JP2007025394A - Pattern forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pattern forming method by tilting a light modulating means to image for exposure, by which a permanent pattern such as a wiring pattern is efficiently formed with high definition by forming a desired imaged pattern on an exposure face of a photosensitive layer while suppressing production of jaggy without decreasing an exposure speed. <P>SOLUTION: The pattern forming method is characterized in that: at least one of the arrangement pitch (a), tilt angle (b), drawing pitch (c) and phase difference (d) of drawn pixels is set so as to control at least either the jaggy pitch or the jaggy amplitude of jaggy produced by reproducing an image in the pixels formed by imaging units to a specified value or smaller; and the imaging units are controlled by modulation at a predetermined timing based on the pattern information. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a pattern forming method including performing exposure on a photosensitive layer based on pattern information using an exposure head that is relatively moved in a predetermined scanning direction along a surface to be exposed of the photosensitive layer.

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, a pattern forming method that can form a permanent pattern such as a wiring pattern with high definition and efficiency by forming a desired drawing pattern with reduced jaggies on the exposed surface without reducing the exposure speed. Has not been provided yet, and further improvements and development are 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 a desired jaggy is suppressed on the exposed surface of the photosensitive layer without reducing the exposure speed. It is an object of the present invention to provide a pattern forming method capable of forming a permanent pattern such as a wiring pattern with high definition and efficiency by forming a drawing pattern.

Means for solving the problems are as follows. That is,
<1> After laminating the photosensitive layer in the pattern forming material having the photosensitive layer on the support on the substrate to be processed,
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,
The exposure is
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 pattern forming method is characterized in that at least one of the above is set and modulation of the picture element portion is controlled at a predetermined timing based on the pattern information. In the pattern forming method according to <1>, an exposure head provided with a light modulation unit is moved relative to the photosensitive layer in a predetermined scanning direction along the exposed surface of the photosensitive layer, and Exposure is performed based on the pattern information, and (a) the arrangement pitch, (b) the tilt angle, (c) the drawing pitch, and so that at least one of the jaggy pitch and the jaggy amplitude is equal to or less than a predetermined value. (D) Since at least one of the phase differences is set, and each pixel part is modulated and controlled at a predetermined timing according to the pattern information, means for increasing the number of drawing pixels per unit area, etc. It is possible to draw a drawing pattern (image) in which optimum drawing conditions are set and generation of jaggies is suppressed without taking or reducing the exposure speed (drawing speed). As a result, the pattern forming material is exposed with high definition. For example, a high-definition pattern is formed by developing the photosensitive layer thereafter.
<2> The pattern forming method according to <1>, wherein the light modulation unit is a spatial light modulation element.
<3> The pattern forming method according to any one of <1> to <2>, wherein the spatial light modulation element is a digital micromirror device (DMD).

<4> 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 <3>.
<5> The pattern formation according to any one of <1> to <4>, wherein either the entire exposure head or the light modulation unit is rotated by the drawing pixel group rotation unit to change the tilt angle (b). Is the method.
<6> 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). > To <4>.
<7> The timing according to any one of <1> to <4>, wherein the drawing timing changing unit changes the drawing timing of the photosensitive layer on the exposed surface of the photosensitive layer and adjusts the drawing pitch (c). This is a pattern forming method.
<8> The pattern formation according to any one of <1> to <4>, 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). Is the method.
<9> The pattern formation according to any one of <1> to <4>, 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). Is the method.

<10> The pattern forming method according to any one of <1> to <9>, 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.
<11> A plurality of drawing pixel groups each including 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 pattern forming method according to any one of <1> to <10>, wherein at least one of the above is individually set.
<12> An arrangement pitch (a) having a plurality of drawing pixel groups each including a plurality of pixel parts, and an average value of jaggy pitches and jaggy amplitudes generated in each of the pixel parts groups being equal to or less than a predetermined value. The pattern forming method according to any one of <1> to <10>, wherein at least one of tilt angle (b), drawing pitch (c), and phase difference (d) is set.
<13> Any one of <1> to <12> 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 The pattern forming method according to claim 1.
<14> The 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 inclination angle of the drawing pattern with respect to the scanning direction. To <13>.
<15> Arrangement pitch (a), inclination angle (b), and drawing so that any one of jaggy pitch and jaggy amplitude generated in a drawing pattern orthogonal or substantially orthogonal to the scanning direction is equal to or less than a predetermined value. The pattern forming method according to any one of <1> to <14>, wherein at least one of pitch (c) and phase difference (d) is set.

<16> 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 pattern forming method according to any one of <1> to <15>, which is performed by controlling at least one of the method so that jaggy of a drawing pattern is reduced.
<17> 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 Find the correlation with the shape of the jaggy defined by
The pattern forming method according to <16>, wherein any one of (e) to (h) is set or changed based on the correlation.
<18> 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 pattern forming method according to any one of <16> to <17>, wherein the condition is defined as a selection condition.
<19> 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 pattern forming method according to any one of <16> to <17>, wherein the condition is defined as a prohibited condition.
<20> 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 pattern forming method according to any one of <16> to <18>, wherein a correlation with a jaggy shape defined by at least one of a jaggy pitch and a jaggy amplitude is obtained.
<21> The pattern forming method according to <20>, wherein a direction of the drawing pattern is a representative direction of the drawing pattern included in a predetermined region of the drawing pattern.
<22> The pattern forming method according to <21>, 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.
<23> For each drawing pattern in a predetermined area, 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 pattern forming method according to any one of <17> to <18>, 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.
<24> 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) It is a pattern formation method as described in said <23> which sets or changes these.

<25> 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
<17 obtained based on a calculated value obtained from 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). > To <24>.
<26> The pitch of the control point sequence from the preset pattern (e), the arrangement direction (f), the pitch of the control point with respect to the scanning direction (g), 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 pattern forming method according to any one of <17> to <24>, wherein the correlation is obtained by measuring a correlation with the pattern.

<30> The pattern forming method according to any one of <1> to <29>, wherein the light irradiation unit emits laser light emitted from the semiconductor laser element.
<31> The pattern forming method according to <30>, wherein the light irradiation unit can synthesize and irradiate two or more lights.

<32> The pattern forming method according to any one of <1> to <31>, wherein the photosensitive layer is developed after the exposure.
<33> The pattern forming method according to any one of <1> to <32>, wherein a permanent pattern is formed after development.
<34> The pattern forming method according to <33>, wherein the permanent pattern is a wiring pattern, and the formation of the permanent pattern is performed by at least one of an etching process and a plating process.

