (e), the arrangement direction (f) of the control point sequence, the pitch (g) of the control point with respect to the scanning direction, and the phase difference (h), and at least one of the jaggy pitch and the jaggy amplitude Correlation with the shape of jaggy defined by
Said <34 calculated | required based on the calculated value calculated | required from at least any one of the pitch (e) of a control point row | line | column, the arrangement direction (f), the pitch (g) with respect to the said scanning direction of the said control point, and a phase difference (h). > To <41>.
<43> The pitch of the control point sequence from the pitch (e), the arrangement direction (f), the pitch (g) of the control point with respect to the scanning direction, and the drawing pattern based on the phase difference (h). (E) Jagged shape defined by at least one of the arrangement direction (f), the pitch (g) of the control points with respect to the scanning direction, and the phase difference (h), and at least one of the jaggy pitch and the jaggy amplitude. The method for forming a permanent pattern according to any one of <34> to <41>, wherein the correlation is obtained by measuring a correlation with the pattern.

<44> The permanent pattern forming method according to any one of <1> to <43>, wherein the light irradiation unit emits laser light emitted from a semiconductor laser element.
<45> The method for forming a permanent pattern according to <1> to <44>, wherein the light irradiation unit can synthesize and irradiate two or more lights.
<46> The above <1>, wherein the light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that condenses the laser beams emitted from the plurality of lasers and couples the laser beams to the multimode optical fiber. > To <45>.
<47> The method for forming a permanent pattern according to any one of <44> to <46>, wherein the wavelength of the laser beam is 395 to 415 nm.

<48> The method for forming a permanent pattern according to any one of <1> to <47>, wherein the photosensitive layer is subjected to a curing treatment after development.
<49> The permanent pattern forming method according to <48>, 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.
<50> The method for forming a permanent pattern according to any one of <1> to <49>, wherein at least one of a protective film, an interlayer insulating film, and a solder resist pattern is formed.

  According to the present invention, a conventional problem can be solved, and in the pattern forming method for performing exposure by drawing the light modulation means while tilting the light modulation means, on the exposed surface of the photosensitive layer without reducing the exposure speed. To provide a permanent pattern forming method capable of forming a permanent pattern such as a protective film, an insulating film, and a solder resist pattern with high definition and efficiency by forming a desired drawing pattern in which generation of jaggies is suppressed. Can do.

(Permanent pattern forming method)
The permanent pattern forming method of the present invention includes at least an exposure step and a development step, preferably includes a curing treatment step, and further includes other steps appropriately selected as necessary.

[Exposure process]
In the exposing step, the photosensitive layer is irradiated with light, and n (where n is a natural number of 2 or more) two-dimensionally arranged pixels that receive and emit light from the light irradiating means. An exposure head having a light modulation means capable of controlling the drawing unit according to pattern information, wherein a column direction of the drawing unit is inclined at a predetermined inclination with respect to a scanning direction of the exposure head. This is a step of performing exposure by using an exposure head arranged at an angle and moving the exposure head relatively in the scanning direction.

In the drawing pattern corresponding to the pattern information, the exposure is performed so that at least one of the jaggy pitch and the jaggy amplitude of jaggy generated by being reproduced by the drawing pixels formed by the picture element portion is a predetermined value or less.
(A) an arrangement pitch of the drawing pixels formed by the adjacent picture element portions;
(B) an inclination angle of the two-dimensional drawing pixel group composed of a plurality of the drawing pixels with respect to the scanning direction;
(C) a drawing pitch of the drawing pixels with respect to the scanning direction, and (d) a phase difference of a drawing position with respect to the scanning direction of the drawing pixels formed adjacent to a direction substantially orthogonal to the scanning direction,
Is set, and the pixel part is modulated and controlled at a predetermined timing based on the pattern information.

  Hereinafter, an example of an exposure apparatus related to the exposure process of the permanent pattern forming method of the present invention will be described with reference to the drawings. The exposure method in the exposure step will be clarified through the description of the exposure apparatus.

<Configuration of exposure apparatus>
<< Appearance of exposure apparatus >>
FIG. 1 shows an exposure apparatus 10 of a flat bed type that is a drawing apparatus according to an embodiment of the present invention.
The exposure apparatus 10 includes a surface plate 14 that is supported by a plurality of legs 12 and is extremely small in deformation. On the surface plate 14, an exposure stage 18 reciprocates in the direction of an arrow via two guide rails 16. It is installed as possible. The exposure stage 18 adsorbs a substrate on which a sheet film F, which is a laminate (hereinafter sometimes referred to as “photosensitive material”), in which the photosensitive layer is laminated on a substrate to be processed. Retained.

  A gate-shaped column 20 is installed at the center of the surface plate 14 so as to straddle the guide rail 16. Cameras 22 a and 22 b for detecting alignment marks recorded on the sheet film F are fixed to one side of the column 20, and a drawing pattern (image) for the sheet film F is fixed to the other side. A scanner 26 in which a plurality of exposure heads 24a to 24j (drawing heads) to be formed is positioned and held is fixed.

FIG. 2 shows the configuration of each of the exposure heads 24a to 24j.
For example, laser beams L output from a plurality of semiconductor lasers constituting the light source unit 28 serving as the light irradiation unit are combined and introduced into the exposure heads 24 a to 24 j through the optical fiber 30. A rod lens 32, a reflection mirror 34, and a digital micromirror device (DMD) 36 are arranged in order at the exit end of the optical fiber 30 into which the laser beam L is introduced.

As shown in FIG. 3, the DMD 36 includes a large number of micromirrors 40 (drawing elements) arranged in a lattice on an SRAM cell (memory cell) 38 in a swingable state. A material having high reflectivity such as aluminum is deposited on the surface of the mirror 40. When a digital signal according to the drawing data is written in the SRAM cell 38, each micromirror 40 is inclined in a predetermined direction centered on a diagonal line as shown in FIGS. 4 and 5 according to the state of the signal.
4 shows a case where the micromirror 40 is tilted in the direction of the on state, and FIG. 5 shows a case where the micromirror 40 is tilted in the direction of the off state. Therefore, by controlling the inclination of each micromirror 40 of the DMD 36 with the modulation signal based on the pattern information (drawing data) supplied from the control unit 42, the laser beam L is selectively transferred to the sheet film F according to the drawing data. Thus, a desired drawing pattern (image) can be drawn.

In the emission direction of the laser beam L reflected by the micromirror 40 in the on state, a large number of lenses are arranged corresponding to the first imaging optical lenses 44 and 46 that are the magnifying optical system and each micromirror 40 of the DMD 36. The microlens array 48 and the second imaging optical lenses 50 and 52, which are a zoom optical system, are sequentially arranged.
Before and after the micro lens array 48, micro aperture arrays 54 and 56 for removing stray light and adjusting the laser beam L to a predetermined diameter are disposed.

As shown in FIG. 6, the exposure heads 24 a to 24 j configured as described above are arranged in a staggered pattern in two rows in a direction orthogonal to the scanning direction of the sheet film F (the moving direction of the exposure stage 18).
As shown in FIG. 7, the DMD 36 incorporated in each of the exposure heads 24a to 24j is set in a state inclined at a predetermined angle with respect to the scanning direction in order to achieve a high resolution. That is, by inclining the DMD 36 with respect to the scanning direction of the sheet film F, the interval with respect to the direction orthogonal to the scanning direction of the micromirrors 40 constituting the DMD 36 is narrowed, thereby reducing the resolution with respect to the direction orthogonal to the scanning direction. Can be high.
It should be noted that the exposure areas 58a to 58j by the exposure heads 24a to 24j are set so as to overlap in a direction orthogonal to the scanning direction so that a joint between the exposure heads 24a to 24j does not occur.

  FIG. 8 is a block diagram of the main part of the control circuit of the exposure apparatus 10. A control unit 42 (control means) that controls the exposure apparatus 10 includes a synchronization signal generator 64 that generates a synchronization signal based on the position data of the exposure stage 18 detected by the encoder 62, and exposure based on the generated synchronization signal. An exposure stage driving unit 66 that moves the stage 18 in the scanning direction, a drawing data storage unit 68 that stores drawing data of a drawing pattern (image) drawn on the sheet film F, and the DMD 36 based on the synchronization signal and the drawing data. A DMD modulation unit 70 that controls the modulation of the SRAM cell 38 and drives the micromirror 40 is provided.

  The control unit 42 also adjusts the synchronization signal generated by the synchronization signal generation unit 64, such as a frequency changing unit 72 (drawing timing changing unit), a phase difference changing unit 74 (phase difference changing unit), and a moving speed changing unit 75 ( It is preferable that a moving speed changing means is provided.

The frequency changing unit 72 serving as the drawing timing changing unit changes the frequency for determining the on / off control timing with respect to the scanning direction of the micromirror 40 constituting the DMD 36 and supplies the same to the synchronization signal generating unit 64 for drawing on the sheet film F. The interval in the scanning direction of the pixels to be adjusted is adjusted.
The phase difference changing unit 74 as the phase difference changing unit changes the phase difference of the on / off control timings of the micromirrors 40 arranged adjacent to each other in a direction substantially orthogonal to the scanning direction and supplies the same to the synchronization signal generating unit 64. Then, the phase difference of the pixels drawn on the sheet film F with respect to the scanning direction is adjusted.
The moving speed changing unit 75 as the moving speed changing unit adjusts the moving speed of the exposure stage 18 by changing the moving speed of the exposure stage 18 and supplying the changed moving speed to the synchronization signal generating unit 64.

  Further, the control unit 42 is preferably provided with an exposure head rotation driving unit 76 (drawing pixel group rotating unit) and an optical magnification changing unit 78 (drawing magnification changing unit) as necessary.

The exposure head rotation driving unit 76 serving as the drawing pixel group rotating unit rotates the exposure heads 24a to 24j by a predetermined angle around the optical axis of the laser beam L, and the scanning direction of the pixel array formed on the sheet film F is changed. Adjust the tilt angle. Note that the inclination angle of the pixel array may be adjusted by rotating some of the optical members of the exposure heads 24a to 24j.
The optical magnification changing unit 78 as the drawing magnification changing means controls the zoom optical system 79 constituted by the second imaging optical lenses 50 and 52 of the exposure heads 24a to 24j to change the optical magnification, and the adjacent micro The arrangement pitch of pixels formed on the sheet film F by the mirror 40 or the drawing pitch by the same micromirror 40 is adjusted.

<< Operation of exposure apparatus >>
The exposure apparatus 10 is basically configured as described above, and the operation when performing exposure using the exposure apparatus will be described below.
After the sheet film F is sucked and held on the exposure stage 18, the control unit 42 drives the exposure stage drive unit 66 to move the exposure stage 18 in one direction along the guide rail 16 of the surface plate 14. When the exposure stage 18 passes between the columns 20, the cameras 22 a and 22 b read the alignment marks recorded at predetermined positions on the sheet film F. The control unit 42 calculates the position correction data of the sheet film F based on the read position data of the alignment mark.

  After the position correction data is calculated, the control unit 42 moves the exposure stage 18 in the other direction, and starts exposure of the drawing pattern (image) on the sheet film F by the scanner 26.

  That is, the laser beam L output from the light source unit 28 as the light irradiating means is introduced into each exposure head 24 a to 24 j via the optical fiber 30. The introduced laser beam L enters the DMD 36 from the rod lens 32 via the reflection mirror 34.

  On the other hand, the drawing data (pattern information) read from the drawing data storage unit 68 and corrected by the position correction data is modulated by the DMD modulation unit 70 at a timing according to the synchronization signal supplied from the synchronization signal generation unit 64. And supplied to the DMD 36. As a result, each micromirror 40 constituting the DMD 36 is on / off controlled at a timing according to the synchronization signal according to the drawing data.

  As shown in FIGS. 4 and 5, the laser beam L selectively reflected in the desired direction by each micromirror 40 constituting the DMD 36 is expanded by the first imaging optical lenses 44 and 46, and then microscopically reflected. It is adjusted to a predetermined diameter via the aperture array 54, the microlens array 48, and the microaperture array 56, and then adjusted to a predetermined magnification by the second imaging optical lenses 50 and 52 constituting the optical magnification changing unit 78. Guided to the sheet film F.

  In this case, the exposure stage 18 moves along the surface plate 14, and a desired two-dimensional pattern is formed on the sheet film F by a plurality of exposure heads 24a to 24j arranged in a direction orthogonal to the moving direction of the exposure stage 18. (Hereinafter referred to as “two-dimensional image”) is drawn.

  By the way, the two-dimensional image drawn on the sheet film F as described above is constituted by a set of a large number of discrete pixels based on the micromirrors 40 constituting the DMD 36. In this case, the original image before drawing is reproduced by being mapped to discrete drawing points on the sheet film F, and therefore, from the pixel corresponding to the pixel part, depending on the relationship between the original image and the arrangement of the drawing points. In such a reproduced image, there is a risk that a jaggy having a jagged end portion of the image may occur, or a defect such as a decrease in line width accuracy of the original image may occur.

The exposure method in the permanent pattern forming method of the present invention can suppress the occurrence of jaggies and adjust the arrangement of the drawing pixels formed on the sheet film (laminate) F, thereby forming an appropriate drawing pattern. It is what.
The parameters that define the arrangement of the drawing pixels include (a) an arrangement pitch of the drawing pixels formed by the adjacent pixel parts, and (b) a two-dimensional drawing pixel group composed of a plurality of the drawing pixels. An inclination angle with respect to the scanning direction, (c) a drawing pitch of the drawing pixels with respect to the scanning direction, and (d) a drawing position with respect to the scanning direction of the drawing pixels formed adjacent to a direction substantially orthogonal to the scanning direction. Of at least one of them, and by setting at least one of these and controlling the modulation of the picture element portion at a predetermined timing, the occurrence of jaggy can be suppressed.
As a method of adjusting the parameters (a) to (d), a control point is defined as a center point of a drawing pixel formed on the exposed surface of the photosensitive layer by the picture element unit. (E) the pitch of the control point sequence along the substantially scanning direction of the control point, (f) the arrangement direction of the control point sequence, (g) the pitch of the control point with respect to the scanning direction, and (h) the scanning direction. And a phase difference with respect to the scanning direction of the control points adjacent to each other in a direction substantially perpendicular to the scanning direction, and a method of controlling at least one of them so that the jaggy of the drawing pattern is reduced.
Hereinafter, as an example, a case where jaggy caused by one DMD 36 is suppressed will be described.

FIG. 9 is a diagram schematically showing the arrangement of a large number of micromirrors 40 constituting one DMD 36.
In FIG. 9, the scanning direction of the sheet film F is defined as y, the direction orthogonal to the scanning direction y is defined as x, and the row of micromirrors 40 arranged substantially along the scanning direction y is defined as a swath 77. In this case, the swath 77 is set to a predetermined angle θs with respect to the x direction (hereinafter referred to as a swath inclination angle θs (≠ 90 °)) in order to increase the resolution of the drawn image in the x direction. Two micromirrors 40 adjacent on the swath 77 are designated as DMD pixels A and B.

FIG. 10 shows a control point (hereinafter referred to as an “address grid point”) defined by the DMD 36 and defined as the center point of the drawing pixel formed on the sheet film F, as shown in FIG. FIG. 6 is a diagram schematically showing a relationship with a desired drawing pattern (hereinafter referred to as “original image”). In FIG. 9, the address lattice points are indicated by solid circles and dotted circles, and the original image 80 is indicated as a linear drawing pattern.
In this case, the original image 80 is reproduced by a plurality of address lattice points indicated by solid line circles. The laser beam L forms pixels with a predetermined beam diameter (dot diameter) centering on each address lattice point. Accordingly, the image actually formed on the sheet film F is an image that is wider than the outline of the address lattice points indicated by the solid line, as indicated by the outline line 82.