<35> The pattern forming method according to any one of <1> to <34>, wherein the photosensitive layer includes a binder, a polymerizable compound, and a photopolymerization initiator.
<36> The pattern forming method according to <35>, wherein the binder has an acidic group.
<37> The pattern forming method according to any one of <35> to <36>, wherein the binder is a vinyl copolymer.
<38> The pattern forming method according to any one of <35> to <37>, wherein the binder has an acid value of 70 to 250 mgKOH / g.
<39> The pattern forming method according to any one of <35> to <38>, wherein the polymerizable compound includes a monomer having at least one of a urethane group and an aryl group.
<40> The photopolymerization initiator includes at least one selected from halogenated hydrocarbon derivatives, hexaarylbiimidazoles, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, and metallocenes. The pattern forming method according to any one of <35> to <39>.
<41> The pattern forming method according to any one of <1> to <40>, wherein the photosensitive layer contains 10 to 90% by mass of a binder and 5 to 90% by mass of a polymerizable compound.
<42> The pattern forming method according to any one of <1> to <41>, wherein the photosensitive layer has a thickness of 1 to 100 μm.
<43> The pattern forming method according to any one of <1> to <42>, wherein the support includes a synthetic resin and is transparent.
<44> The pattern forming method according to any one of <1> to <43>, wherein the support has a long shape.
<45> The pattern forming method according to any one of <1> to <44>, wherein the pattern forming material is long and wound in a roll shape.
<46> The pattern forming method according to any one of <1> to <45>, wherein a protective film is formed on the photosensitive layer in the pattern forming material.

  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. By forming a desired drawing pattern in which the occurrence of jaggies is suppressed, a pattern forming method capable of forming a permanent pattern such as a wiring pattern with high definition and efficiency can be provided.

(Pattern formation method)
The pattern forming method of the present invention includes at least an exposure step of exposing the photosensitive layer after laminating the photosensitive layer in the pattern forming material on the substrate to be processed, and includes other steps appropriately selected.

[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 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 is attached with a sheet film F, which is a laminate (hereinafter also referred to as “photosensitive material”) in which the photosensitive layer of the pattern forming material is laminated on a substrate to be processed. The substrate is sucked and held.

  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 pattern forming method of the present invention is to adjust the arrangement of the drawing pixels formed on the sheet film F, thereby suppressing the occurrence of jaggies and making it possible to form an appropriate drawing pattern. .
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.

<Laminated body>
The subject of the exposure is not particularly limited as long as it is the photosensitive layer in the pattern forming material having a photosensitive layer on the support and is laminated on the substrate to be processed. Can be selected as appropriate. As the laminate, for example, a layer other than the photosensitive layer in the pattern forming material may be laminated.

<Pattern forming material>
The pattern forming material is not particularly limited as long as it has a photosensitive layer on a support, and can be appropriately selected according to the purpose.

The photosensitive layer is not particularly limited and can be appropriately selected from known pattern forming materials. For example, the photosensitive layer includes a binder, a polymerizable compound, and a photopolymerization initiator, and other selected appropriately. Those containing components are preferred.
Moreover, there is no restriction | limiting in particular as the number of lamination | stacking of a photosensitive layer, According to the objective, it can select suitably, For example, one layer may be sufficient and two or more layers may be sufficient.

<< 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.

There is no restriction | limiting in particular as said 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, Among these, a carboxyl group is preferable.
Examples of the binder having a carboxyl group include a vinyl copolymer having a carboxyl group, a polyurethane resin, a polyamic acid resin, and a modified epoxy resin. Among these, the solubility in a coating solvent, the solubility in an alkali developer, and the like. A vinyl copolymer having a carboxyl group is preferable from the viewpoint of solubility, suitability for synthesis, ease of adjustment of film properties, and the like. From the viewpoint of developability, a copolymer of at least one of styrene and a styrene derivative is also preferable.

  The vinyl copolymer having a carboxyl group can be obtained by copolymerization of at least (1) a vinyl monomer having a carboxyl group, and (2) a monomer copolymerizable therewith.

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 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 Examples include (meth) acrylate. Among these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like.
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.

  The other copolymerizable monomer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, and maleic acid diesters. , Fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes (eg styrene, styrene derivatives, etc.), (meth) acrylonitrile, complex substituted with vinyl groups Cyclic groups (for example, vinylpyridine, vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinylcaprolactone, 2-acrylamido-2-methylpropanesulfonic acid, monophosphate ( 2-Acryllo Ciethyl ester), phosphoric acid mono (1-methyl-2-acryloyloxyethyl ester), vinyl monomers having a functional group (for example, urethane group, urea group, sulfonamide group, phenol group, imide group) and the like. Among these, the styrenes (styrene and styrene derivatives) are preferable in that a permanent pattern such as a wiring pattern can be formed with high definition and the tent property of the pattern can be improved.

  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-hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meta ) 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, Nylphenoxypolyethylene glycol (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) Examples thereof include 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 styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloro Examples include methylstyrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, α-methylstyrene, and the like.

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

  Examples of the method for synthesizing the vinyl monomer having a 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 compound containing one hydroxyl group. Alternatively, an addition reaction with 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 can be given.

  Examples of the monomer having an isocyanate group include compounds represented by the following structural formulas (1) to (3).

However, in the above structural formula (1) ~ (3), R 1 represents a hydrogen atom or a methyl group.

  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 following structural formulas (4) to (12).

However, in the structural formulas (4) to (12), R ¹ represents a hydrogen atom or a methyl group, and n represents an integer of 1 or more.

  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.

  Examples of the other copolymerizable monomers other than those described above include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, and (meth) acrylic. Preferable examples include 2-ethylhexyl acid, styrene, chlorostyrene, bromostyrene, and hydroxystyrene.

  The said other copolymerizable monomer may be used individually by 1 type, and may use 2 or more types together.

  The vinyl copolymer can be prepared by copolymerizing the corresponding monomers by a known 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.

  The suitable solvent used in the solution polymerization method is not particularly limited and may be appropriately selected depending on the monomer used and the solubility of the copolymer to be produced. For example, methanol, ethanol, propanol, Examples include isopropanol, 1-methoxy-2-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, toluene and the like. These solvents may be used alone or in combination of two or more.

  The radical polymerization initiator is not particularly limited, and examples thereof include 2,2′-azobis (isobutyronitrile) (AIBN) and 2,2′-azobis- (2,4′-dimethylvaleronitrile). Examples thereof include peroxides such as azo compounds and benzoyl peroxide, and persulfates such as potassium persulfate and ammonium persulfate.

There is no restriction | limiting in particular as content rate of the polymeric compound which has a carboxyl group in the said vinyl copolymer, Although it can select suitably according to the objective, For example, 5-50 mol% is preferable, 10-40 mol % Is more preferable, and 15 to 35 mol% is particularly preferable.
If the content is less than 5 mol%, the developability to alkaline water may be insufficient, and if it exceeds 50 mol%, the developer resistance of the cured portion (image portion) may be insufficient.

There is no restriction | limiting in particular as molecular weight of the binder which has the said carboxyl group, Although it can select suitably according to the objective, For example, 2,000-300,000 are preferable as a mass mean molecular weight, 4,000-150 1,000 is more preferable.
When the mass average molecular weight is less than 2,000, the strength of the film tends to be insufficient and stable production may be difficult, and when it exceeds 300,000, developability may be deteriorated.

  The binder which has the said carboxyl group may be used individually by 1 type, and may use 2 or more types together. When two or more binders are used in combination, for example, a combination of two or more binders composed of different copolymer components, two or more binders having different mass average molecular weights, and two or more binders having different dispersities Is mentioned.

  The binder having a carboxyl group may be partially or entirely neutralized with a basic substance. The binder may be used in combination with resins having different structures such as polyester resin, polyamide resin, polyurethane resin, epoxy resin, polyvinyl alcohol, and gelatin.

  Moreover, as the binder, a resin soluble in an alkaline aqueous solution described in Japanese Patent No. 2873889 and the like can be used.

There is no restriction | limiting in particular as content of the said binder in the said photosensitive layer, Although it can select suitably according to the objective, For example, 10-90 mass% is preferable, 20-80 mass% is more preferable, 40- 80% by mass is particularly preferred.
When the content is less than 10% by mass, alkali developability and adhesion to a printed wiring board forming substrate (for example, a copper-clad laminate) may be deteriorated. Stability and strength of the cured film (tent film) may be reduced. The content may be the total content of the binder and the polymer binder used in combination as necessary.

When the binder is a substance having a glass transition temperature (Tg), the glass transition temperature is not particularly limited and may be appropriately selected depending on the intended purpose. For example, tack and edge of the pattern forming material 80 degreeC or more is preferable, 100 degreeC or more is more preferable, and 120 degreeC or more is especially preferable from the viewpoint of at least any one of suppression of fusion and the peelability improvement of the said support body.
When the glass transition temperature is less than 80 ° C., tack and edge fusion of the pattern forming material may increase, or the peelability of the support may deteriorate.

The acid value of the binder is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 70 to 250 (mgKOH / g), more preferably 90 to 200 (mgKOH / g), 100 to 180 (mg KOH / g) is particularly preferable.
When the acid value is less than 70 (mgKOH / g), developability may be insufficient, resolution may be inferior, and permanent patterns such as wiring patterns may not be obtained with high definition. / G), at least one of the developer resistance and adhesion of the pattern deteriorates, and a permanent pattern such as a wiring pattern may not be obtained with high definition.

<< 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 a 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, Diisocyanates such as 3,3′dimethyl-4,4′-diphenyl diisocyanate; polyadducts of the diisocyanate with bifunctional alcohols (in this case, both ends are isocyanate groups); burettes and isocyanurates 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 (13) or the structural formula (14) is preferable, and it is particularly preferable that at least the compound represented by the structural formula (14) is included 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 (13) and (14), 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 the structural formulas (13) and (14), m1 to m3 represent an integer of 1 to 60, preferably 2 to 30, and more preferably 4 to 15.

In the structural formulas (13) and (14), 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 (13) and (14), n represents an integer of 3 to 6, and 3, 4 or 6 is preferable from the viewpoint of feedability of raw materials for synthesizing a polymerizable monomer.

  In the structural formulas (13) and (14), Z 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. m4 represents an integer of 1 to 20. n represents an integer of 3 to 6. A represents an n-valent (trivalent to hexavalent) organic group.

  Examples of A include an n-valent aliphatic group, an n-valent aromatic group, and an alkylene group, an arylene group, an alkenylene group, an alkynylene group, a carbonyl group, an oxygen atom, a sulfur atom, an imino group, and an imino group. Are preferably a combination of a substituted imino group in which the hydrogen atom is substituted with a monovalent hydrocarbon group or a sulfonyl group, an n-valent aliphatic group, an n-valent aromatic group, or an alkylene group or arylene A group in which a group and an oxygen atom are combined is more preferable, and an n-valent aliphatic group, and a group in which an n-valent aliphatic group is combined with an alkylene group and an oxygen atom are particularly preferable.

  As the number of carbon atoms of A, for example, an integer of 1 to 100 is preferable, an integer of 1 to 50 is more preferable, and an integer of 3 to 30 is particularly preferable.

The n-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-valent aliphatic group or aromatic group may further have a substituent. Examples of the substituent include a hydroxyl group, a halogen atom (for example, a fluorine atom, a chlorine atom, a 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 ( Examples thereof include an acetoxy group, a butyryloxy group), an alkoxycarbonyl group (for example, a methoxycarbonyl group, an ethoxycarbonyl group), an aryloxycarbonyl group (for example, a 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 are as follows.

  Examples of the compounds represented by the structural formulas (13) and (14) include compounds represented by the following structural formulas (15) to (34).

  However, in said structural formula (15)-(34), n, n1, n2 and m mean 1-60, l means 1-20, R represents a hydrogen atom or 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, a compound represented by the following structural formula (35) is preferable.

In the structural formula (35), R ⁴ and R ⁵ represent a hydrogen atom or an alkyl group.

In the structural formula (35), X ₅ and X ₆ represent an alkylene oxide group, which may be used alone or in combination of two or more. 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 (35), m5 and m6 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 (35), 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 (35), 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 (for example, 2 to 20 ethoxy groups substituted with one phenolic OH group) 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) acryloyloxydecaetoxy) ) Phenyl) propane, 2,2-bis (4-((meth) acryloyloxypentadecaethoxy) phenyl) propane), 2,2-bis [4-((meth) acryloxypropoxy) phenyl] propane, phenol 2,2-bis (4-((meth) acryloyloxypolypropoxy) phenyl) propane (for example, 2,2-bis (4 -((Meth) acryloyloxydipropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxypenta) Propoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxydecapropoxy) phenyl) Lopan, 2,2-bis (4-((meth) acryloyloxypentadecapropoxy) phenyl) propane, or the like, or a polyether moiety of these compounds contains both a polyethylene oxide skeleton and a polypropylene oxide skeleton in the same molecule Compound having a bisphenol skeleton and a urethane group (for example, a compound described in WO01 / 98832 or a commercially available product, Shin-Nakamura Chemical Co., Ltd., BPE-200, BPE-500, BPE-1000) 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 pattern forming method of the present invention, a polymerizable monomer other than the monomer containing the urethane group and the monomer having an aryl group may be used in combination as long as the characteristics as the pattern forming material are not deteriorated.