  As shown in FIG. 10, there are three types of address lattice points, lattice point sequence 1, lattice point sequence 2, and lattice point sequence 3. The parameters characterizing each grid point sequence include the inclination angle θgi (i = 1 to 3) of the grid point sequence 1 to 3 with respect to the x direction, and the grid point pitch pgi ( i = 1 to 3) and the row pitch dgi (i = 1 to 3) of the lattice point rows 1 to 3.

  These parameters are the arrangement pitch of address lattice points (hereinafter also referred to as address lattice points A and B) formed on the sheet film F by the adjacent DMD pixels A and B (see FIG. 9) on the swath 77. ps (pitch of control point sequence (e)), swath inclination angle θs (arrangement direction of control point sequence (f)) (however, counterclockwise with respect to the x direction as +), and each address lattice point It is determined by the drawing pitch py with respect to the y direction (pitch (g) with respect to the scanning direction of the control point). Hereinafter, the relationship between these parameters will be described.

<(I) Inclination angle θgi (i = 1 to 3)>
Consider three adjacent address grid points A, B ′, B ″ shown in FIG. 11. The tilt angle θg3 of the grid point array 3 is:
θg3 = 90 ° Formula (1)
It is. In addition, regarding the inclination angles θg1 and θg2 of the grid points 1 and 2,
N1 = integer (ps · sin θs / py)
(Integer represents a truncation operation.)
N2 = N1 + 1
Then, the distance Δy1 in the y direction of the address grid points B ′ and B ″ with respect to the address grid point A,
Δy2 (the phase difference (h) of the control point adjacent to the direction substantially orthogonal to the scanning direction with respect to the scanning direction) is
Δyi = ps · sin θs−py · N1 (i = 1, 2)
It becomes. Further, the drawing pitch px in the x direction of the address lattice points A, B ′, B ″ is
px = ps · cos θs
Because
tan θgi = Δyi / py (i = 1, 2) Equation (2)
It becomes. Therefore, the inclination angles θg1 and θg2 of the lattice point rows 1 to 3 are
θgi = tan ⁻¹ {(ps · sin θs−py · Ni) / (ps · cos θs)}
(I = 1, 2) Formula (3)
It is obtained as

<(II) Lattice point pitch pgi (i = 1 to 3)>
Since the lattice point sequence 3 is composed of address lattice points arranged in the y direction,
pg3 = py Formula (4)
It is. Also,
pgi = px / cos θgi (i = 1, 2) Equation (5)
It is.

<(III) row pitch dgi (i = 1 to 3)>
The row pitch dg3 of the lattice point row 3 is
dg3 = px equation (6)
It is. Also,
dgi = py · cos θgi (i = 1, 2) Equation (7)
It is.

On the other hand, jaggies that are generated when the original image 80 is reproduced by the address lattice points are generated by the lattice point sequences 1 to 3, and therefore, the parameters of the lattice point sequences 1 to 3 obtained above and the x direction of the original image 80 are determined. It can be defined using the inclination angle θL.
In this case, jaggy is defined by jaggy pitches pj1 to pj3 and jaggy amplitudes aj1 to aj3.

<(IV) Jaggy pitch pji (i = 1 to 3)>
The jaggy pitch pji is determined by the row pitch dgi of the lattice point rows 1 to 3 and the difference between the inclination angle θgi of the lattice point rows 1 to 3 and the inclination angle θL of the original image 80 (θgi−θL).
In this case, assuming that address lattice points are continuously formed on each lattice point sequence 1 to 3, the jaggy pitch pji as an average value is
pji = dgi / sin (θgi−θL) (i = 1 to 3) Equation (8)
It becomes.

<(V) Jaggy amplitude aji (i = 1 to 3)>
FIG. 12 is an explanatory diagram of jaggy that occurs between the grid point sequence 1 and the original image 80. In this case, the distance between the intersections of the boundary of the original image 80 and the grid point row 1 is the jaggy pitch pj1.
Further, the jaggy amplitude aj1 can be defined between the lattice point sequence 1 and the lattice point sequence 2, and the lattice point sequence 1 and the lattice point sequence 3. When the smaller one of these jaggy amplitudes aj1 is selected as the jaggy amplitude aj1 as a representative value, from the relationship shown in FIG.
aj1 = pj1 · tan θ′1 · tan θ′2 / (tan θ′2−tan θ′1)
(Θ′1 = θg1−θL)
It becomes. Therefore, the jaggy amplitude aji is
aji = pji · tan θ′i · tan θ′k / (tan θ′k−tan θ′i)
(I = 1 to 3, θ′i = θgi−θL, k = 1 to 3, i ≠ k)
Formula (9)
It is. Θ′k is an angle formed by the selected lattice point sequence having a small jaggy amplitude aji and the original image 80.

Jaggy in the drawing pattern reproduced on the sheet film F is visually recognized when both the jaggy pitch pji and the jaggy amplitude aji are large to some extent.
Since each pixel constituting the drawing pattern is drawn with a predetermined diameter based on the beam diameter of the laser beam L with the address lattice point shown in FIG. 10 as the center, when the jaggy pitch pji is small, the jaggy amplitude aji is Even if it is large, no jaggy is visible. Therefore, in order to reduce the visibility of jaggy, it is only necessary to set parameters so that either the jaggy pitch pji or the jaggy amplitude aji is equal to or less than a predetermined value.
The predetermined values of the jaggy pitch and the jaggy amplitude can be the dot diameter of the drawing pixel formed on the exposed surface of the photosensitive layer, that is, the beam diameter of the laser beam L.

The jaggy pitch pji and the jaggy amplitude aji are obtained from the equations (1) to (9), and the drawing pixel A formed by the DMD adjacent on the inclination angle θL, swath inclination angle θs, and swath 77 with respect to the x direction of the original image 80. And the arrangement pitch ps of B and the drawing pitch py with respect to the y direction of the address lattice points.
Accordingly, (a) an arrangement pitch of the drawing pixels formed by the adjacent picture element portions corresponding to these parameters, and (b) a two-dimensional drawing pixel group composed of a plurality of the drawing pixels with respect to the scanning direction. An inclination angle, (c) a drawing pitch of the drawing pixels with respect to the scanning direction, and (d) a phase difference of a drawing position with respect to the scanning direction of the drawing pixels formed adjacent to a direction substantially orthogonal to the scanning direction. By adjusting each parameter, it is possible to suppress the occurrence of jaggy and reproduce an image with reduced jaggy. Each parameter may be individually adjusted and set, or a plurality of parameters may be adjusted simultaneously.

In this case, the inclination angle θL, that is, the inclination angle (b) of the two-dimensional drawing pixel group composed of a plurality of drawing pixels with respect to the scanning direction is determined in advance by the original image 80 formed on the sheet film F.
The swath tilt angle θs is determined by the tilt angle of the DMD 36 incorporated in the exposure heads 24a to 24j. This tilt angle is determined by the exposure head rotation drive unit 76 by moving the exposure heads 24a to 24j around the optical axis by a predetermined angle. It can be adjusted by rotating. Note that the tilt angle can be adjusted by rotating some of the optical members of the exposure heads 24a to 24j, for example, the microlens array 48 and the microaperture arrays 54 and 56. It is also possible to arrange an image rotating element such as a Dove prism for rotating the optical image and adjust the tilt angle by rotating the image rotating element. The image rotation element can be disposed after the second imaging optical lenses 50 and 52. In the case of an apparatus configuration in which the laser beam L is directly imaged on the sheet film F by the microlens array 48 without providing the second imaging optical lenses 50 and 52, the image rotation element is connected to the microlens array. 48 can be placed after.

The arrangement pitch ps, that is, the arrangement pitch (a) of the drawing pixels formed by the adjacent picture element portions depends on the interval between the micromirrors 40 constituting the DMD 36, but is zoomed by the optical magnification changing unit 78. The arrangement pitch ps on the sheet film F can be adjusted by changing the positions of the second imaging optical lenses 50 and 52 constituting the optical system 79.
The drawing pitch py, that is, the drawing pitch (c) of the drawing pixels with respect to the scanning direction is adjusted by the frequency change signal from the frequency changing unit 72 by adjusting the output timing of the synchronizing signal generated by the synchronizing signal generating unit 64, or Then, the moving speed change signal from the moving speed changing unit 75 is supplied to the synchronization signal generating unit 64 to change the output timing of the synchronizing signal, and the exposure stage driving unit 66 changes the moving speed of the exposure stage 18 in the y direction. Can be adjusted.

  For the original image 80 in which the inclination angle θL changes depending on the position in the y direction, it is difficult to quickly change the swath inclination angle θs according to the inclination angle θL of the original image 80. It is appropriate to change the drawing pitch py by the changing unit 72.

  Further, the jaggy pitch pji and the jaggy amplitude aji, for example, in FIG. 10, do not draw the drawing pixels A and B formed by DMD at the same time, but instead of drawing the DMD pixels A and B in the y direction by the phase difference changing unit 74. By shifting the drawing timing by a predetermined time, the phase difference Δyi between the DMD pixels B ′ and B ″ formed adjacent to the DMD pixel A in the x direction, that is, adjacent to the scanning direction is formed. The phase difference (d) of the drawing position of the drawing pixel with respect to the scanning direction can be changed, and as a result, the inclination angle θgi can be changed and adjusted.

FIGS. 13 to 15 and FIGS. 16 to 18 show that the respective parameters are set to predetermined values, and the jaggy pitches pji and the jaggy amplitudes aji of the respective lattice point sequences 1 to 3 are set according to the equations (8) and (9). The calculation result is shown.
Note that the absolute value of the smaller value is selected for the jaggy amplitude generated between grid point sequences. Further, the allowable range of the jaggy pitch pji is -5 μm to +5 μm, and the allowable range of the jaggy amplitude aji is −1 μm to +1 μm.

  In the grid point sequence 1 shown in FIG. 13, an unacceptable jaggy occurs in the range of the tilt angle θL = 0 ° to 55 ° of the original image 80, and in the grid point sequence 2 shown in FIG. An unacceptable jaggy occurs in the range of 110 ° to 135 °, and it is predicted that no jaggy occurs in the lattice point array 3 shown in FIG. In this case, for example, if the original image 80 includes a straight line having an inclination angle of about 15 °, there is a possibility that an unacceptable jaggy due to the grid point sequence 1 may occur on the straight line.

  On the other hand, in the grid point sequences 1 to 3 shown in FIGS. 16 to 18 in which the parameters are changed, jaggies do not occur before and after the inclination angle 15 ° of the original image 80, and therefore, good drawing is achieved. It is expected that a pattern will be obtained.

As described above, the case of suppressing jaggy caused by one DMD 36 has been described, but it is needless to say that the same adjustment can be performed on each DMD 36 constituting the plurality of exposure heads 24a to 24j. In other words, a plurality of drawing pixel groups each having a plurality of picture element portions can be provided, and the average value of any one of the jaggy pitch and the jaggy amplitude generated in each picture element portion group can be adjusted to be a predetermined value or less.
In this case, each parameter may be adjusted individually for each DMD of the exposure heads 24a to 24j. However, in order to reduce jaggies in the entire drawn image, the jaggy pitch of the jaggy generated by each exposure head 24a to 24j. Alternatively, for example, the moving speed of the exposure stage 18 may be adjusted so that the average value of the jaggy amplitude is not more than a predetermined value.

Each parameter may be set or changed according to the pattern of the original image 80, for example, the inclination angle θL with respect to the y direction of each original image 80.
In particular, when the pattern of the original image 80 is a line pattern extending in the x direction or the direction close to the x direction in which jaggy is conspicuous, it is preferable to adjust the parameters so that the jaggy with respect to this pattern is reduced most. .

  In addition, the correlation between the jaggy shape of the original image 80 defined by the jaggy pitch or the jaggy amplitude and each parameter for adjusting the jaggy is obtained, and an optimum parameter is set based on this correlation. Alternatively, if a parameter has already been set, an appropriate image can be easily obtained by changing the parameter.

In addition, a condition for each parameter capable of keeping the shape of the jaggy within an allowable range is obtained as a selection condition, and a desired parameter corresponding to the original image 80 is selected and set, or the shape of the jaggy is determined. It is also possible to obtain a parameter condition outside the allowable range as a prohibition condition, and prohibit the selection of the parameter according to the original image 80.
As an allowable range, an arbitrary range can be set. For example, the allowable range can be set based on the line width accuracy and edge roughness of the pattern to be formed.

  The correlation between the original image 80 and each of the parameters (e) to (h) indicates the direction of the pattern constituting the original image 80, for example, the direction of the dominant pattern in a predetermined region of the original image 80, the average The direction in which the histogram of values and directions becomes maximum can be selected and obtained. The original image 80 may be divided into a plurality of regions, the correlation is obtained for each region, and a parameter capable of reducing jaggy is set for each region.

Furthermore, parameters for reducing jaggies are set by drawing an image with initial parameters set, measuring the correlation between each parameter and the jaggy shape, etc., and searching for the optimum parameters. It is also possible.
That is, the control point sequence pitch (e), the arrangement direction (f), the pitch of the control points with respect to the scanning direction (g), and the drawing pattern based on the phase difference (h), the pitch of the control point sequence ( e) at least one of the alignment direction (f), the pitch (g) of the control points with respect to the scanning direction, and the phase difference (h), and the jaggy shape defined by at least one of the jaggy pitch and the jaggy amplitude; Can be obtained by measuring the correlation.

  In the above-described exposure method, the DMD 36 in which the micromirrors 40 are arranged on orthogonal grids is used, and the exposure is performed by inclining them. If the arranged DMDs are used, the DMDs can be incorporated into the exposure heads 24a to 24j without tilting to form an image in which jaggies are suppressed.

In the above-described exposure method, the DMD 36 that is a reflective spatial light modulator is used as the light modulator. However, as the light modulator other than the DMD, a transmissive spatial light modulator ( LCD) can also be used. For example, a liquid crystal shutter such as a MEMS (Micro Electro Mechanical Systems) type spatial light modulator (SLM), an optical element (PLZT element) that modulates transmitted light by an electro-optic effect, or a liquid crystal shutter (FLC). It is also possible to use a spatial light modulation element other than the MEMS type, such as an array. Note that MEMS is a general term for micro systems that integrate micro-sized sensors, actuators, and control circuits based on micro-machining technology based on IC manufacturing processes, and MEMS-type spatial light modulators have an electrostatic force. It means a spatial light modulation element that is driven by the electromechanical operation used.
Further, a plurality of grating light valves (GLVs) arranged in a two-dimensional shape can be used. In the configuration using these reflective spatial light modulation elements (GLV) and transmissive spatial light modulation elements (LCD), a lamp or the like can be used as a light source in addition to a laser as the light irradiation means.

  In the above-described exposure method, the light irradiation means has been described with respect to a mode in which a semiconductor laser is used as a light source. However, in addition to the semiconductor laser, for example, a solid laser, ultraviolet LD, infrared LD, or the like can be used. . Furthermore, a light source (for example, an LD array, an organic EL array, etc.) in which a plurality of light emitting points are arranged two-dimensionally can also be used.