  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-oxetanyl) Methoxy) methyl] benzene, etc.), epoxy compounds, oxetanes (for example, compounds described in WO01 / 22165), N-β-hydroxyethyl-β- (methacrylamide) ethyl acrylate, N, N-bis (β -Methacryloxyethyl) A compound having two or more different ethylenically unsaturated double bonds such as 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, Japanese Patent No. 2548016, etc. Is mentioned.

As content of the polymeric compound in the said photosensitive layer, 5-90 mass% is preferable, for example, 15-60 mass% is more preferable, and 20-50 mass% is especially preferable.
If the content is 5% by mass, the strength of the tent film may be reduced, and if it exceeds 90% by mass, edge fusion during storage (exudation failure from the end of the roll) may be deteriorated. .
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 initiator >>
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, and it may be an activator that produces some kind of action with a photoexcited sensitizer and generates active radicals, and initiates cationic polymerization depending on the type of monomer. 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).

  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, and metallocenes. Among these, halogenated hydrocarbons having a triazine skeleton, oxime derivatives, ketone compounds, hexaarylbiimidazoles from the viewpoints of the sensitivity and storage stability of the photosensitive layer and the adhesion between the photosensitive layer and the printed wiring board forming substrate. System compounds are preferred.

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

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

  Examples of the compound described in the British Patent 1388492 include 2-styryl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methylstyryl) -4,6- Bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl)- 4-amino-6-trichloromethyl-1,3,5-triazine and the like can be mentioned.

  Examples of the compounds described in JP-A-53-133428 include 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2 -(4-Ethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl]- 4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5- Examples include triazine and 2- (acenaphtho-5-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

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

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

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

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

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

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

  Examples of the oxime derivative suitably used in the present invention include compounds represented by the following structural formulas (36) to (69).

  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 (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, η5- Cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), JP-A-53-133428, JP-B-57-1819, JP-A-57-6096, and US Pat. Examples thereof include compounds described in the specification of 3615455.

  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 No., JP-A-2002-363207, JP-A-2002-363208, JP-A-2002-363209, etc.), amines (for example, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate) N-butyl acid, 4-dimethylaminobenzoic acid phenethyl, 4-dimethyl 2-phthalimidoethyl tilaminobenzoate, 2-methacryloyloxyethyl 4-dimethylaminobenzoate, pentamethylenebis (4-dimethylaminobenzoate), phenethyl of 3-dimethylaminobenzoic acid, pentamethylene ester, 4-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylaminobenzyl alcohol, ethyl (4-dimethylaminobenzoyl) acetate, 4-piperidinoacetophenone, 4-dimethylaminobenzoin, N, N-dimethyl-4-toluidine, N, N-diethyl-3-phenetidine, tribenzylamine, dibenzylphenylamine, N-methyl-N-phenylbenzylamine, 4-bromo-N, N-dimethylaniline, tridodecylamine, amino Nofluoranes (ODB, ODBII, etc.), crystal violet lactone, leuco crystal violet, etc., acylphosphine oxides (for example, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) ) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, etc.).

  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 Onium Such compounds.

  The said photoinitiator may be used individually by 1 type, and may use 2 or more types together. Examples of the combination of two or more include, for example, a combination of hexaarylbiimidazole and 4-aminoketone described in US Pat. No. 3,549,367, a benzothiazole compound described in Japanese Patent Publication No. 51-48516, and trihalomethyl- Combinations of s-triazine compounds, combinations of aromatic ketone compounds (such as thioxanthone) and hydrogen donors (such as dialkylamino-containing compounds and phenol compounds), combinations of hexaarylbiimidazole and titanocene, and coumarins And combinations of titanocene and phenylglycines.

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

<< Other ingredients >>
Examples of the other components include sensitizers, thermal polymerization inhibitors, plasticizers, color formers, colorants, and the like, and further adhesion promoters to the substrate surface and other auxiliary agents (for example, pigments, Conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, thermal crosslinking agents, surface tension adjusting agents, chain transfer agents, etc.) may be used in combination. By appropriately containing these components, it is possible to adjust properties such as stability, photographic properties, print-out properties, and film properties of the target pattern forming material.

-Sensitizer-
The sensitizer can be appropriately selected by visible light, ultraviolet light, visible light laser, or the like as a light irradiation means to be 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

  The sensitizer is not particularly limited and may be appropriately selected from known sensitizers. For example, known polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, , Fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, indocarbocyanine, thiacarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, Methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squariums (eg, squalium), acridones (eg, acridone, chloroacrine) Don, N-methylacridone, N-butylacridone, N-butyl-chloroacridone, etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl)- 7- (1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3 '-Carbonylbis (5,7-di-n-propoxycoumarin), 3,3'-carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7- Diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin Examples thereof include 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, and others, and JP-A-5-19475, JP-A-7-271028, and JP2002-2002. No. 363206, JP-A No. 2002-363207, JP-A No. 2002-363208, JP-A No. 2002-363209, and the like.

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

As content of the said sensitizer, 0.05-30 mass% is preferable with respect to all the components of the photosensitive resin composition, 0.1-20 mass% is more preferable, 0.2-10 mass% is Particularly preferred.
When the content is less than 0.05% by mass, the sensitivity to active energy rays decreases, the exposure process takes time, and the productivity may decrease. When the content exceeds 30% by mass, the photosensitive layer May precipitate during storage.

-Thermal polymerization inhibitor-
The thermal polymerization inhibitor may be added to prevent thermal polymerization or temporal polymerization of the polymerizable compound in the photosensitive layer.
Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine. , Chloranil, naphthylamine, β-naphthol, 2,6-di-tert-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid 4-toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, 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 of the said photosensitive layer, 0.005-2 mass% is more preferable, 0.01-1 mass% Is particularly preferred.
When the content is less than 0.001% by mass, stability during storage may be reduced, and when it exceeds 5% by mass, sensitivity to active energy rays may be reduced.

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

  As content of the said plasticizer, 0.1-50 mass% is preferable with respect to all the components of the said photosensitive layer, 0.5-40 mass% is more preferable, 1-30 mass% is especially preferable.