  As the exposure apparatus, the flat bed type exposure apparatus 10 is taken as an example, but an exposure apparatus other than the flat bed type may be used. For example, an outer drum type in which a photosensitive material is wound around the outer peripheral surface of the drum. The exposure apparatus may be an inner drum type exposure apparatus in which a photosensitive material is mounted on the inner peripheral surface of the cylinder.

[Laminate]
As long as the object of the exposure is a laminate having a photosensitive layer formed on the surface of the substrate with a photosensitive composition containing at least a binder, a polymerizable compound, a photopolymerization initiator, and a thermal crosslinking agent. There is no particular limitation, and it can be appropriately selected according to the purpose.
As the photosensitive layer, the photosensitive composition of the first aspect formed by applying the photosensitive composition to the surface of a substrate and drying, and the support and the photosensitive composition are laminated on the support. The photosensitive layer of the 2nd aspect formed by laminating | stacking the photosensitive film which has the formed photosensitive layer on the surface of a base material under at least any one of a heating and pressurization is mentioned.

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

[Photosensitive composition]
The photosensitive composition contains at least a binder, a polymerizable compound, a photopolymerization initiator, and a thermal crosslinking agent, and preferably contains a sensitizer, and if necessary, a coloring pigment or an extender pigment. , And other components such as a thermal polymerization inhibitor and a surfactant.

<Binder>
For example, the binder is preferably swellable in an alkaline aqueous solution, and more preferably soluble in an alkaline aqueous solution.
As the binder exhibiting swellability or solubility with respect to the alkaline aqueous solution, for example, those having an acidic group are preferably exemplified.

  The binder is not particularly limited and may be appropriately selected depending on the intended purpose. For example, JP-A Nos. 51-131706, 52-94388, 64-62375, and JP-A-2 -97513, JP-A-3-289656, JP-A-61-2243869, JP-A-2002-296976, etc., an epoxy acrylate compound having an acidic group, and a (meth) acryloyl group in the side chain and Examples thereof include a vinyl copolymer having an acidic group, an epoxy acrylate compound and a vinyl copolymer having a (meth) acryloyl group and an acidic group in the side chain, and a maleic anhydride copolymer.

  The epoxy acrylate compound is a compound having a skeleton derived from an epoxy compound and containing an ethylenically unsaturated double bond and a carboxyl group in the molecule. Such a compound can be obtained by, for example, 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 having an isocyanurate skeleton (“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 novolak type epoxy resin, glycidylamine type epoxy resin (eg, 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. "); polyphenol compounds obtained by condensation reaction of phenolic compounds such as phenol, o-cresol, naphthol and aromatic aldehydes having phenolic hydroxyl groups and epi Reaction product of lorhydrin; reaction product of polyphenol compound obtained by addition reaction of phenol compound and diolefin compound such as divinylbenzene or dicyclopentadiene and epichlorohydrin; ring-opening polymer of 4-vinylcyclohexene-1-oxide Epoxidized with peracetic acid, etc .; epoxy resin having a heterocyclic ring such as triglycidyl isocyanurate; glycidyl methacrylate copolymer epoxy resin (“CP-50S, CP-50M; manufactured by NOF Corporation”), cyclohexyl Copolymerized epoxy resin of maleimide and glycidyl methacrylate; epoxy resin obtained by glycidyl etherification of one kind selected from phenol and cresol and p-hydroxybenzaldehyde condensate; bis (glycidyloxyphenyl) fluorene Type epoxy resin; bis (glycidyloxyphenyl) adamantane type epoxy resin; and the like. 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-cyanocinnamic acid. Acrylic acid dimer; In addition, addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic acid anhydride such as maleic anhydride, phthalic anhydride, cyclohexanedicarboxylic anhydride; The reaction product with a halogen-containing carboxylic acid compound, ω-carboxy-polycaprolactone mono (meth) acrylate, and the like can be mentioned. 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, 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 , Phthalic anhydride, tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydro Phthalic anhydride, Hydrochlorendic acid and dibasic acid anhydrides such as 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trimellitic anhydride, pyromellitic anhydride Polybasic acid anhydrides such as 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.

  Further, compounds obtained by adding an acid anhydride to an epoxy acrylate having a fluorene skeleton (a compound having no carboxyl group) described in JP-A-5-70528 can also be used as the epoxy acrylate.

  The molecular weight of the epoxy acrylate compound is preferably 1,000 to 100,000, and more preferably 2,000 to 50,000. When the molecular weight is less than 1,000, the tackiness of the surface of the photosensitive layer may become strong, and the film quality may become brittle or the surface hardness may deteriorate after curing of the photosensitive layer described later. If it exceeds 1,000, developability may deteriorate. Also, synthesis of the resin becomes difficult.

  An acrylic resin having at least one polymerizable group such as an acidic group or a double bond described in JP-A-6-295060 can also be used. Specifically, at least one polymerizable double bond in the molecule, for example, an acrylic group such as a (meth) acrylate group or (meth) acrylamide group, various polymerizations such as vinyl ester of carboxylic acid, vinyl ether, allyl ether Sex double bonds can be used. More specifically, acrylic resins containing carboxyl groups as acidic groups, glycidyl esters of unsaturated fatty acids such as glycidyl acrylate, glycidyl methacrylate, cinnamic acid, and epoxy groups such as cyclohexene oxide in the same molecule (meth) Examples thereof include compounds obtained by adding an epoxy group-containing polymerizable compound such as a compound having an acryloyl group. 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.

  Furthermore, as the binder, a vinyl copolymer having a (meth) acryloyl group and an acidic group in the side chain can be used. Specifically, for example, (1) a vinyl monomer having an acidic group, (2) (Co) heavy obtained by vinyl (co) polymerization of a vinyl monomer having a functional group that can be used in the polymer reaction described later, if necessary, and (3) other copolymerizable vinyl monomers as necessary And (4) a (meth) acryloyl group and a functional group having reactivity with at least one of an acidic group in the (co) polymer or a functional group available for polymer reaction. It is obtained by polymer-reacting with a compound having it.

There is no restriction | limiting in particular as an acidic group of the vinyl monomer which has said (1) acidic group, According to the objective, it can select suitably, For example, a carboxyl group, a sulfonic acid group, a phosphoric acid group etc. are mentioned, These Among these, a carboxyl group is preferable. Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, and a monomer having a hydroxyl group. An addition reaction product of a monomer (for example, 2-hydroxyethyl (meth) acrylate) and a cyclic anhydride (for example, maleic anhydride, phthalic anhydride, cyclohexanedicarboxylic anhydride), ω-carboxy-polycaprolactone mono ( And (meth) acrylate. Among these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like. Moreover, these monomers may be used individually by 1 type, and may use 2 or more types together.
Moreover, you may use the monomer which has anhydrides, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group.

  In the vinyl monomer having a functional group usable for the polymer reaction of (2), the functional group usable for the polymer reaction is a hydroxyl group, an amino group, an isocyanate group, an epoxy group, an acid halide group, an active halide group, Etc. Moreover, the carboxyl group and acid anhydride group of the above-mentioned (1) are also mentioned as usable functional groups.

  Examples of the vinyl monomer having a hydroxyl group include compounds represented by the following structural formulas (1) to (9).

In the structural formulas (1) to (9), R ′ represents a hydrogen atom or a methyl group, and n ₁ , n ₂ , and n ₃ each represents an integer of 1 or more.

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

  Examples of the monomer having an isocyanate group include compounds represented by the following structural formulas (10) to (12).

  However, in said structural formula (10)-(12), R 'represents a hydrogen atom or a methyl group.

  Examples of the vinyl monomer having an epoxy group include glycidyl (meth) acrylate and a compound represented by the following structural formula (13).

However, in said structural formula (13), R 'represents either a hydrogen atom or a methyl group.

Examples of the vinyl monomer having an acid halide group include (meth) acrylic acid chloride.
Examples of the vinyl monomer having an active halide group include chloromethylstyrene.
Moreover, each said monomer may be used individually by 1 type, and may use 2 or more types together.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Examples of commercially available binders include “Kaneka Resin AX; manufactured by Kaneka Chemical Co., Ltd.”, “CYCLOMER A-200; manufactured by Daicel Chemical Industries, Ltd.”, and “CYCLOMER M”. -200; manufactured by Daicel Chemical Industries, Ltd. "," SPCP1X, SPCP2X, SPCP3X; manufactured by Showa Polymer Co., Ltd. "can be used.
Furthermore, a reaction product of hydroxyalkyl acrylate or hydroxyalkyl methacrylate described in JP-A No. 50-59315 and any of polycarboxylic acid anhydride and epihalohydrin can be used.

  Further, a compound obtained by adding an acid anhydride to an epoxy acrylate having a fluorene skeleton described in JP-A-5-70528, a polyamide (imide) resin described in JP-A-11-288087, and JP-A-2-097502 Polyimide precursors described in Japanese Patent Laid-Open No. 11-282155, and the like can be used. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

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

As the binder, a copolymer obtained by reacting one or more primary amine compounds with an anhydride group of a maleic anhydride copolymer can also be used. The copolymer is a maleamic acid-based copolymer having at least a maleamic acid unit B having a maleic acid half amide structure and a unit A not having the maleic acid half amide structure, represented by the following structural formula (14). It is preferably a coalescence.
The unit A may be one type or two or more types. For example, assuming that the unit B is one type, when the unit A is one type, the maleamic acid-based copolymer means a binary copolymer, and the unit A is 2 When it is a seed, the maleamic acid-based copolymer means a terpolymer.
The unit A is an aryl group which may have a substituent and a vinyl monomer described later, and the glass transition temperature (Tg) of the homopolymer of the vinyl monomer is less than 80 ° C. A combination with the vinyl monomer (c) is preferred.

However, in said structural formula (14), ^R93 and ^R94 represent either a hydrogen atom or a lower alkyl group. x and y represent the mole fraction of the repeating unit. For example, when the unit A is one, x is 85 to 50 mol%, and y is 15 to 50 mol%.

In the structural formula (14), as R ⁹¹ , for example, (—COOR ⁹⁵ ), (—CONR ⁹⁶ R ⁹⁷ ), an aryl group which may have a substituent, (—OCOR ⁹⁸ ), (—OR ⁹⁹ ), (—COR ¹⁰⁰ ) and the like. Wherein said ^R 95 ^{to R 100} is a hydrogen atom (-H), which may have a substituent alkyl group, an aryl group and aralkyl group. The alkyl group, aryl group and aralkyl group may have a cyclic structure or a branched structure.
Examples of R ^{95 to} R ¹⁰⁰ include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, pentyl, allyl, n-hexyl, and cyclohexyl. 2-ethylhexyl, dodecyl, methoxyethyl, phenyl, methylphenyl, methoxyphenyl, benzyl, phenethyl, naphthyl, chlorophenyl and the like.
Specific examples of R ⁹¹ include, for example, benzene derivatives such as phenyl, α-methylphenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl; n-propyloxycarbonyl, Examples include n-butyloxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, n-butyloxycarbonyl, n-hexyloxycarbonyl, 2-ethylhexyloxycarbonyl, methyloxycarbonyl and the like.

Examples of R ⁹² include an alkyl group, an aryl group, and an aralkyl group that may have a substituent. These may have a cyclic structure or a branched structure. Specific examples of R ⁹² include, for example, benzyl, phenethyl, 3-phenyl-1-propyl, 4-phenyl-1-butyl, 5-phenyl-1-pentyl, 6-phenyl-1-hexyl, and α-methyl. Benzyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2- (p-tolyl) ethyl, β-methylphenethyl, 1-methyl-3-phenylpropyl, 2-chlorobenzyl, 3-chlorobenzyl, 4-chlorobenzyl, 2-fluorobenzyl, 3-fluorobenzyl, 4-fluorobenzyl, 4-bromophenethyl, 2- (2-chlorophenyl) ethyl, 2- (3-chlorophenyl) ethyl, 2- (4-chlorophenyl) Ethyl, 2- (2-fluorophenyl) ethyl, 2- (3-fluorophenyl) ethyl, 2- (4-fluorophenyl) Ethyl, 4-fluoro-α, α-dimethylphenethyl, 2-methoxybenzyl, 3-methoxybenzyl, 4-methoxybenzyl, 2-ethoxybenzyl, 2-methoxyphenethyl, 3-methoxyphenethyl, 4-methoxyphenethyl, methyl, Ethyl, propyl, i-propyl, butyl, t-butyl, sec-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, lauryl, phenyl, 1-naphthyl, methoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 3 -Methoxypropyl, 2-butoxyethyl, 2-cyclohexyloxyethyl, 3-ethoxypropyl, 3-propoxypropyl, 3-isopropoxypropylamine and the like.

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

-(B) Aromatic vinyl monomer-
The aromatic vinyl monomer is not particularly limited and may be appropriately selected depending on the intended purpose. However, the surface hardness of the photosensitive layer formed using the photosensitive composition can be increased. Thus, a compound having a glass transition temperature (Tg) of the homopolymer of 80 ° C. or higher is preferable, and a compound of 100 ° C. or higher is more preferable.
Specific examples of the aromatic vinyl monomer include, for example, styrene (homopolymer Tg = 100 ° C.), α-methylstyrene (homopolymer Tg = 168 ° C.), 2-methylstyrene (homopolymer Tg = 136 ° C.), 3-methylstyrene (homopolymer Tg = 97 ° C.), 4-methylstyrene (homopolymer Tg = 93 ° C.), 2,4-dimethylstyrene (homopolymer Tg = 112 ° C.) Preferred examples include derivatives. These may be used individually by 1 type and may use 2 or more types together.

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

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

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

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

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

  5-80 mass% is preferable and, as for solid content in solid content of the said photosensitive composition of the said binder, 10-70 mass% is more preferable. When the solid content is less than 5% by mass, the film strength of the photosensitive layer tends to be weak, and the tackiness of the surface of the photosensitive layer may be deteriorated. When it exceeds 50% by mass, the exposure sensitivity is increased. May decrease.

<Polymerizable compound>
There is no restriction | limiting in particular as said polymeric compound, Although it can select suitably according to the objective, For example, the monomer or oligomer which has at least any one of a urethane group and an aryl group is mentioned suitably. Moreover, it is preferable that these have 2 or more types of polymeric groups.

  Examples of the polymerizable group include an ethylenically unsaturated bond (for example, (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). Etc.) and a polymerizable cyclic ether group (for example, epoxy group, oxetane group, etc.) and the like. Among these, an ethylenically unsaturated bond is preferable.

--Monomer having urethane group--
The monomer having a urethane group is not particularly limited as long as it has a urethane group, and can be appropriately selected depending on the purpose. For example, JP-B-48-41708, JP-A-51-37193, JP-B-5 -50737, Japanese Patent Publication No. 7-7208, Japanese Patent Application Laid-Open No. 2001-154346, Japanese Patent Application Laid-Open No. 2001-356476, and the like. For example, a polyisocyanate compound having two or more isocyanate groups in the molecule And an adduct of a vinyl monomer having a hydroxyl group in the molecule.

  Examples of the polyisocyanate compound having two or more isocyanate groups in the molecule include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, toluene diisocyanate, phenylene diisocyanate, norbornene diisocyanate, diphenyl diisocyanate, diphenylmethane diisocyanate, A diisocyanate such as 3,3′dimethyl-4,4′-diphenyl diisocyanate; a polyaddition product of the diisocyanate with a bifunctional alcohol (in this case, both ends are isocyanate groups); a burette or isocyanurate of the diisocyanate; Trimer; the diisocyanate or diisocyanates and trimethylolpropane, pe Taeritoritoru, polyfunctional alcohols such as glycerin, or the like adducts of other functional alcohol obtained of such these ethylene oxide adducts and the like.