-Color former-
The color former may be added to give a visible image (printing function) to the photosensitive layer after exposure.
Examples of the color former include tris (4-dimethylaminophenyl) methane (leuco crystal violet), tris (4-diethylaminophenyl) methane, tris (4-dimethylamino-2-methylphenyl) methane, tris (4- Diethylamino-2-methylphenyl) methane, bis (4-dibutylaminophenyl)-[4- (2-cyanoethyl) methylaminophenyl] methane, bis (4-dimethylaminophenyl) -2-quinolylmethane, tris (4-di Aminotriarylmethanes such as propylaminophenyl) methane; 3,6-bis (dimethylamino) -9-phenylxanthine, 3-amino-6-dimethylamino-2-methyl-9- (2-chlorophenyl) xanthine, etc. Aminoxanthines; 3,6-bis (diethyl Aminothioxanthenes such as mino) -9- (2-ethoxycarbonylphenyl) thioxanthene and 3,6-bis (dimethylamino) thioxanthene; 3,6-bis (diethylamino) -9,10-dihydro-9- Amino-9,10-dihydroacridine such as phenylacridine, 3,6-bis (benzylamino) -9,10-dividro-9-methylacridine; aminophenoxazine such as 3,7-bis (diethylamino) phenoxazine Aminophenothiazines such as 3,7-bis (ethylamino) phenothiazone; aminodihydrophenazines such as 3,7-bis (diethylamino) -5-hexyl-5,10-dihydrophenazine; bis (4-dimethylamino) Aminophenylmethanes such as phenyl) anilinomethane; 4-amino-4 Aminohydrocinnamic acids such as dimethylaminodiphenylamine, 4-amino-α, β-dicyanohydrocinnamic acid methyl ester; hydrazines such as 1- (2-naphthyl) -2-phenylhydrazine; 1,4-bis (Ethylamino) -2,3-dihydroanthraquinones amino-2,3-dihydroanthraquinones; N, N-diethyl-4-phenethylaniline and other phenethylanilines; 10-acetyl-3,7-bis (dimethyl Acyl derivatives of leuco dyes containing basic NH such as amino) phenothiazine; leuco-like that does not have oxidizable hydrogen such as tris (4-diethylamino-2-tolyl) ethoxycarbonylmentane but can oxidize to chromogenic compounds Compound; leucoin digoid pigment; U.S. Pat. Nos. 3,042,515 and 3,043 Organic amines that can be oxidized to a colored form as described in US Pat. No. 5,517 (eg, 4,4′-ethylenediamine, diphenylamine, N, N-dimethylaniline, 4,4′-methylenediamine triphenylamine) N-vinylcarbazole), and among these, triarylmethane compounds such as leucocrystal violet are preferable.

Furthermore, it is generally known that the color former is combined with a halogen compound for the purpose of coloring the leuco body.
Examples of the halogen compound include halogenated hydrocarbons (for example, carbon tetrabromide, iodoform, ethylene bromide, methylene bromide, amyl bromide, isoamyl bromide, amyl iodide, isobutylene bromide, butyl iodide, Diphenylmethyl bromide, hexachloroethane, 1,2-dibromoethane, 1,1,2,2-tetrabromoethane, 1,2-dibromo-1,1,2-trichloroethane, 1,2,3-tribromopropane 1-bromo-4-chlorobutane, 1,2,3,4-tetrabromobutane, tetrachlorocyclopropene, hexachlorocyclopentadiene, dibromocyclohexane, 1,1,1-trichloro-2,2-bis (4 -Chlorophenyl) ethane and the like; halogenated alcohol compounds (for example, 2,2,2-trichloroethanol, Libromoethanol, 1,3-dichloro-2-propanol, 1,1,1-trichloro-2-propanol, di (iodohexamethylene) aminoisopropanol, tribromo-t-butyl alcohol, 2,2,3-trichlorobutane -1,4-diol and the like; halogenated carbonyl compounds (for example, 1,1-dichloroacetone, 1,3-dichloroacetone, hexachloroacetone, hexabromoacetone, 1,1,3,3-tetrachloroacetone, 1, 1,1-trichloroacetone, 3,4-dibromo-2-butanone, 1,4-dichloro-2-butanone-dibromocyclohexanone, etc .; halogenated ether compounds (for example, 2-bromoethyl methyl ether, 2-bromoethyl ethyl) Ether, di (2-bromoethyl) ether, 1,2 Halogenated ester compounds (eg, bromoethyl acetate, ethyl trichloroacetate, trichloroethyl trichloroacetate, homopolymers and copolymers of 2,3-dibromopropyl acrylate, trichloroethyl dibromopropionate, α, β) Halogenated amide compounds (for example, chloroacetamide, bromoacetamide, dichloroacetamide, trichloroacetamide, tribromoacetamide, trichloroethyltrichloroacetamide, 2-bromoisopropionamide, 2,2,2- Trichloropropionamide, N-chlorosuccinimide, N-bromosuccinimide, etc.); compounds having sulfur or phosphorus (for example, tribromomethylphenylsulfone, 4-ni B phenyl tribromomethyl sulfone, 4-chlorophenyl tribromomethyl sulfone, tris (2,3-dibromopropyl) phosphate, etc.), e.g., 2,4-bis (trichloromethyl) 6- phenyltriazole and the like. As the organic halogen compound, a halogen compound having two or more halogen atoms bonded to the same carbon atom is preferable, and a halogen compound having three halogen atoms per carbon atom is more preferable. The said organic halogen compound may be used individually by 1 type, and may use 2 or more types together. Among these, tribromomethylphenyl sulfone and 2,4-bis (trichloromethyl) -6-phenyltriazole are preferable.

  The content of the color former is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, and particularly preferably 0.1 to 5% by mass with respect to all components of the photosensitive layer. Moreover, as content of the said halogen compound, 0.001-5 mass% is preferable with respect to all the components of the said photosensitive layer, and 0.005-1 mass% is more preferable.

-Dye-
In the photosensitive layer, a dye can be used for the purpose of coloring the photosensitive resin composition for improving handleability or imparting storage stability.
Examples of the dye include brilliant green (for example, sulfate thereof), eosin, ethyl violet, erythrosine B, methyl green, crystal violet, basic fuchsin, phenolphthalein, 1,3-diphenyltriazine, alizarin red S, thymolphthalein. , Methyl violet 2B, quinaldine red, rose bengal, metanil-yellow, thymol sulfophthalein, xylenol blue, methyl orange, orange IV, diphenyltylocarbazone, 2,7-dichlorofluorescein, paramethyl red, Congo red, benzo Purpurin 4B, α-naphthyl-red, Nile blue A, phenacetalin, methyl violet, malachite green, parafuxin, oil blue # 603 (Orien Chemical Co., Ltd.), Rhodamine B, Rhodamine 6G, etc. Victoria Pure Blue BOH can be cited, among these cationic dyes (e.g., Malachite Green oxalate, malachite green sulfates) are preferable. The counter anion of the cationic dye may be a residue of an organic acid or an inorganic acid, for example, a residue such as bromic acid, iodic acid, sulfuric acid, phosphoric acid, oxalic acid, methanesulfonic acid, toluenesulfonic acid ( Anion) and the like.

  As content of the said dye, 0.001-10 mass% is preferable with respect to all the components of the said photosensitive layer, 0.01-5 mass% is more preferable, 0.1-2 mass% is especially preferable.