  Examples of the vinyl monomer having a hydroxyl group in the molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, and triethylene. Glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, octaethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate , Tetrapropylene glycol mono (meth) acrylate, octapropylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) Chryrate, dibutylene glycol mono (meth) acrylate, tributylene glycol mono (meth) acrylate, tetrabutylene glycol mono (meth) acrylate, octabutylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate, trimethylolpropane Examples include di (meth) acrylate and pentaerythritol tri (meth) acrylate. Moreover, the one terminal (meth) acrylate body of the diol body which has different alkylene oxide parts, such as a copolymer (random, a block, etc.) of ethylene oxide and propylene oxide, etc. are mentioned.

  In addition, examples of the monomer having a urethane group include compounds having an isocyanurate ring such as tri ((meth) acryloyloxyethyl) isocyanurate, di (meth) acrylated isocyanurate, and tri (meth) acrylate of ethylene oxide-modified isocyanuric acid. Is mentioned. Among these, the compound represented by the following structural formula (15) or the structural formula (16) is preferable, and at least the compound represented by the structural formula (16) is particularly preferable from the viewpoint of tent properties. Moreover, these compounds may be used individually by 1 type, and may use 2 or more types together.

In the structural formulas (15) and (16), R ′ ^{1 to} R ′ ³ each represent a hydrogen atom or a methyl group. X ₁ to X ₃ represents an alkylene oxide, may be alone or in combination of two or more thereof.

  Examples of the alkylene oxide group include an ethylene oxide group, a propylene oxide group, a butylene oxide group, a pentylene oxide group, a hexylene oxide group, and a group in which these are combined (may be combined in any of random or block). Among these, an ethylene oxide group, a propylene oxide group, a butylene oxide group, or a combination thereof is preferable, and an ethylene oxide group and a propylene oxide group are more preferable.

In structural formulas (15) and (16), m _{4 to} m ₆ represent an integer of 1 to 60, preferably 2 to 30, and more preferably 4 to 15.

In the structural formulas (15) and (16), Y ¹ and Y ² represent a divalent organic group having 2 to 30 carbon atoms, for example, an alkylene group, an arylene group, an alkenylene group, an alkynylene group, a carbonyl group. (—CO—), an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino group in which the hydrogen atom of the imino group is substituted with a monovalent hydrocarbon group, Preferred examples include a sulfonyl group (—SO ₂ —) or a combination thereof, and among these, an alkylene group, an arylene group, or a combination thereof is preferable.

  The alkylene group may have a branched structure or a cyclic structure, for example, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, pentylene group, neopentylene group, hexylene group, trimethyl hexene. Preferable examples include a xylene group, a cyclohexylene group, a heptylene group, an octylene group, a 2-ethylhexylene group, a nonylene group, a decylene group, a dodecylene group, an octadecylene group, or any of the groups shown below.

  The arylene group may be substituted with a hydrocarbon group, and examples thereof include a phenylene group, a tolylene group, a diphenylene group, a naphthylene group, and the groups shown below.

  Examples of the group in which these are combined include a xylylene group.

  The alkylene group, arylene group, or a combination thereof may further have a substituent. Examples of the substituent include a halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine). Atom), aryl group, alkoxy group (for example, methoxy group, ethoxy group, 2-ethoxyethoxy group), aryloxy group (for example, phenoxy group), acyl group (for example, acetyl group, propionyl group), acyloxy group (for example, , Acetoxy group, butyryloxy group), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group) and the like.

In the structural formulas (15) and (16), n ₆ represents an integer of 3 to 6, and 3, 4 or 6 is preferable from the viewpoint of raw material supply for synthesizing a polymerizable monomer.

In the structural formulas (15) and (16), Z ₁ represents an n-valent (trivalent to hexavalent) linking group, and examples thereof include any of the groups shown below.

However, _{X 4} represents an alkylene oxide. m ₇ represents an integer of 1 to 20. n ₇ represents an integer of 3 to 6. A ₂ represents an n ₇ valent (trivalent to 6 valent) organic group.

Examples of A ₂ include a trivalent to hexavalent aliphatic group, a trivalent to hexavalent aromatic group, and an alkylene group, an arylene group, an alkenylene group, an alkynylene group, a carbonyl group, an oxygen atom, and sulfur. A group in which an atom, an imino group, a substituted imino group in which a hydrogen atom of an imino group is substituted with a monovalent hydrocarbon group, or a combination with a sulfonyl group is preferable, a trivalent to hexavalent aliphatic group, a trivalent to 6 A valent aromatic group or a group obtained by combining these with an alkylene group, an arylene group or an oxygen atom is more preferred, a trivalent to hexavalent aliphatic group, a trivalent to hexavalent aliphatic group and an alkylene group, oxygen A group in combination with an atom is particularly preferred.

As the number of carbon atoms of _{A 2,} for example, preferably an integer of 1 to 100, more preferably an integer of 1 to 50, particularly preferably an integer of 3 to 30.

The n _7- valent (trivalent to 6-valent) aliphatic group may have a branched structure or a cyclic structure.
As a carbon atom number of the said aliphatic group, the integer of 1-30 is preferable, for example, the integer of 1-20 is more preferable, and the integer of 3-10 is especially preferable.
The number of carbon atoms of the aromatic group is preferably an integer of 6 to 100, more preferably an integer of 6 to 50, and particularly preferably an integer of 6 to 30.

The n _7- valent (trivalent to 6-valent) aliphatic group or aromatic group may further have a substituent. Examples of the substituent include a hydroxyl group and a halogen atom (for example, fluorine). Atom, chlorine atom, bromine atom, iodine atom), aryl group, alkoxy group (for example, methoxy group, ethoxy group, 2-ethoxyethoxy group), aryloxy group (for example, phenoxy group), acyl group (for example, acetyl group) , Propionyl group), acyloxy group (for example, acetoxy group, butyryloxy group), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group) and the like.

The alkylene group may have a branched structure or a cyclic structure.
As a carbon atom number of the said alkylene group, the integer of 1-18 is preferable, for example, and the integer of 1-10 is more preferable.

The arylene group may be further substituted with a hydrocarbon group.
As the number of carbon atoms of the arylene group, an integer of 6 to 18 is preferable, and an integer of 6 to 10 is more preferable.

  As a carbon atom number of the monovalent hydrocarbon group of the said substituted imino group, the integer of 1-18 is preferable and the integer of 1-10 is more preferable.

Preferred examples of A ₂ are as follows.

  Examples of the compounds represented by the structural formulas (15) and (16) include compounds represented by the following structural formulas (17) to (36).

However, the structural formula _{(17) ~ (36),} n 8, n 9, n 10, and _{m 8} refers to 1 to 60, l refers to 1 to 20, R is a hydrogen atom Or represents a methyl group.

--Monomer having an aryl group--
The monomer having an aryl group is not particularly limited as long as it has an aryl group, and can be appropriately selected depending on the purpose. For example, a polyhydric alcohol compound having a aryl group, a polyvalent amine compound, and a polyvalent Examples thereof include esters or amides of at least one of amino alcohol compounds and unsaturated carboxylic acid.

  Examples of the polyhydric alcohol compound, polyamine compound or polyhydric amino alcohol compound having an aryl group include polystyrene oxide, xylylene diol, di- (β-hydroxyethoxy) benzene, 1,5-dihydroxy-1, 2,3,4-tetrahydronaphthalene, 2,2-diphenyl-1,3-propanediol, hydroxybenzyl alcohol, hydroxyethyl resorcinol, 1-phenyl-1,2-ethanediol, 2,3,5,6-tetra Methyl-p-xylene-α, α′-diol, 1,1,4,4-tetraphenyl-1,4-butanediol, 1,1,4,4-tetraphenyl-2-butyne-1,4- Diol, 1,1′-bi-2-naphthol, dihydroxynaphthalene, 1,1′-methylene-di-2-naphth 1,2,4-benzenetriol, biphenol, 2,2′-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (hydroxyphenyl) methane, catechol, 4-chlororesorcinol, hydroquinone, hydroxybenzyl alcohol, methyl hydroquinone, methylene-2,4,6-trihydroxybenzoate, phloroglicinol, pyrogallol, resorcinol, α- (1-aminoethyl) -p-hydroxybenzyl alcohol, α -(1-aminoethyl) -p-hydroxybenzyl alcohol, 3-amino-4-hydroxyphenylsulfone and the like can be mentioned. In addition, compounds obtained by adding α, β-unsaturated carboxylic acid to glycidyl compounds such as xylylene bis (meth) acrylamide, novolac epoxy resin and bisphenol A diglycidyl ether, phthalic acid, trimellitic acid, etc. Esterified products obtained from vinyl monomers containing hydroxyl groups in the molecule, diallyl phthalate, triallyl trimellitic acid, diallyl benzenedisulfonate, cationically polymerizable divinyl ethers (for example, bisphenol A divinyl ether), epoxy as a polymerizable monomer Compound (for example, novolac type epoxy resin, bisphenol A diglycidyl ether, etc.), vinyl ester (for example, divinyl phthalate, divinyl terephthalate, divinylbenzene-1,3-disulfonate, etc.), styrene Compounds such as divinylbenzene, p-allylstyrene, p-isopropenestyrene, and the like. Among these, the compound represented by the following structural formula (37) is preferable.

In the structural formula (37), R ′ ⁴ and R ′ ⁵ represent a hydrogen atom or an alkyl group.

In the structural formula (37), X ₅ and X ₆ represents an alkylene oxide group may be singly or in combination of two or more thereof. Examples of the alkylene oxide group include an ethylene oxide group, a propylene oxide group, a butylene oxide group, a pentylene oxide group, a hexylene oxide group, a group in which these are combined (which may be combined in any of random and block), Among these, an ethylene oxide group, a propylene oxide group, a butylene oxide group, or a group combining these is preferable, and an ethylene oxide group and a propylene oxide group are more preferable.

In the structural formula (37), m ₉ and m ₁₀ are preferably an integer of 1 to 60, more preferably an integer of 2 to 30, and particularly preferably an integer of 4 to 15.

In the structural formula (37), T represents a divalent linking group, and examples thereof include methylene, ethylene, MeCMe, CF ₃ CCF ₃ , CO, and SO ₂ .

In the structural formula (37), Ar ¹ and Ar ² represent an aryl group which may have a substituent, and examples thereof include phenylene and naphthylene. Examples of the substituent include an alkyl group, an aryl group, an aralkyl group, a halogen group, an alkoxy group, or a combination thereof.

  Specific examples of the monomer having an aryl group include 2,2-bis [4- (3- (meth) acryloxy-2-hydroxypropoxy) phenyl] propane, 2,2-bis [4-((meth)). (Acryloxyethoxy) phenyl] propane, 2,2-bis (4-((meth) acryloyloxypolyethoxy) phenyl) propane having 2 to 20 ethoxy groups substituted with one phenolic OH group (For example, 2,2-bis (4-((meth) acryloyloxydiethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxytetraethoxy) phenyl) propane, 2,2-bis (4-((Meth) acryloyloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxydecae) Xyl) phenyl) propane, 2,2-bis (4-((meth) acryloyloxypentadecaethoxy) phenyl) propane), 2,2-bis [4-((meth) acryloxypropoxy) phenyl] propane, 2,2-bis (4-((meth) acryloyloxypolypropoxy) phenyl) propane (e.g. 2,2-bis (2) having 2 to 20 ethoxy groups substituted with one phenolic OH group 4-((meth) acryloyloxydipropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxy) Pentapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxydecapropoxy) pheny ) Propane, 2,2-bis (4-((meth) acryloyloxypentadecapropoxy) phenyl) propane, or the like, or both the polyethylene oxide skeleton and the polypropylene oxide skeleton in the same molecule as the polyether moiety Compounds (for example, compounds described in WO01 / 98832 etc., or commercially available, Shin-Nakamura Chemical Co., Ltd., BPE-200, BPE-500, BPE-1000), bisphenol skeleton and urethane group Examples thereof include a polymerizable compound. These compounds may be compounds obtained by changing the part derived from the bisphenol A skeleton to bisphenol F or bisphenol S.

  Examples of the polymerizable compound having a bisphenol skeleton and a urethane group include an isocyanate group and a polymerizable group in a compound having a hydroxyl group at the terminal obtained as an adduct such as bisphenol and ethylene oxide or propylene oxide, or a polyaddition product. Examples thereof include compounds (for example, 2-isocyanatoethyl (meth) acrylate, α, α-dimethyl-vinylbenzyl isocyanate, etc.).

-Other polymerizable monomers-
In the photosensitive composition, a polymerizable monomer other than the monomer containing the urethane group and the monomer having an aryl group is used in a range that does not deteriorate the characteristics of the photosensitive layer formed using the photosensitive composition. May be.

  Examples of the polymerizable monomer other than the monomer containing a urethane group and the monomer containing an aromatic ring include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) And an ester of an aliphatic polyhydric alcohol compound and an amide of an unsaturated carboxylic acid and a polyvalent amine compound.

  Examples of the monomer of the ester of the unsaturated carboxylic acid and the aliphatic polyhydric alcohol compound include (meth) acrylic acid ester, ethylene glycol di (meth) acrylate, and polyethylene glycol having 2 to 18 ethylene groups. Di (meth) acrylate (for example, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, dodecaethylene glycol di (meth) acrylate , Tetradecaethylene glycol di (meth) acrylate, etc.), propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate having 2 to 18 propylene groups (for example, , Dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, dodecapropylene glycol di (meth) acrylate, etc.), neopentyl glycol di (meth) acrylate, ethylene oxide modified Neopentyl glycol di (meth) acrylate, propylene oxide modified neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ) Ether, trimethylolethane tri (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,3-butanediol (Meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, 1,2,4-butanetriol tri (meth) acrylate, 1,5-bentanediol (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, di Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol penta (meth) acrylate Rate, sorbitol hexa (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, tricyclodecane di (meth) acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate A di (meth) acrylate of an alkylene glycol chain having at least one ethylene glycol chain / propylene glycol chain (for example, a compound described in WO01 / 98832), at least one of ethylene oxide and propylene oxide Trimethylolpropane tri (meth) acrylate, polybutylene glycol di (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate Examples include relate and xylenol di (meth) acrylate.

  Among the (meth) acrylic acid esters, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meta) from the viewpoint of easy availability. ) Acrylate, di (meth) acrylate of alkylene glycol chain each having at least one ethylene glycol chain / propylene glycol chain, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol triacrylate, penta Erythritol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (Meth) acrylate, diglycerin di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,2,4-butanetriol tri (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, 1, Preference is given to 5-pentanediol (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate added with ethylene oxide, and the like.

  Examples of the ester (itaconic acid ester) of the itaconic acid and the aliphatic polyhydric alcohol compound include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4- Examples include butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, and sorbitol tetritaconate.

  Examples of the ester (crotonate ester) of the crotonic acid and the aliphatic polyhydric alcohol compound include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Can be mentioned.

  Examples of the ester of the isocrotonic acid and the aliphatic polyhydric alcohol compound (isocrotonate ester) include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocrotonate, and the like.

  Examples of the ester of maleic acid and the aliphatic polyhydric alcohol compound (maleic acid ester) include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of the amide derived from the polyvalent amine compound and the unsaturated carboxylic acid include methylene bis (meth) acrylamide, ethylene bis (meth) acrylamide, 1,6-hexamethylene bis (meth) acrylamide, and octamethylene bis ( And (meth) acrylamide, diethylenetriamine tris (meth) acrylamide, and diethylenetriamine bis (meth) acrylamide.

  In addition to the above, as the polymerizable monomer, for example, butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, Compound obtained by adding α, β-unsaturated carboxylic acid to glycidyl group-containing compound such as hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, glycerin triglycidyl ether, Polyester acrylate and polyester (meth) acrylate as described in JP-B-6183, JP-B-49-43191 and JP-B-52-30490. Rate oligomers, epoxy compounds (eg, butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether , Pentaerythritol tetraglycidyl ether, glycerin triglycidyl ether, etc.) and (meth) acrylic acid and other polyfunctional acrylates and methacrylates such as epoxy acrylates, Journal of Japan Adhesion Association Vol. 20, No. 7, 300-308 Photocurable monomers and oligomers and allyl esters described in page (1984) (eg diallyl phthalate, diallyl adipate, malonic acid) Allyl, diallylamide (eg, diallylacetamide), cationically polymerizable divinyl ethers (eg, butanediol-1,4-divinyl ether, cyclohexanedimethanol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, dipropylene glycol) Divinyl ether, hexanediol divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, glycerin trivinyl ether, etc.), epoxy compounds (eg, butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, ethylene glycol di) Glycidyl ether, diethylene glycol diglycidyl ether, dipropylene group Recall diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, glycerin triglycidyl ether, etc.), oxetanes (for example, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) ) Methyl] benzene, etc.), epoxy compounds, oxetanes (for example, compounds described in WO01 / 22165), N-β-hydroxyethyl-β- (methacrylamide) ethyl acrylate, N, N-bis (β- And compounds having two or more different ethylenically unsaturated double bonds, such as methacryloxyethyl) acrylamide and allyl methacrylate.

  Examples of the vinyl esters include divinyl succinate and divinyl adipate.

  These polyfunctional monomers or oligomers may be used alone or in combination of two or more.

If necessary, the polymerizable monomer may be used in combination with a polymerizable compound (monofunctional monomer) containing one polymerizable group in the molecule.
Examples of the monofunctional monomer include the compounds exemplified as the raw material of the binder, and the dibasic mono ((meth) acryloyloxyalkyl ester) mono (halohydroxyalkyl ester) described in JP-A-6-236031. Monofunctional monomers such as γ-chloro-β-hydroxypropyl-β′-methacryloyloxyethyl-o-phthalate, etc., compounds described in Japanese Patent No. 2744443, WO00 / 52529 pamphlet, Japanese Patent No. 2548016, etc. Is mentioned.

  The polymerizable compound is preferably a compound having at least one addition-polymerizable group in the molecule and having a boiling point of 100 ° C. or higher at normal pressure. For example, among the above monomers, (meth) Preferable examples include at least one selected from monomers having an acrylic group.

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

5-50 mass% is preferable and, as for solid content in the said photosensitive composition solid content of the said polymeric compound, 10-40 mass% is more preferable. If the solid content is less than 5% by mass, problems such as deterioration of developability and reduction in exposure sensitivity may occur, and if it exceeds 50% by mass, the adhesiveness of the photosensitive layer may become too strong. Yes, not preferred.
Moreover, as content of the polyfunctional monomer which has 2 or more of the said polymeric groups in a polymeric compound, 5-100 mass% is preferable, 20-100 mass% is more preferable, 40-100 mass% is especially preferable. .

<Photopolymerization initiation compound>
The photopolymerization initiating compound comprises a photopolymerization initiator (such as a radical generator and a hydrogen donor) and a sensitizer.
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, it is visible from the ultraviolet region. It is preferable to have photosensitivity to the light of the above, and may be an activator that generates an active radical by causing some action with the photosensitized sensitizer, and initiates cationic polymerization according to the type of monomer. Such an initiator may be used.
The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a range of about 300 to 800 nm (more preferably 330 to 500 nm).

<< photopolymerization initiator >>
Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton), hexaarylbiimidazoles, oxime derivatives, organic peroxides, thio compounds, Examples include ketone compounds, aromatic onium salts, metallocenes, and acylphosphine oxide compounds.

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

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

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

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

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

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

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

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

  Examples of the compound described in US Pat. No. 4,221,976 include 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorophenyl). -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (2-naphthyl) -1,3 , 4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl) -1,3,4-oxadiazole 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) -1,3,4-oxadiazole, 2-trichl Romethyl-5- (4-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5 -(4-n-butoxystyryl) -1,3,4-oxadiazole, 2-tribromomethyl-5-styryl-1,3,4-oxadiazole and the like.

  Examples of the hexaarylbiimidazole include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-fluorophenyl)- 4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-bromophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis ( 2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (3-methoxyphenyl) ) Biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (4-methoxyphenyl) biimidazole, 2,2'-bis (4-methoxyphenyl) -4 , 4 ', , 5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-nitrophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-methylphenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-Trifluoromethylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, compounds described in WO00 / 52529, and the like.

  The biimidazoles are described in, for example, Bull. Chem. Soc. Japan, 33, 565 (1960); Org. It can be easily synthesized by the method disclosed in Chem, 36 (16) 2262 (1971).

  Examples of the oxime derivative include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutan-2-one, and 2-acetoxyiminopentane-3-one. 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxy And carbonyloxyimino-1-phenylpropan-1-one.

  Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzolphenone, benzophenonetetracarboxylic acid or tetramethyl ester thereof, 4,4′-bis (dialkylamino) benzophenone (for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′- Bisdicyclohexylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4′-dimethylamino Nzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chloro -Thioxanthone, 2,4-diethylthioxanthone, fluorenone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether, In propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloro acridone, N- methyl acridone, N- butyl acridone, N- butyl - such as chloro acrylic pyrrolidone.

Examples of the metallocenes include bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, ⁵ -cyclopentadienyl-η ⁶ -cumenyl-iron (1 +)-hexafluorophosphate (1-), JP-A-53-133428, JP-B-57-1819, JP-A-57-6096, and Examples thereof include compounds described in US Pat. No. 3,615,455.

  Examples of the acylphosphine oxide compound include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO. Etc.

  Further, as photopolymerization initiators other than the above, acridine derivatives (for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N-phenylglycine, Carbon tetrabromide, phenyltribromomethylsulfone, phenyltrichloromethylketone, etc.), coumarins (eg, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) ) Coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis (5 , 7-di-n-propoxycoumarin), 3,3′-carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, JP-A-5-19475, JP-A-7-271028, JP-A-2002-363206 , Coumarin compounds described in JP-A No. 2002-363207, JP-A No. 2002-363208, JP-A No. 2002-363209, etc.), amines (for example, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate) N-butyl acid, phenethyl 4-dimethylaminobenzoate, 4-Dimethylaminobenzoic acid 2-phthalimidoethyl, 4-dimethylaminobenzoic acid 2-methacryloyloxyethyl, pentamethylenebis (4-dimethylaminobenzoate), phenethyl of 3-dimethylaminobenzoic acid, pentamethylene ester, 4-dimethyl Aminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylaminobenzyl alcohol, ethyl (4-dimethylaminobenzoyl) acetate, 4-piperidinoacetophenone, 4-dimethylaminobenzoin, N, N-dimethyl-4 -Toluidine, N, N-diethyl-3-phenetidine, tribenzylamine, dibenzylphenylamine, N-methyl-N-phenylbenzylamine, 4-bromo-N, N-dimethylaniline, tridodecylami And aminofluoranes (ODB, ODBII, etc.), crystal violet lactone, leuco crystal violet, etc.).

  Further, vicinal polyketaldonyl compounds described in US Pat. No. 2,367,660, acyloin ether compounds described in US Pat. No. 2,448,828, and US Pat. No. 2,722,512 are described. An aromatic acyloin compound substituted with α-hydrocarbon, a polynuclear quinone compound described in US Pat. Nos. 3,046,127 and 2,951,758, an organoboron compound described in JP-A-2002-229194, and a radical Generator, triarylsulfonium salt (for example, salt with hexafluoroantimony or hexafluorophosphate), phosphonium salt compound (for example, (phenylthiophenyl) diphenylsulfonium salt, etc.) (effective as a cationic polymerization initiator), WO01 / 71428 Onion A salt compounds.

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

  As content in the said photosensitive composition of the said photoinitiator, 0.1-30 mass% is preferable, 0.5-20 mass% is more preferable, 0.5-15 mass% is especially preferable.

<< 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-methoxy bear 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 Compounds rings are condensed (fused ring compounds), as well as amine compounds substituted with either of at least two aromatic hydrocarbon rings and 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.

[Disubstituted aminobenzophenone compounds]
As the di-substituted aminobenzophenone compound, a compound represented by the following general formula (I) is preferable.

In the general formula ^{(I), R 1, R} 2, R 5, and ^{R 6} each independently represent any one of an aliphatic group and an aromatic ^{group, R 3, R 4, R} 7 , R ⁸ , and R ^{9 to} R ¹² each independently represent a hydrogen atom or a monovalent substituent. R ¹ and R ² , R ⁵ and R ⁶ , R ¹ and R ³ , R ² and R ⁴ , R ⁵ and R ⁷ , and R ⁶ and R ⁸ each independently form a nitrogen-containing heterocycle. It may be.

  In the general formula (I), the aliphatic group represents an alkyl group, an alkenyl group, or an alkynyl group that may have a substituent, and the aromatic group has a substituent. Represents an aryl group or a heterocyclic (heterocyclic) group, and the monovalent substituent may be a halogen atom, an amino group which may have a substituent, an alkoxycarbonyl group, a hydroxyl group, an ether group, or a thiol group. , A thioether group, a silyl group, a nitro group, a cyano group, and an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and 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 Groups, naphthyl groups, anthryl groups, phenanthryl groups, indenyl groups, acenaphthenyl groups, and fluorenyl groups. Among them, phenyl groups and naphthyl groups are 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 that may have a substituent, an alkoxycarbonyl group, a hydroxyl group, an ether group, a thiol group, a thioether group, a silyl group, a nitro group, and a cyano group. An alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group which may have a hydrogen atom is preferred.

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

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

Examples of the substituent of the alkyl group which may have a substituent include a substituent composed of a monovalent 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.

Examples of R ⁰¹ of the acyl group (R ⁰¹ CO—) include a hydrogen atom, and the alkyl group and 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 divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms. Preferable specific examples of the substituted alkyl group obtained by combining such a substituent and an alkylene group include a chloromethyl group, a bromomethyl group, a 2-chloroethyl group, a trifluoromethyl group, a methoxymethyl group, and an isopropoxymethyl group. , Butoxymethyl group, s-butoxybutyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, pyridylmethyl group, tetramethylpiperidinylmethyl group, N-acetyltetra Methylpiperidinylmethyl group, trimethylsilylmethyl group, methoxyethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl Group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxycarbonylbutyl group, chloro Phenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group, Sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphonov Nyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl Group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1- Examples include a propenylmethyl group, a 2-butenyl group, a 2-methylallyl group, a 2-methylpropenylmethyl group, a 2-propynyl group, a 2-butynyl group, and a 3-butynyl group.

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

  Specific examples of the compound represented by the general formula (I) include, for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and structural formulas shown below. And the like.

[Disubstituted amino-benzene compound <1>]
As a disubstituted amino-benzene compound having a heterocyclic group as a substituent at a para carbon atom with respect to an amino group on the benzene ring, the heterocyclic group contains a nitrogen atom, an oxygen atom, and a sulfur atom. A 5-membered ring or a 6-membered ring is preferable, and a 5-membered ring having a condensed benzene ring is more preferable, and examples thereof include compounds represented by the following general formula (II).

However, in said general formula (II), R <^21> and R < ²² > respectively independently represents either an aliphatic group and an aromatic group, and R < ²³ > -R < ³⁰ > respectively independently represents a hydrogen atom and X represents any of monovalent substituents, and X represents any of an oxygen atom, a sulfur atom, a dialkylmethylene group, an imino group, and an imino group substituted with an aliphatic group or an aromatic group. R ²¹ and R ²² , R ²¹ and R ²³ , and R ²² and R ²⁴ may each independently form a nitrogen-containing heterocyclic ring, and the benzene ring condensed to the heterocyclic ring has a substituent. It may be.

  In the general formula (II), examples of the aliphatic group, the aromatic group, and the monovalent substituent include those shown as examples in the general formula (I).

  Specific examples of the compound represented by the general formula (II) include, for example, 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl). ) Benzo [4,5] benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2- (p-dimethylaminophenyl) benzothiazole, 2- (p-diethylaminophenyl) benzothiazole 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2- (p-dimethylaminophenyl) -3,3-dimethyl-3H-indole, 2- (p-diethylamino) Phenyl) -3,3-dimethyl-3H-indole and below And compounds represented by the structural formulas shown below.

  On the other hand, among di-substituted amino-benzene compounds having a heterocyclic group as a substituent at a carbon atom para to the amino group on the benzene ring, compounds other than the compound represented by the general formula (II) Are, for example, 2- (p-dimethylaminophenyl) pyridine, 2- (p-diethylaminophenyl) pyridine, 2- (p-dimethylaminophenyl) quinoline, 2- (p-diethylaminophenyl) quinoline, 2- (p -Dimethylaminophenyl) pyrimidine, 2- (p-diethylaminophenyl) pyrimidine, 2,5-bis (p-diethylaminophenyl) -1,3,4-oxadiazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-thiadiazole and the like.

[Disubstituted amino-benzene compound <2>]
As the disubstituted amino-benzene compound having a substituent containing a sulfonylimino group at the para-position carbon atom with respect to the amino group on the benzene ring, for example, a compound represented by the following general formula (III) is preferable. .

However, in said general formula (III), R <^31> and R ^<32 > respectively independently represents either an aliphatic group or an aromatic group, R < ³³ > -R < ³⁷ > respectively independently represents a hydrogen atom and represents any monovalent substituent, R ³⁸ represents a monovalent substituent. R ³¹ and R ³² , R ³¹ and R ³³ , and R ³² and R ³⁴ may each independently form a nitrogen-containing heterocycle.

  In the general formula (III), examples of the aliphatic group, the aromatic group, and the monovalent substituent include those shown as examples in the general formula (I).

  Specific examples of the compound represented by the general formula (III) include, for example, compounds represented by the structural formulas shown below.

[Disubstituted amino-benzene compound <3>]
As the disubstituted amino-benzene compound having the carbostyryl skeleton, for example, a compound represented by the following general formula (IV) is preferable.

However, the general formula ^{(IV), R 41} and ^{R 42} each independently represent any one of an aliphatic group and an aromatic ^group, R 43 ^{to R 47} are each independently a hydrogen atom, and A monovalent substituent is represented, Y represents an oxygen atom or NR ⁴⁸ , and R ⁴⁸ represents a hydrogen atom or a monovalent substituent. R ⁴¹ and R ⁴² , R ⁴¹ and R ⁴³ , and R ⁴² and R ⁴⁴ may each independently form a nitrogen-containing heterocycle.

  In the general formula (IV), examples of the aliphatic group, the aromatic group, and the monovalent substituent include those shown as examples in the general formula (I).

  Specific examples of the compound represented by the general formula (IV) include, for example, compounds described in JP-A No. 2004-221958, coumarin compounds (for example, coumarin-1, coumarin-152, coumarin-307, coumarin- 106, Coumarin-340, etc.).