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

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

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

  The photosensitive layer is, for example, J.I. It may contain organic sulfur compounds, peroxides, redox compounds, azo or diazo compounds, photoreducible dyes, organic halogen compounds, etc. as described in Chapter 5 of “Light Sensitive Systems” Good.

  Examples of the organic sulfur compound include di-n-butyl disulfide, dibenzyl disulfide, 2-mercaptobenzthiazole, 2-mercaptobenzoxazole, thiophenol, ethyltrichloromethane sulfenate, and 2-mercaptobenzimidazole. Is mentioned.

  Examples of the peroxide include di-t-butyl peroxide, benzoyl peroxide, and methyl ethyl ketone peroxide.

  The redox compound is a combination of a peroxide and a reducing agent, and examples thereof include ferrous ions and persulfate ions, ferric ions and peroxides.

  Examples of the azo and diazo compounds include α, α′-azobisiributyronitrile, 2-azobis-2-methylbutyronitrile, and diazonium such as 4-aminodiphenylamine.

  Examples of the photoreducible dye include rose bengal, erythrosine, eosin, acriflavine, lipoflavin, and thionine.

-Surfactant-
In order to improve the surface unevenness generated when the pattern forming material of the present invention is produced, a known surfactant can be added.
The surfactant can be appropriately selected from, for example, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and a fluorine-containing surfactant.

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

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

  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, 1-100 micrometers is preferable, 2-50 micrometers is more preferable, and 4-30 micrometers is especially preferable.

[Manufacture of pattern forming materials]
The pattern forming material can be manufactured, for example, as follows.
First, the above-mentioned various materials are dissolved, emulsified or dispersed in water or a solvent to prepare a photosensitive resin composition solution.

  There is no restriction | limiting in particular as a solvent of the said photosensitive resin composition solution, According to the objective, it can select suitably, For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, n- Alcohols such as hexanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone; 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, monochlorobenze Halogenated hydrocarbons such as tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxy-2-propanol and the like; dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane and the like It is done. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.

Next, the said photosensitive resin composition solution is apply | coated on a support body, a photosensitive layer is formed by making it dry, and a pattern formation material can be manufactured.
The method for applying the photosensitive resin composition solution is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a spray method, a roll coating method, a spin coating method, a slit coating method, and an extrusion coating. Various coating methods such as a coating method, a curtain coating method, a die coating method, a gravure coating method, a wire bar coating method, and a knife coating method may be 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.

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

  The support is preferably made of synthetic resin and transparent, for example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester, poly ( (Meth) acrylic acid ester copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoro Various plastic films, such as ethylene, a cellulose film, and a nylon film, are mentioned, Among these, polyethylene terephthalate is particularly preferable. These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular as thickness of the said support body, Although it can select suitably according to the objective, For example, 2-150 micrometers is preferable, 5-100 micrometers is more preferable, and 8-50 micrometers is especially preferable.

  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.

<< Protective film >>
The pattern forming material may form a protective film on the photosensitive layer.
Examples of the protective film include those used for the support, paper, paper laminated with polyethylene, polypropylene, and the like. Among these, polyethylene film and polypropylene film are preferable.
There is no restriction | limiting in particular as thickness of the said protective film, Although it can select suitably according to the objective, For example, 5-100 micrometers is preferable, 8-50 micrometers is more preferable, 10-30 micrometers is especially preferable.
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.

  It is preferable that the pattern forming material is wound around a cylindrical core, wound into a long roll, and stored. There is no restriction | limiting in particular as length of the said elongate pattern formation material, 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. The roll-shaped pattern forming material may be slit into a sheet shape. From the viewpoint of protecting the end face and preventing edge fusion during storage, it is preferable to install a separator (especially moisture-proof and desiccant-containing) on the end face, and use a low moisture-permeable material for packaging. Things are preferable.

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

<Substrate to be treated>
There is no restriction | limiting in particular as said to-be-processed base | substrate (henceforth a "base | substrate"), From the well-known material, what has high surface smoothness and what has an uneven surface can be selected suitably. However, a plate-like substrate (substrate) is preferable. Specifically, a known printed wiring board forming substrate (for example, a copper-clad laminate), a glass plate (for example, a soda glass plate), or a synthetic resin film , Paper, metal plate and the like.

  The substrate can be used by forming a laminate on which the photosensitive layer of the pattern forming material is laminated on the substrate. That is, by exposing the photosensitive layer of the pattern forming material in the laminate, the exposed region can be cured, and a pattern can be formed by a development process described later.

  The pattern forming material can be widely used for pattern formation of printed wiring boards, color filters, column materials, rib materials, spacers, partition members and other display members, holograms, micromachines, proofs, and the like. It can be suitably used for the forming method.

[Other processes]
There is no restriction | limiting in particular as said other process, Although selecting suitably from the process in well-known pattern formation is mentioned, For example, a image development process, an etching process, a plating process, etc. are mentioned. These may be used alone or in combination of two or more.
The developing step is a step of forming a pattern by exposing the photosensitive layer by the exposing step, curing the exposed region of the photosensitive layer, and then developing the uncured region 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.

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

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

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

The etching step can be performed by a method appropriately selected from known etching methods.
There is no restriction | limiting in particular as an etching liquid used for the said etching process, Although it can select suitably according to the objective, For example, when the said metal layer is formed with copper, a cupric chloride solution, Examples thereof include a ferric chloride solution, an alkali etching solution, and a hydrogen peroxide-based etching solution. Among these, a ferric chloride solution is preferable from the viewpoint of an etching factor.
A permanent pattern can be formed on the surface of the substrate by removing the pattern after performing the etching process in the etching step.
There is no restriction | limiting in particular as said permanent pattern, According to the objective, it can select suitably, For example, a wiring pattern etc. are mentioned suitably.

The plating step can be performed by an appropriately selected method selected from known plating processes.
Examples of the plating treatment include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high flow solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfamate, and hard gold plating. And gold plating such as soft gold plating.
A permanent pattern can be formed on the surface of the substrate by removing the pattern after the plating process in the plating process, and further removing unnecessary portions by an etching process or the like as necessary.

  The pattern forming method of the present invention reduces the variation in resolution and density of the pattern formed on the exposed surface of the pattern forming material, and suppresses distortion of the image to be formed, thereby suppressing the pattern to be formed in high definition. In addition, since it can be formed efficiently, it can be suitably used for forming various patterns that require high-definition exposure, and particularly suitable for forming high-definition wiring patterns. it can.