Among the sensitizers represented by the general formulas (I) to (IV), the compounds represented by the general formulas (I), (III) and (IV) are preferable.
The sensitizer is more preferably a compound having a structure in which at least two aromatic rings represented by the following general formulas (V) to (VII) are bonded to a nitrogen atom.

However, in the general formulas (V) to (VII), the rings A to G each independently have an aromatic hydrocarbon ring or an aromatic heterocyclic ring as a basic skeleton, and the rings A and B Ring D and Ring E, Ring F and Ring G may be bonded to each other to form a bond ring containing N.
In the general formula (VI), the linking group L represents a linking group containing at least one of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and the linking groups L and N represent the aromatic hydrocarbon ring and aromatic group. And n represents an integer of 2 or more.
In the general formula (VII), R represents an alkyl group which may have a substituent.
Rings A to G and linking group L may have a substituent, and these substituents may be bonded to each other to form a ring.

In the general formulas (V) to (VII), the aromatic hydrocarbon rings represented by rings A to G include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, an azulene ring, a fluorene ring, an acenaphthylene ring, and Indene ring and the like can be mentioned, and among these, a benzene ring, a naphthalene ring and an anthracene ring are preferable, and a benzene ring is more preferable.
Examples of the aromatic heterocycle represented by rings A to G include furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, triazole. Ring, pyran ring, thiadizole ring, oxadiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, etc., among which furan ring, thiophene ring, pyrrole ring, pyridine ring, oxazole ring, thiazole ring A furan ring, a thiophene ring, and a pyrrole ring are more preferable.

  Rings included in ring A, ring B, ring D, ring E, ring F, ring G, and linking group L may be bonded to each other to form a condensed ring containing N. In this case, An example is given of forming a carbazole ring containing an N atom to which the ring is attached. When a carbazole ring is formed, any of the rings A to G is exceptionally not a ring structure and may be an arbitrary substituent. In this case, the substituent has a substituent. An alkyl group which may be present is preferred.

Rings A to G may have arbitrary substituents at arbitrary positions, and these substituents may be bonded to each other to form a ring.
In the general formula (VI), the linking group L is a linking group containing at least one of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and N is an aromatic group of the linking group L. It is directly bonded to a hydrocarbon ring or aromatic heterocycle.

Examples of the aromatic hydrocarbon ring and aromatic heterocyclic ring contained in the linking group L include the same as those exemplified as the aromatic hydrocarbon ring and aromatic heterocyclic ring of rings A to G.
As the aromatic hydrocarbon ring contained in the linking group L, a benzene ring, a naphthalene ring and an anthracene ring are preferable, and a benzene ring is more preferable.
The aromatic heterocyclic ring contained in the linking group L is preferably a furan ring, a thiophene ring, a pyrrole ring, a pyridine ring, an oxazole ring, a thiazole ring, a thiadizole ring, or an oxadiazole ring, a furan ring, a thiophene ring, or a pyrrole. A ring is more preferred.

  When the linking group L contains two or more of at least one of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, these rings may be directly connected, or a divalent or higher valent linking group ( The linking group is not limited to a divalent or higher valent group but may include a divalent or higher valent atom). In this case, examples of the divalent or higher valent linking group include known alkylene groups such as an alkylene group represented by the following formula (a), an acetylene group represented by the following formula (b), an amine group, an O atom, S atom, ketone group, thioketone group, -C (= O) O-, amide group, Se, Te, P, As, Sb, Bi, Si, B and other metal atoms, aromatic hydrocarbon ring group, aromatic Examples include a heterocyclic group (unsaturated heterocyclic group), a non-aromatic heterocyclic group (saturated heterocyclic group), and any combination thereof.

However, in said formula (a) and (b), m represents an integer greater than or equal to 1.

Examples of the linking group that can be sandwiched between at least one of the aromatic hydrocarbon ring and the aromatic heterocycle included in the linking group L include an alkylene group represented by the following formula (a) and a formula represented by the following formula (b). Acetylene group, amine group, O atom, S atom, ketone group, -C (= O) O-, amide group, aromatic hydrocarbon ring group, aromatic heterocyclic group, -C = N-, -C = N—N =, a saturated or unsaturated heterocyclic group is preferred, an alkylene group having 1 to 3 carbon atoms, —OCH ₂ O—, —OCH ₂ CH ₂ O—, —O—, a ketone group, a benzene ring A group, a furan ring group, a thiophene ring group, and a pyrrole ring group are more preferable.

  Moreover, in the said general formula (XII), it is preferable that n is 2-5.

In the linking group L, it is desirable to provide an absorption maximum and appropriate absorption in the wavelength region of 350 to 430 nm by adjusting the combination of the aromatic hydrocarbon ring or aromatic heterocyclic ring and the unsaturated linking group.
The ring contained in the linking group L and the linking group that connects the rings may have an arbitrary substituent at an arbitrary position, and these substituents may be connected to each other to form a ring.

Examples of the optional substituent that the rings A to G and the linking group L may have include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; a hydroxyl group; a nitro group; a cyano group; Examples of the monovalent organic group include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, amyl group, tert-amyl group, a linear or branched alkyl group having 1 to 18 carbon atoms such as n-hexyl group, n-heptyl group, n-octyl group, tert-octyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group A cycloalkyl group having 3 to 18 carbon atoms such as a straight chain or branched alkenyl group having 2 to 18 carbon atoms such as a vinyl group, a propenyl group or a hexenyl group; a cyclopentenyl A cycloalkenyl group having 3 to 18 carbon atoms such as cyclohexenyl group; methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, amyloxy group, a linear or branched alkoxy group having 1 to 18 carbon atoms such as a tert-amyloxy group, an n-hexyloxy group, an n-heptyloxy group, an n-octyloxy group, a tert-octyloxy group; a methylthio group, an ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, sec-butylthio group, tert-butylthio group, amylthio group, tert-amylthio group, n-hexylthio group, n-heptylthio group, n-octylthio group, tert- C1-C18 linear or branched alkyl such as octylthio group O group; aryl group having 6 to 18 carbon atoms such as phenyl group, tolyl group, xylyl group and mesityl group; aralkyl group having 7 to 18 carbon atoms such as benzyl group and phenethyl group; vinyloxy group, propenyloxy group, hexenyloxy Table with -COR ^51; alkenylthio group linear or branched 2 to 18 carbon atoms such as vinylthio group, propenylthio group, hexenyl thio group; a straight-chain or branched alkenyloxy group having 2 to 18 carbon atoms group Carboxyl group; acyloxy group represented by —OCOR ⁵² ; amino group represented by —NR ⁵³ R ⁵⁴ ; acylamino group represented by —NHCOR ⁵⁵ ; carbamate group represented by —NHCOOR ⁵⁶ ; A carbamoyl group represented by —CONR ⁵⁷ R ⁵⁸ ; a carboxylic acid ester group represented by —COOR ⁵⁹ ; —SO ₃ Sulfamoyl groups represented by NR ⁶⁰ R _^61; -SO ³ sulfonic acid represented by ^{R 62} ester group; -C = group represented by ^{NR 63; -C = N-NR} 64 group represented by ^{R 65} A saturated or unsaturated heterocyclic group such as a 2-thienyl group, a 2-pyridyl group, a furyl group, an oxazolyl group, a benzoxazolyl group, a thiazolyl group, a benzothiazolyl group, a morpholino group, a pyrrolidinyl group, or a tetrahydrothiophene dioxide group. It is done.

R ^{51 to} R ⁶⁵ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, or an optionally substituted aralkyl. Represents a group. In these substituent groups, the alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkoxy group, alkylthio group, aryl group, aralkyl group, alkenyloxy group, and alkenylthio group are further substituted with a substituent. May be.

There are no particular restrictions on the substitution positions of these substituents in the rings A to G and the linking group L, and when there are a plurality of substituents, these may be the same or different. Also good.
Rings A to G and linking group L are unsubstituted or substituted as a halogen atom, a cyano group, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, or a substituted group. An alkenyl group which may be substituted, an aryl group which may be substituted, an aryl group which may be substituted, an aralkyl group which may be substituted, an alkenyloxy group which may be substituted, an alkenylthio which may be substituted Group, optionally substituted amino group, optionally substituted acyl group, carboxyl group, group represented by —C═NR ⁶³ , group represented by —C═N—NR ⁶⁴ R ⁶⁵ , saturated Alternatively, it is preferably substituted with an unsaturated heterocyclic group. In the case of having a substituent, examples of the substituent include a halogen atom, a cyano group, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkenyl group, and an optionally substituted group. A good alkoxy group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted amino group, a group represented by —C═NR ⁶³ , —C═N—NR ⁶⁴ R; A group represented by ⁶⁵ , a saturated or unsaturated heterocyclic group is preferred.

  When the above optional substituents that the rings A to G and the linking group L may have are further substituted with arbitrary substituents, the substituents include methoxy group, ethoxy group, n-propoxy group, C1-C10 alkoxy groups such as iso-propoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group; methoxymethoxy group, ethoxymethoxy group, propoxymethoxy group, ethoxyethoxy group, propoxyethoxy group, C2-C12 alkoxyalkoxy groups such as methoxybutoxy group; C3-C15 alkoxyalkoxyalkoxy such as methoxymethoxymethoxy group, methoxymethoxyethoxy group, methoxyethoxymethoxy group, ethoxymethoxymethoxy group, and ethoxyethoxymethoxy group Group: 6 carbon atoms such as phenyl group, tolyl group, xylyl group 12 aryl groups (these may be further substituted with a substituent); aryloxy groups having 6 to 12 carbon atoms such as phenoxy group, tolyloxy group, xylyloxy group, naphthyloxy group; vinyloxy group, allyloxy group, etc. C2-C12 alkenyloxy group; acyl group such as acetyl group, propionyl group; cyano group; nitro group; hydroxyl group; tetrahydrofuryl group; amino group; N, N-dimethylamino group, N, N-diethylamino An alkylamino group having 1 to 10 carbon atoms such as a group; an alkylsulfonylamino group having 1 to 6 carbon atoms such as a methylsulfonylamino group, an ethylsulfonylamino group and an n-propylsulfonylamino group; a fluorine atom, a chlorine atom and a bromine atom Halogen atoms such as methoxycarbonyl group, ethoxycarbonyl group, n-propo A C2-C7 alkoxycarbonyl group such as a sicarbonyl group, iso-propoxycarbonyl group, n-butoxycarbonyl group; methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, iso-propylcarbonyloxy group An alkylcarbonyloxy group having 2 to 7 carbon atoms such as n-butylcarbonyloxy group; methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, iso-propoxycarbonyloxy group, n-butoxycarbonyloxy group And an alkoxycarbonyloxy group having 2 to 7 carbon atoms such as tert-butoxycarbonyloxy group; a linear or branched alkenyl group having 2 to 18 carbon atoms such as vinyl group, propenyl group and hexenyl group;

  The sensitizers represented by the general formulas (V) to (VII) preferably have an appropriate absorption in the wavelength range of 390 to 430 nm, and preferably have an absorption maximum in the wavelength range of 330 to 450 nm. More preferably, it has an absorption maximum in the wavelength region of 430 nm. Therefore, the molecule preferably has at least one of four or more aromatic hydrocarbon rings and aromatic heterocycles, and has at least one of five or more aromatic hydrocarbon rings and aromatic heterocycles. It is more preferable.

  Specific examples of the compounds represented by the general formulas (V) to (VII) are shown below, but are not limited thereto.

However, in said formula (Vl), ^R71 , ^R72 , ^R73 represents either of the following groups each independently.

However, in the formula (VI-g), the bonding position is on any two benzene rings of the two terminal phenyl groups or the two terminal tolyl groups.

However, in said formula (VI-j), R <^81> , R < ^{82 >} , R <^83> represents either of the following groups each independently.

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.

<Thermal crosslinking agent>
The thermal crosslinking agent is not particularly limited and may be appropriately selected depending on the purpose.For example, in order to improve the film strength after curing of the photosensitive layer, it does not adversely affect 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.
Examples of the epoxy compound having at least two oxirane rings in one molecule include, for example, a bixylenol type or biphenol type epoxy resin (“YX4000 Japan Epoxy Resin” etc.) or a mixture thereof, a complex having an isocyanurate skeleton, etc. Cyclic epoxy resins ("TEPIC; manufactured by Nissan Chemical Industries", "Araldite PT810; manufactured by Ciba Specialty Chemicals"), bisphenol A type epoxy resin, novolac type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, halogenated epoxy resin (for example, low brominated epoxy resin, high halogenated epoxy resin, odor Phenol novolac type epoxy resin), allyl group-containing bisphenol A type epoxy resin, trisphenol methane type epoxy resin, diphenyldimethanol type epoxy resin, phenol biphenylene type epoxy resin, dicyclopentadiene type epoxy resin ("HP-7200, HP-7200H; manufactured by Dainippon Ink & Chemicals, Inc.), glycidylamine type epoxy resin (diaminodiphenylmethane type epoxy resin, diglycidylaniline, triglycidylaminophenol, etc.), glycidyl ester type epoxy resin (phthalic acid diglycidyl ester) Adipic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer acid diglycidyl ester, etc.) hydantoin type epoxy resin, alicyclic epoxy resin (3,4 Poxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, dicyclopentadiene diepoxide, “GT-300, GT-400, ZEHPE3150; manufactured by Daicel Chemical Industries”, etc. )), Imide type alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A novolak type epoxy resin, tetraphenylolethane type epoxy resin, glycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group-containing epoxy Resin (naphthol aralkyl type epoxy resin, naphthol novolac type epoxy resin, tetrafunctional naphthalene type epoxy resin, commercially available products such as “ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.” HP-4032, EXA-4750, EXA-4700; manufactured by Dainippon Ink & Chemicals, Inc.), polyphenol compounds obtained by addition reaction of phenol compounds with diolefin compounds such as divinylbenzene and dicyclopentadiene, and epichlorohydrin A reaction product of 4-vinylcyclohexene-1-oxide obtained by epoxidation with peracetic acid, an epoxy resin having a linear phosphorus-containing structure, an epoxy resin having a cyclic phosphorus-containing 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 methacrylate copolymer epoxy resin ("CP- 5 0S, CP-50M; manufactured by NOF Corporation, etc.), copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, bis (glycidyloxyphenyl) fluorene type epoxy resin, bis (glycidyloxyphenyl) adamantane type epoxy resin, etc. Although it is mentioned, it is not restricted to these. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.

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

From the viewpoint of storage stability at room temperature, the epoxy compound containing an epoxy group having an alkyl group at the β-position is substituted with β-alkyl in all epoxy groups in the total amount of the epoxy compound contained in the photosensitive composition. The proportion of glycidyl groups is preferably 30% or more, more preferably 40% or more, and particularly preferably 50% or more.
The β-alkyl-substituted glycidyl group is not particularly limited and may be appropriately selected depending on the intended purpose. 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 structural formula (i), a β-alkyl glycidyl ether derived from a polymer obtained from the bisphenol compound and epichlorohydrin, and the following structural formula (ii) Poly-β-alkyl glycidyl ethers of phenol compound-formaldehyde polycondensates are preferred.

In the Structural Formula (i), R "represents any of an alkyl group having 1 to 6 carbon hydrogen and _{carbon, n 11} represents an integer of 0 to 20.
In the Structural Formula (ii), 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 to 20 Represents an integer.
These epoxy compounds containing an epoxy group having an alkyl group at the β-position may be used alone or in combination of two or more. It is also possible to use together an epoxy compound having at least two oxirane rings in one molecule and an epoxy compound containing an epoxy group having an alkyl group at the β-position.

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

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

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

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

  1-50 mass% is preferable and, as for solid content content of the said thermal crosslinking agent in the said photosensitive composition, 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 further adhesion promoters to the substrate surface and other auxiliary agents ( For example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, etc.) may be used in combination. By appropriately containing these components, 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.

  As content of the said thermal-polymerization inhibitor, 0.001-5 mass% is preferable with respect to the said polymeric compound, 0.005-2 mass% is more preferable, 0.01-1 mass% is especially preferable. 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.

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

  The solid content 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.

<< External 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.

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

  Examples of the method for forming the photosensitive layer include a method in which the photosensitive composition is applied to the surface of the substrate and dried, as a first aspect, and a photosensitive film is heated and applied as a second aspect. The method of laminating | stacking on the surface of a base material under at least any one of pressure is mentioned.

In the method for forming a photosensitive layer according to the first aspect, a photosensitive layer is formed by applying and drying the photosensitive composition on the substrate.
The method for coating and drying is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the photosensitive composition is dissolved, emulsified or dispersed on the surface of the base material in water or a solvent. 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, For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, n-hexanol Alcohols such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone, etc .; ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and Esters such as methoxypropyl acetate; aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene; carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, monochlorobenzene Halogenated hydrocarbons of: ethers such as tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane, etc. . These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.

The coating method is not particularly limited and can be appropriately selected depending on the purpose. For example, using a spin coater, a slit spin coater, a roll coater, a die coater, a curtain coater, etc. The method of apply | coating is mentioned.
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.

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

  In the method for forming a photosensitive layer according to the second aspect, a photosensitive film having a support on the surface of the substrate and a photosensitive layer in which a photosensitive composition is laminated on the support is heated and pressurized. Laminate while doing at least one. In addition, when the said photosensitive film has a protective film mentioned later, it is preferable to peel this protective film and to laminate | stack so that the said photosensitive layer may overlap with the said base material.

[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 may be appropriately selected depending on the purpose. For example, the photosensitive layer and the protective film are provided in this order on the support, On the support, the PC layer, the photosensitive layer, and the protective film are arranged in this order. On the support, the cushion layer, the PC layer, the photosensitive layer, and the protective film are arranged in this order. The form which has is mentioned. 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 as 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 as a shape of the said support body, Although it can select suitably according to the objective, A long shape is preferable. There is no restriction | limiting in particular as the length of the said elongate support body, For example, the thing of length 10m-20000m is mentioned.

-Photosensitive layer in photosensitive film-
The photosensitive layer in the photosensitive film is formed of the photosensitive composition.
There is no restriction | limiting in particular as a location provided in the said photosensitive film of the said photosensitive layer, Although it can select suitably according to the objective, Usually, it laminates | stacks on the said support body.

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

  Formation of the photosensitive layer in the photosensitive film can be performed by the same method as the application of the photosensitive composition solution to the substrate and drying (method for forming the photosensitive layer of the first aspect), for example, And a method of applying the photosensitive composition solution using a spin coater, a slit spin coater, a roll coater, a die coater, a curtain coater, or the like.

<Protective film>
The protective film has a function of preventing and protecting the photosensitive layer from being stained and damaged.
There is no restriction | limiting in particular as a location provided in the said photosensitive film of the said protective film, 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 as 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 a discharge irradiation process, an active plasma irradiation process, and a laser beam irradiation process.

Moreover, as a static friction coefficient of the said support body and the said protective film, 0.3-1.4 are preferable and 0.5-1.2 are more preferable.
When the coefficient of static friction is less than 0.3, slipping is excessive, so that winding deviation may occur when the roll is formed. 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 as the length of the said elongate photosensitive film, For example, it can select suitably from the range of 10m-20,000m. Further, slitting may be performed so that the user can easily use, and a long body in the range of 100 m to 1,000 m may be formed into a roll. In this case, it is preferable that the support is wound up so as to be the outermost side. Moreover, you may slit the said roll-shaped photosensitive film in a sheet form. When storing, from the viewpoint of protecting the end face and preventing edge fusion, it is preferable to install a separator (particularly moisture-proof and containing a desiccant) on the end face, and use a low moisture-permeable material for packaging. Is preferred.

The protective film may be surface-treated in order to adjust the adhesion between the protective film and the photosensitive layer. In the surface treatment, for example, an undercoat layer made of a polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, or polyvinyl alcohol is formed on the surface of the protective film. The undercoat layer can be formed by applying the polymer coating solution to the surface of the protective film and then drying at 30 to 150 ° C. (especially 50 to 120 ° C.) for 1 to 30 minutes.
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.

There is no restriction | limiting in particular as said heating temperature, Although it can select suitably according to the objective, For example, 70-130 degreeC is preferable and 80-110 degreeC is more preferable.
There is no restriction | limiting in particular as a pressure of the said pressurization, Although it can select suitably according to the objective, For example, 0.01-1.0 MPa is preferable and 0.05-1.0 MPa is more preferable.

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

The photosensitive film can be widely used for forming a permanent pattern such as a printed wiring board, a color filter, a pillar material, a rib material, a spacer, a display member such as a partition, a hologram, a micromachine, a proof, and the like. It can be suitably used for a pattern forming method.
In particular, since the photosensitive film has a uniform thickness, the film is more precisely laminated on the substrate when a permanent pattern is formed.

  In addition, there is no restriction | limiting in particular as exposure to the laminated body which has the photosensitive layer formed by the formation method of the photosensitive layer of the said 2nd aspect, According to the objective, it can select suitably, For example, the said support body The photosensitive layer may be exposed through the cushion layer and the PC layer, and after the support is peeled off, the photosensitive layer may be exposed through the cushion layer and the PC layer. After peeling off the cushion layer, the photosensitive layer may be exposed through the PC layer, or after peeling off the support, cushion layer, and PC layer, the photosensitive layer may be exposed.

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

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

  The developer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alkali metal or alkaline earth metal hydroxides or carbonates, bicarbonates, aqueous ammonia, and quaternary ammonium. A salt aqueous solution is preferred. Among these, an aqueous sodium carbonate solution is particularly preferable.

  The developer includes a surfactant, an antifoaming agent, an organic base (for example, benzylamine, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.) May be used in combination with an organic solvent (for example, alcohols, ketones, esters, ethers, amides, lactones, etc.). The developer may be an aqueous developer obtained by mixing water or an 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 permanent 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 developing step. The entire surface exposure accelerates the curing of the resin in the photosensitive composition forming the photosensitive layer, and the surface of the permanent pattern is cured.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface exposure, 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 developing step. By heating the entire surface, the film strength of the surface of the permanent pattern is increased.
As heating temperature in the said whole surface heating, 120-250 degreeC is preferable and 120-200 degreeC is more preferable. When the heating temperature is less than 120 ° C., the film strength may not be improved by heat treatment. When the heating temperature exceeds 250 ° C., the resin in the photosensitive composition is decomposed, and the film quality is weak and brittle. Sometimes.
As heating time in the said whole surface heating, 10 to 120 minutes are preferable and 15 to 60 minutes are more preferable.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface heating, According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, IR heater etc. are mentioned.

When the substrate is a printed wiring board such as a multilayer wiring board, the permanent pattern of the present invention can be formed on the printed wiring board, and further soldered as follows.
That is, the development step forms a hardened layer that is the permanent pattern, and the metal layer is exposed on the surface of the printed wiring board. Gold plating is performed on the portion of the metal layer exposed on the surface of the printed wiring board, and then soldering is performed. Then, a semiconductor or a component is mounted on the soldered portion. At this time, the permanent pattern by the hardened layer 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 permanent pattern forming method of the present invention, it is preferable to form at least one of a protective film, an interlayer insulating film, and a solder resist pattern.
The permanent pattern formed by the permanent pattern forming method can protect the wiring from external impact and bending, and particularly in the case of the interlayer insulating film, for example, a multilayer wiring board or a build-up wiring It is useful for high-density mounting of semiconductors and components on a substrate.

  Since the permanent pattern forming method of the present invention can form a permanent pattern with high definition and efficiency by suppressing distortion of an image formed on the photosensitive layer, high-definition exposure is required. In particular, it can be suitably used for forming high-definition permanent patterns.

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

Example 1
-Preparation of photosensitive composition-
A photosensitive composition (solution) was prepared based on the following composition.
[Composition of photosensitive composition solution]
-Phenylglycine 0.2 mass part-Barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., B30) dispersion 63 mass parts-Epoxy acrylate compound: Binder (PR-300, concentration 67%, Showa Polymer Co., Ltd.) 24. 5 parts by mass-Vinyl copolymer having (meth) acryloyl group and carboxyl group in side chain: Binder (SPC-2X, concentration 60%, Showa Polymer Co., Ltd.) 13.8 parts by mass-Structural formula ( 38) Epoxy compound: Thermal crosslinking agent 16.7 parts by mass Dipentaerythritol hexaacrylate: Polymerizable compound 5.5 parts by mass IRGACURE 369 (Ciba Specialty Chemicals) 2.0 parts by mass 1 -Chloro-4-propyloxythioxanthone (the following structural formula (39)) 0.2 part by mass-hydroquinone monomethyl ether 56 parts by mass, dicyandiamide 0.4 parts by mass, 2 MA-OK (manufactured by Shikoku Kasei Kogyo Co., Ltd.) 0.3 parts by mass, phthalocyanine green 0.42 parts by mass, F780F (manufactured by Dainippon Ink Co., Ltd.) 30% by mass Concentration product methyl ethyl ketone solution)
0.066 parts by mass
-Methyl ethyl ketone 60.0 parts by mass The barium sulfate dispersion is composed of 22 parts by mass of barium sulfate (manufactured by Sakai Chemical Co., Ltd., B30), 12 parts by mass of a 67% by mass solution of the above-mentioned PR-300 diethylene glycol monomethyl ether acetate, and methyl ethyl ketone. 29 parts by mass was mixed in advance, and then dispersed with a motor mill M-200 (manufactured by Eiger) using zirconia beads having a diameter of 1.0 mm at a peripheral speed of 9 m / s for 3.5 hours.

-Production of photosensitive film-
The obtained photosensitive composition solution was applied onto a PET (polyethylene terephthalate) film having a thickness of 16 μm as the support and dried to form a photosensitive layer having a thickness of 35 μm. Next, a 20 μm-thick polypropylene film as the protective film was laminated on the photosensitive layer with a laminate to produce a photosensitive film.

-Formation of permanent pattern-
--- Preparation of photosensitive laminate--
Next, as the base material, a surface of a copper-clad laminate (no through hole, copper thickness 12 μm) on which wiring was formed was prepared by chemical polishing treatment. A vacuum laminator (VP130, manufactured by Nichigo Morton Co., Ltd.) was peeled off the protective film on the photosensitive film so that the photosensitive layer of the photosensitive film was in contact with the copper-clad laminate. The photosensitive laminate was prepared by laminating the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) in this order.
The pressure bonding conditions were a vacuum drawing time of 40 seconds, a pressure bonding temperature of 70 ° C., a pressure bonding pressure of 0.2 MPa, and a pressure application time of 10 seconds.

  Using the photosensitive film and the laminate, the exposure sensitivity and resolution of the photosensitive layer were measured by the following methods, and the formed pattern was evaluated for jaggy and edge roughness. The results are shown in Table 1.

<Measurement of exposure sensitivity>
-Measurement of the shortest development time-
The laminate was allowed to stand at room temperature for 10 minutes, and then the polyethylene terephthalate film (support) was peeled off from the laminate, and the photosensitive layer was developed. The development process is performed by showering the entire surface of the photosensitive layer on the copper-clad laminate with a 1% by weight sodium carbonate aqueous solution as an alkaline developer at 30 ° C., and the photosensitive layer is completely removed. The time required until this time was measured, and this was taken as the shortest development time.
As a result, the shortest development time was 20 seconds.

-Measurement of exposure sensitivity-
The photosensitive layer in the laminate, from the polyethylene terephthalate film (support) side, using the following exposure device, light energy from 0.1 mJ / cm ² to 100 mJ / cm ² at ^{2 1/2} times the interval The exposure was performed by irradiating different amounts of light, and a part of the photosensitive layer was cured. After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) is peeled off from the laminate, and an aqueous sodium carbonate solution (30 ° C., 1% by mass) is applied to the entire surface of the photosensitive layer on the copper clad laminate. Spraying was performed twice as long as the shortest development time determined by the above method, and 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 thus obtained, the amount of light energy when the thickness of the cured region was the same as that before exposure was determined as the amount of light energy necessary for curing the photosensitive layer. Table 1 shows the amount of light energy (exposure sensitivity) required to cure the photosensitive layer thus obtained.

<< Exposure equipment >>
As the exposure apparatus, the flat bed type exposure apparatus having the appearance shown in FIG. 1 and the exposure head having the configuration shown in FIG. 2 was used. The control unit 42 has a control circuit shown in FIG. In the exposure head, a semiconductor laser light source as the light irradiating means, and 1024 micromirrors 40 are arranged in the main scanning direction in the DMD 36 schematically shown in FIG. 3 as the light modulating means, and 768 in the sub scanning direction. A DMD 36 controlled so as to drive only 1024 × 256 rows among the array is provided.
The exposure head was arranged so that the DMD column direction was 15 ° with respect to the scanning direction, and exposure was performed by moving the exposure head relative to the scanning direction.

  Each parameter was set in the same manner as the values shown in FIG. 16, and exposure was performed. At this time, as apparent from FIG. 16, it is expected that no jaggy occurs before and after the inclination angle of 15 ° of the original image 80 and a good drawing pattern is obtained.

<Measurement of resolution>
The laminate was prepared by the same method as above, and allowed to stand at room temperature (23 ° C., 55% RH) for 10 minutes. From the obtained polyethylene terephthalate film (support) of the laminate, using the pattern forming device, line / space = 1/1, and line widths of 5 to 20 μm are exposed in increments of 1 μm. Each line width was exposed in 5 μm increments until the line width was 20-50 μm. The exposure amount at this time is the amount of light energy necessary for effecting the photosensitive layer, obtained by measuring the exposure sensitivity.
After exposure, after standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) is peeled off from the laminate, and an aqueous sodium carbonate solution (as a developer) is applied to the entire surface of the photosensitive layer on the copper clad laminate. 30 ° C., 1% by mass) was sprayed at a spray pressure of 0.15 MPa twice the shortest development time determined by the above method to dissolve and remove uncured regions.
The surface of the copper-clad laminate with the cured resin pattern thus obtained was observed with an optical microscope, and the minimum line width without any abnormalities such as tsumari and twist was measured on the cured resin pattern line. did. The resolution is better as the numerical value is smaller. The results are shown in Table 1.

-Formation and evaluation of permanent patterns-
After exposing the entire area of 2 × 10 cm from the polyethylene terephthalate film (support) of the laminate to the exposure sensitivity determined by the measurement of the exposure sensitivity, and leaving it at room temperature for 10 minutes. The polyethylene terephthalate film (support) is peeled off from the laminate, and a 1% by weight sodium carbonate aqueous solution is used as the developer, and sprayed at 30 ° C. for twice the shortest development time as described above. Was dissolved and removed, washed with water, and dried to form a pattern.
The entire surface of the laminate on which the pattern was formed was subjected to heat treatment at 150 ° C. for 60 minutes to cure the pattern, increase the film strength, and obtain a permanent pattern. When the obtained permanent pattern was visually observed, no bubbles were observed on the surface.
As a result of measuring the pencil hardness based on JIS K-5400, the permanent pattern was 5H or more.
The printed wiring board on which the permanent pattern was formed was subjected to gold plating according to a conventional method and then subjected to a water-soluble flux treatment. Subsequently, it was immersed three times in a solder bath set at 260 ° C. for 5 seconds, and the flux was removed by washing with water. When the permanent pattern was visually observed after removing the flux, no peeling, blistering, or discoloration of the cured film was observed.