[Method of manufacturing printed wiring board]
The pattern forming method of the present invention can be suitably used for the production of a printed wiring board, particularly for the production of a printed wiring board having a hole portion such as a through hole or a via hole. Hereinafter, the manufacturing method of the printed wiring board using the pattern formation method of this invention is demonstrated.

  In particular, as a method of manufacturing a printed wiring board having a hole portion such as a through hole or a via hole, (1) the pattern forming material is placed on the printed wiring board forming substrate having the hole portion as the base, and the photosensitive layer is (2) The photosensitive layer is cured by irradiating the wiring pattern formation region and the hole portion formation region with light from the opposite side of the laminate to the substrate. (3) The support in the pattern forming material is removed from the laminate, and (4) the photosensitive layer in the laminate is developed to form a pattern by removing uncured portions in the laminate. can do.

  The removal of the support in (3) may be performed between (1) and (2) instead of between (2) and (4).

  Thereafter, in order to obtain a printed wiring board, a method of etching or plating the printed wiring board forming substrate using the formed pattern (for example, a known subtractive method or additive method (for example, a semi-additive method) And the full additive method)). Among these, in order to form a printed wiring board by industrially advantageous tenting, the subtractive method is preferable. After the treatment, the cured resin remaining on the printed wiring board forming substrate is peeled off. In the case of the semi-additive method, a desired printed wiring board can be manufactured by further etching the copper thin film portion after peeling. it can. A multilayer printed wiring board can also be manufactured in the same manner as the printed wiring board manufacturing method.

  Next, the manufacturing method of the printed wiring board which has a through hole using the said pattern formation material is further demonstrated.

  First, a printed wiring board forming substrate having through holes and having a surface covered with a metal plating layer is prepared. As the printed wiring board forming substrate, for example, a copper-clad laminate substrate and a substrate in which a copper plating layer is formed on an insulating base material such as glass-epoxy, or an interlayer insulating film is laminated on these substrates, and a copper plating layer is formed. A formed substrate (laminated substrate) can be used.

Next, when a protective film is provided on the pattern forming material, the protective film is peeled off so that the photosensitive layer in the pattern forming material is in contact with the surface of the printed wiring board forming substrate. Is used for pressure bonding (lamination process). Thereby, the laminated body which has the said board | substrate for printed wiring board formation and the said laminated body in this order is obtained.
There is no restriction | limiting in particular as lamination | stacking temperature of the said pattern formation material, For example, room temperature (15-30 degreeC) or under heating (30-180 degreeC) is mentioned, Among these, under heating (60-140 degreeC) ) Is preferred.
There is no restriction | limiting in particular as roll pressure of the said crimping | compression-bonding roll, For example, 0.1-1 Mpa is preferable.
There is no restriction | limiting in particular as the speed | rate of the said crimping | compression-bonding, and 1-3 m / min is preferable.
The printed wiring board forming substrate may be preheated or laminated under reduced pressure.

  In addition to the method of forming the laminate by laminating the photosensitive layer in the pattern forming material on the printed wiring board forming substrate, a photosensitive resin composition for producing the photosensitive layer of the pattern forming material is used. A method may be used in which a physical solution is directly applied to the surface of the printed wiring board forming substrate and dried.

  Next, the photosensitive layer is cured by irradiating light from the surface of the laminate opposite to the substrate. At this time, exposure may be performed after peeling the support as necessary (for example, when the light transmittance of the support is insufficient).

  At this point, if the support has not yet been peeled off, the support is peeled off from the laminate (support peeling step).

  Next, the uncured region of the photosensitive layer on the printed wiring board forming substrate is dissolved and removed with an appropriate developer to form a pattern of the cured layer for forming the wiring pattern and the cured layer for protecting the metal layer of the through hole. And a metal layer is exposed on the surface of the printed wiring board forming substrate (developing step).

  Moreover, you may perform the process which further accelerates | stimulates the hardening reaction of a hardening part by post-heat processing or post-exposure processing as needed after image development. The development may be a wet development method as described above or a dry development method.

  Next, the metal layer exposed on the surface of the printed wiring board forming substrate is dissolved and removed with an etching solution (etching step). Since the opening of the through hole is covered with a cured resin composition (tent film), the metal plating of the through hole is predetermined without etching liquid entering the through hole and corroding the metal plating in the through hole. It will remain in the shape. Thus, a wiring pattern is formed on the printed wiring board forming substrate.

  There is no restriction | limiting in particular as said etching liquid, Although it can select suitably according to the objective, For example, when the said metal layer is formed with copper, a cupric chloride solution, a ferric chloride solution , Alkaline etching solutions, hydrogen peroxide-based etching solutions, and the like. Among these, ferric chloride solutions are preferable from the viewpoint of etching factors.

Next, it removes from the said board | substrate for printed wiring board formation by making the said hardened layer into a peeling piece with strong alkaline aqueous solution etc. (hardened | cured material removal process).
There is no restriction | limiting in particular as a base component in the said strong alkali aqueous solution, For example, sodium hydroxide, potassium hydroxide, etc. are mentioned.
As pH of the said strong alkali aqueous solution, about 12-14 are preferable, for example, and about 13-14 are more preferable.
There is no restriction | limiting in particular as said strong alkali aqueous solution, For example, 1-10 mass% sodium hydroxide aqueous solution or potassium hydroxide aqueous solution etc. are mentioned.

The printed wiring board may be a multilayer printed wiring board.
The pattern forming material may be used not only for the above etching process but also for a plating process. Examples of the plating method include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high flow solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfamate, and hard gold plating. And gold plating such as soft gold plating.

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

Example 1
-Production of pattern forming material-
A photosensitive resin composition solution having the following composition was applied to a polyethylene terephthalate film having a thickness of 20 μm as the support and dried to form a photosensitive layer having a thickness of 15 μm, thereby producing the pattern forming material.

[Composition of photosensitive resin composition solution]
Methacrylic acid / methyl methacrylate / styrene copolymer (copolymer composition (mass ratio):
29/19/52, mass average molecular weight: 60,000, acid value 189) 11.8 parts by mass • 5.6 parts by mass of polymerizable monomer represented by the following structural formula (70) • hexamethylene diisocyanate and pentaethylene oxide mono 1/2 mole ratio adduct of methacrylate 5.0 parts by mass, dodecapropylene glycol diacrylate 0.56 parts by mass, N-methylacridone 0.11 parts by mass, 2,2-bis (o-chlorophenyl) -4 , 4 ', 5,5'-tetraphenylbiimidazole 2.17 parts by mass, 0.23 parts by mass of 2-mercaptobenzimidazole, 0.02 parts by mass of malachite green oxalate, 0.26 parts by mass of leuco crystal violet 40 parts by mass of methyl ethyl ketone
・ 20 parts by mass of 1-methoxy-2-propanol

However, m + n represents 10 in Structural Formula (70). Structural formula (70) is an example of a compound represented by the structural formula (35).