<With or without jaggy>
Using the exposure apparatus, the laminate was exposed to light so that a horizontal line pattern in a direction orthogonal to the scanning direction of the exposure head was formed, and a permanent pattern was formed in the same manner as the resolution measurement. .
Among the formed permanent patterns, arbitrary five portions of a line having a line width of 40 μm were observed using a laser microscope (VK-9500, manufactured by Keyence Corporation; objective lens 50 ×) to evaluate the presence or absence of jaggies. . The allowable range of the jaggy pitch pji was −5 μm to +5 μm, the allowable range of the jaggy amplitude aji was −1 μm to +1 μm, and those outside the allowable range were evaluated as having jaggy.

<Edge roughness>
The photosensitive layer was exposed using the exposure apparatus such that a horizontal line pattern in a direction perpendicular to the scanning direction of the exposure head was formed, and a permanent pattern was formed in the same manner as the resolution measurement.
Among the formed permanent patterns, arbitrary five points of a line having a line width of 40 μm were observed using a laser microscope (VK-9500, manufactured by Keyence Corporation; objective lens 50 ×), and the edge position in the field of view was observed. Among them, the difference between the most swollen part (mountain peak) and the most constricted part (valley bottom) was obtained as an absolute value, and the average value of the five observed points was calculated, and this was used as edge roughness. The edge roughness is preferably as the value is small because it exhibits good performance.

(Example 2)
In Example 1, a permanent pattern is formed in the same manner as in Example 1 except that exposure is performed by setting the parameters in the exposure apparatus in the same manner as the values shown in FIG. , And edge roughness were evaluated. The results are shown in Table 1.
At this time, as is apparent from FIG. 18, it is expected that no jaggy occurs before and after an inclination angle of 15 ° of the original image 80 and a good drawing pattern is obtained.

(Example 3)
In Example 1, 0.2 part by mass of 1-chloro-4-propyloxythioxanthone in the photosensitive composition was changed to 0.25 part by mass of 2-chloro-10-butylacridone (the following structural formula (40)). The photosensitive composition was prepared like Example 1 except having replaced. Using the obtained photosensitive composition, the photosensitive film and the laminate were produced in the same manner as in Example 1, and a permanent pattern was formed, and the exposure sensitivity of the photosensitive layer in the same manner as in Example 1, The resolution was measured, and the formed permanent pattern was evaluated for the presence or absence of jaggies and the edge roughness. The results are shown in Table 1.

Example 4
In Example 1, 0.2 part by mass of 1-chloro-4-propyloxythioxanthone in the photosensitive composition is replaced with 0.2 part by mass of the disubstituted amino-benzene compound represented by the following structural formula (41). A photosensitive composition was prepared in the same manner as in Example 1 except that. Using the obtained photosensitive composition, the photosensitive film and the laminate were produced in the same manner as in Example 1, and a permanent pattern was formed, and the exposure sensitivity of the photosensitive layer in the same manner as in Example 1, The resolution was measured, and the formed permanent pattern was evaluated for the presence or absence of jaggies and the edge roughness. The results are shown in Table 1.

(Comparative Example 1)
In Example 1, except that exposure was performed without setting and changing each parameter, a photosensitive film and a laminate were prepared in the same manner as in Example 1, a permanent pattern was formed, exposure sensitivity, The resolution, presence / absence of jaggies, and edge roughness were evaluated. The results are shown in Table 1.
The shortest development time was 20 seconds.

  From the results shown in Table 1, compared with the permanent pattern of Comparative Example 1, the permanent patterns of Examples 1 to 4 formed by the permanent pattern forming method of the present invention have reduced jaggy, small edge roughness, and high definition. I found out that In addition, in the exposure process for forming the permanent pattern of Examples 1 to 4, a desired pattern could be formed without reducing the exposure speed. It was found that it can be formed.

  In the permanent pattern forming method of the present invention, a desired drawing pattern with reduced jaggies is formed on an exposed surface without reducing the exposure speed, so that a permanent film such as a protective film, an insulating film, and a solder resist pattern is formed. Permanent patterns that can form patterns with high definition and efficiency can be formed with high definition and efficiency, so they can be used suitably for the formation of various patterns that require high-definition exposure. In particular, it can be suitably used for forming a high-definition protective film, insulating film, and solder resist pattern.

FIG. 1 is an external perspective view of the exposure apparatus. FIG. 2 is a schematic block diagram of an exposure head in the exposure apparatus. FIG. 3 is a partially enlarged view showing a configuration of a digital micromirror device (DMD) as a light modulation means. FIG. 4 is an explanatory diagram when the micromirrors constituting the DMD shown in FIG. 3 are set to the on state. FIG. 5 is an explanatory diagram when the micromirrors constituting the DMD shown in FIG. 3 are set in the OFF state. FIG. 6 is a diagram illustrating the relationship between the exposure head in the exposure apparatus and the sheet film (exposed surface of the photosensitive layer) positioned on the exposure stage. FIG. 7 is a diagram for explaining the relationship between the exposure head in the exposure apparatus and the exposure area on the sheet film (the exposed surface of the photosensitive layer). FIG. 8 is a block diagram of the control circuit of the exposure apparatus. FIG. 9 is an explanatory diagram of an arrangement state of micromirrors constituting a DMD used for an exposure head in the exposure apparatus. FIG. 10 is an explanatory diagram of parameters of a drawing pattern formed by the exposure head. FIG. 11 is an explanatory diagram of parameters of a drawing pattern formed by the exposure head. FIG. 12 is an explanatory diagram of parameters of a drawing pattern formed by the exposure head. FIG. 13 is an explanatory diagram of calculation results of jaggy pitch and jaggy amplitude of a drawing pattern formed by the exposure head. FIG. 14 is an explanatory diagram of calculation results of jaggy pitch and jaggy amplitude of a drawing pattern formed by the exposure head. FIG. 15 is an explanatory diagram of calculation results of jaggy pitch and jaggy amplitude of a drawing pattern formed by the exposure head. FIG. 16 is an explanatory diagram of calculation results of jaggy pitch and jaggy amplitude of a drawing pattern formed by the exposure head. FIG. 17 is an explanatory diagram of calculation results of jaggy pitch and jaggy amplitude of a drawing pattern formed by the exposure head. FIG. 18 is an explanatory diagram of calculation results of jaggy pitch and jaggy amplitude of a drawing pattern formed by the exposure head.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Exposure apparatus 18 Exposure stage 24a-24j Exposure head 26 Scanner 28 Light source unit 36 DMD
38 SRAM cell 40 Micro mirror 42 Control unit 48 Micro lens array 58a to 58j Exposure area 64 Sync signal generation unit 66 Exposure stage drive unit 68 Drawing data storage unit 70 DMD modulation unit 72 Frequency change unit 74 Phase difference change unit 75 Movement speed change Section 76 Exposure head rotation drive section 77 Swath 78 Optical magnification changing section 79 Zoom optical system 80 Original image F Sheet film (laminate)
L Laser beam

Claims (36)

For the photosensitive layer formed on the surface of the substrate with a photosensitive composition containing at least a binder, a polymerizable compound, a photopolymerization initiation compound, and a thermal crosslinking agent,
A light irradiating means, and n (where n is a natural number of 2 or more) two-dimensionally arranged picture elements that receive and emit light from the light irradiating means, and according to the pattern information, An exposure head provided with a light modulation means capable of controlling a picture element portion, wherein the exposure head is arranged such that a column direction of the picture element portion forms a predetermined inclination angle with respect to a scanning direction of the exposure head. And performing exposure by moving the exposure head relative to the scanning direction,
In the drawing pattern corresponding to the pattern information, at least one of jaggy pitch and jaggy amplitude generated by being reproduced by the drawing pixel formed by the picture element portion is equal to or less than a predetermined value,
(A) an arrangement pitch of the drawing pixels formed by the adjacent picture element portions;
(B) an inclination angle of the two-dimensional drawing pixel group composed of a plurality of the drawing pixels with respect to the scanning direction;
(C) a drawing pitch of the drawing pixels with respect to the scanning direction, and (d) a phase difference of a drawing position with respect to the scanning direction of the drawing pixels formed adjacent to a direction substantially orthogonal to the scanning direction,
A permanent pattern forming method characterized in that at least one of the above is set, the picture element portion is subjected to modulation control at a predetermined timing based on the pattern information, exposed, and developed.   The permanent pattern forming method according to claim 1, wherein the light modulation means is a spatial light modulation element.   The permanent pattern forming method according to claim 1, wherein the spatial light modulation element is a digital micromirror device (DMD).   The method for forming a permanent pattern according to any one of claims 1 to 3, wherein the photosensitive layer is formed by applying the photosensitive composition to the surface of the substrate and drying.   The photosensitive layer is formed by laminating a photosensitive film having a support and a photosensitive layer formed by laminating a photosensitive composition on the support on the surface of the substrate under at least one of heating and pressing. The permanent pattern formation method according to claim 1, wherein the permanent pattern formation method is performed.   The binder according to any one of claims 1 to 5, wherein the binder contains at least one of an epoxy acrylate compound and at least one of a vinyl copolymer having a (meth) acryloyl group and an acidic group in a side chain. Permanent pattern forming method.   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 permanent pattern formation method as described.   The permanent pattern formation method in any one of Claim 1 to 7 in which a photosensitive composition contains a sensitizer.   The sensitizer is at least one selected from a condensed ring compound and an amine compound substituted with at least two aromatic hydrocarbon rings and aromatic heterocyclic rings. Permanent pattern forming method.   The permanent pattern forming method according to claim 5, wherein the support includes a synthetic resin and is transparent.   The permanent pattern forming method according to claim 5, wherein the support has a long shape.   The method for forming a permanent pattern according to claim 5, wherein the photosensitive film has a long shape and is wound in a roll shape.   The permanent pattern formation method in any one of Claim 5 to 12 in which a photosensitive film has a protective film on a photosensitive layer.   The method for forming a permanent pattern according to claim 1, wherein the photosensitive layer has a thickness of 3 to 100 μm.   The permanent pattern forming method according to claim 1, wherein the base material is a printed wiring board on which wiring has been formed.   16. The exposure according to claim 1, wherein the exposure is performed using an exposure apparatus including at least one of a drawing pixel group rotating unit, a drawing magnification changing unit, a drawing timing changing unit, a moving speed changing unit, and a phase difference changing unit. A method for forming a permanent pattern according to claim 1.   The permanent pattern forming method according to any one of claims 1 to 16, wherein the tilt angle (b) is changed by rotating either the entire exposure head or the light modulating means by the drawing pixel group rotating means.   The drawing magnification changing means changes the drawing magnification of the drawing pixels formed on the exposed surface of the photosensitive layer, and adjusts either the arrangement pitch (a) or the drawing pitch (c). The permanent pattern formation method in any one.   The permanent pattern formation method according to any one of claims 1 to 16, wherein the drawing timing changing means adjusts the drawing pitch (c) by changing the drawing timing on the exposed surface of the photosensitive layer by the drawing portion.   The permanent pattern forming method according to any one of claims 1 to 16, wherein the moving pitch changing means adjusts the drawing pitch (c) by changing the relative moving speed of the exposure head with respect to the exposed surface of the photosensitive layer.   The permanent pattern forming method according to any one of claims 1 to 16, wherein the phase difference changing means changes the phase difference of the modulation control timing of adjacent picture element portions to change the phase difference (d).   The permanent pattern according to any one of claims 1 to 21, wherein at least one of an arrangement pitch (a), an inclination angle (b), a drawing pitch (c), and a phase difference (d) is set according to the drawing pattern. Forming method.   23. Any one of the arrangement pitch (a), the inclination angle (b), the drawing pitch (c), and the phase difference (d) is set according to the inclination angle of the drawing pattern with respect to the scanning direction. A method for forming a permanent pattern according to claim 1.   The arrangement pitch (a), the inclination angle (b), and the drawing pitch (c) so that any one of the jaggy jaggy pitch and the jaggy amplitude generated in the drawing pattern orthogonal or substantially orthogonal to the scanning direction is equal to or less than a predetermined value. ) And a phase difference (d) are set. The permanent pattern forming method according to any one of claims 1 to 23. Adjustment of arrangement pitch (a), inclination angle (b), drawing pitch (c), and phase difference (d)
(E) the pitch of the control point sequence along the substantially scanning direction of the control point, the control point defined as the center point of the drawing pixel formed on the exposed surface of the photosensitive layer by the picture element unit,
(F) the arrangement direction of the control point sequence;
(G) a pitch of the control points with respect to the scanning direction, and (h) a phase difference of the control points adjacent to the direction substantially orthogonal to the scanning direction with respect to the scanning direction,
The permanent pattern forming method according to claim 1, wherein the permanent pattern forming method is performed by controlling at least one of the method so as to reduce jaggy of a drawing pattern. Defined by at least one of pitch (e), arrangement direction (f) of control point sequence, pitch (g) of control point with respect to scanning direction, and phase difference (h), and at least one of jaggy pitch and jaggy amplitude Find the correlation with the shape of the jaggy
The permanent pattern forming method according to claim 25, wherein any one of (e) to (h) is set or changed based on the correlation.   The control point sequence pitch (e), the arrangement direction (f), the pitch (g) of the control points with respect to the scanning direction, and the phase difference (h) at which the jaggy shape falls within the allowable range is set. 27. The permanent pattern forming method according to claim 25, wherein the permanent pattern forming method is defined as a selection condition.   The control point sequence pitch (e), the arrangement direction (f), the pitch (g) of the control points with respect to the scanning direction, and the phase difference (h) at which the jaggy shape falls outside the allowable range is set. 27. The permanent pattern forming method according to claim 25, which is defined as a prohibition condition.   Corresponding to the direction of the drawing pattern, at least one of the pitch (e) of the control point sequence, the arrangement direction (f), the pitch (g) of the control point with respect to the scanning direction, and the phase difference (h), and the jaggy pitch 29. The permanent pattern forming method according to claim 25, wherein a correlation with a jaggy shape defined by at least one of the amplitude and the jaggy amplitude is obtained.   For each drawing pattern in a predetermined region, at least one of the pitch (e) of the control point sequence, the arrangement direction (f), the pitch (g) of the control points with respect to the scanning direction, and the phase difference (h), jaggy 28. The permanent pattern forming method according to claim 26, wherein a correlation with a jaggy shape defined by at least one of pitch and jaggy amplitude is obtained.   The permanent pattern formation method according to any one of claims 1 to 30, wherein the light irradiation means can synthesize and irradiate two or more lights.   32. The light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that condenses the laser beams emitted from the plurality of lasers and couples them to the multimode optical fiber. The permanent pattern formation method in any one.   The method for forming a permanent pattern according to claim 32, wherein the wavelength of the laser beam is 395 to 415 nm.   The permanent pattern forming method according to claim 1, wherein after the development, the photosensitive layer is subjected to a curing process.   The permanent pattern formation method according to claim 34, wherein the curing process is at least one of an entire surface exposure process and an entire surface heat treatment performed at 120 to 200 ° C. 36. The permanent pattern forming method according to claim 1, wherein at least one of a protective film, an interlayer insulating film, and a solder resist pattern is formed.