A 20 μm thick polyethylene film was laminated as the protective film on the photosensitive layer of the pattern forming material.
Next, a photosensitive layer of the pattern forming material is peeled off from the surface of a copper-clad laminate (no through-hole, copper thickness 12 μm) whose surface is polished, washed and dried as the substrate. In contact with the copper-clad laminate using a laminator (MODEL8B-720-PH, manufactured by Taisei Laminator Co., Ltd.), the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) Body) was laminated in this order.
The pressure bonding conditions were a pressure roll temperature of 105 ° C., a pressure roll pressure of 0.3 MPa, and a laminating speed of 1 m / min.

  The photosensitive layer of the pattern forming material in the prepared laminate was exposed by the method using the following exposure apparatus, and the resolution, the presence / absence of jaggy, and the edge roughness were evaluated by the following methods. The results are shown in Table 1.

<Resolution>
(1) Measuring method of shortest development time The support is peeled off from the laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. is sprayed on the entire surface of the photosensitive layer on the copper clad laminate at a pressure of 0.15 MPa. The time required from the start of spraying of the aqueous sodium carbonate solution until the photosensitive layer on the copper clad laminate was dissolved and removed was measured, and this was taken as the shortest development time.
As a result, the shortest development time was 10 seconds.

(2) Measurement of sensitivity With respect to the photosensitive layer of the pattern forming material in the prepared laminate, from the support side, an exposure apparatus described below is used at intervals of 0.1 mJ / cm ² to 2 ^1/2 times. Light with different light energy amounts up to 100 mJ / cm ² was irradiated to cure a part of the photosensitive layer. After standing at room temperature for 10 minutes, the support was peeled off from the laminate, and a 1% by mass aqueous sodium carbonate solution at 30 ° C. was applied to the entire surface of the photosensitive layer on the copper clad laminate at a spray pressure of 0.15 MPa. Spraying was performed twice as long as the shortest development time determined in (1) above, the uncured area was dissolved and removed, and the thickness of the remaining cured area was measured. Subsequently, the relationship between the light irradiation amount and the thickness of the cured layer was plotted to obtain a sensitivity curve. From the sensitivity curve, the amount of light energy when the thickness of the cured region was 15 μm, which was the same as that of the photosensitive layer before exposure, was determined as the amount of light energy necessary for curing the photosensitive layer.
As a result, the amount of light energy necessary for curing the photosensitive layer was 3.5 mJ / cm ² .

<< 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.

(3) Measurement of resolution The laminate was prepared by the same method and conditions as the evaluation method for the shortest development time in (1), and allowed to stand at room temperature (23 ° C., 55% RH) for 10 minutes. From the obtained polyethylene terephthalate film (support) of the laminate, the exposure apparatus is used to expose each line width in increments of 1 μm from 10 μm to 50 μm in line width / space = 1/1. The exposure amount at this time is the amount of light energy necessary for curing the photosensitive layer of the pattern forming material measured in (2). After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) is peeled off from the laminate. A 1 mass% sodium carbonate aqueous solution at 30 ° C. is sprayed over the entire surface of the photosensitive layer on the copper clad laminate at a spray pressure of 0.15 MPa for twice the shortest development time determined in (1) above, and the uncured area is Dissolve and remove. The surface of the copper-clad laminate with a cured resin pattern obtained in this way is observed with an optical microscope, and the cured resin pattern line is free of irregularities such as lumps and twists, and the minimum line width that allows space formation is measured. This is the resolution. The smaller the numerical value, the better the resolution.

<With or without jaggy>
Using the exposure apparatus, the laminate is exposed to light so that a horizontal line pattern perpendicular to the scanning direction of the exposure head is formed, and a part of the photosensitive layer is measured for the resolution. A pattern was formed in the same manner as in (3).
Among the formed patterns, arbitrary five portions of a line having a line width of 30 μm were observed using a laser microscope (VK-9500, manufactured by Keyence Corporation; objective lens 50 ×) to evaluate the presence or absence of jaggy. 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>
Using the exposure apparatus, the laminate is exposed to light so that a horizontal line pattern perpendicular to the scanning direction of the exposure head is formed, and a part of the photosensitive layer is measured for the resolution. A pattern was formed in the same manner as in (3). Among the obtained patterns, any five points of a line having a line width of 30 μm were observed using a laser microscope (VK-9500, manufactured by Keyence Corporation; objective lens 50 ×), and among the edge positions in the field of view Then, the difference between the most swollen portion (mountain peak portion) and the most constricted portion (valley bottom portion) was obtained as an absolute value, and an average value of five observed positions was calculated, and this was defined as edge roughness. The edge roughness is preferably as the value is small because it exhibits good performance.

(Example 2)
In Example 1, the pattern was formed in the same manner as in Example 1 except that exposure was performed by setting the respective parameters in the exposure apparatus in the same manner as the values shown in FIG. 18, and the resolution, presence / absence of jaggy, And edge roughness was 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, except that the ½ molar ratio adduct of hexamethylene diisocyanate and pentaethylene oxide monomethacrylate in the photosensitive resin composition solution was replaced with a compound represented by the following structural formula (71), Example 1 In the same manner as above, a pattern forming material and a laminate were prepared, a pattern was formed, and resolution, presence / absence of jaggies, and edge roughness were evaluated. The results are shown in Table 1.
The shortest development time was 10 seconds, and the amount of light energy necessary for curing the photosensitive layer was 3.5 mJ / cm ² . In addition, the compound represented by the structural formula (71) is an example of the compound represented by the structural formula (24).

Example 4
In Example 1, Example 1 except that the 1/2 mole ratio adduct of hexamethylene diisocyanate and pentaethylene oxide monomethacrylate in the photosensitive resin composition solution was replaced with the compound represented by the following structural formula (72). Similarly, a pattern forming material and a laminate were prepared, a pattern was formed, and resolution, presence / absence of jaggies, and edge roughness were evaluated. The results are shown in Table 1.
The shortest development time was 10 seconds, and the amount of light energy necessary for curing the photosensitive layer was 3.5 mJ / cm ² . Further, the compound represented by the structural formula (72) is an example of the compound represented by the structural formula (22).

(Example 5)
In Example 1, methacrylic acid / methyl methacrylate / styrene copolymer (copolymer composition (mass ratio): 29/19/52, mass average molecular weight: 60,000, acid value 189) was converted to methyl methacrylate / styrene / Except having replaced with the benzyl methacrylate / methacrylic acid copolymer (Copolymer composition (mass ratio): 8/30/37/25, mass average molecular weight: 60,000, acid value 163), it carried out similarly to Example 1, and. Then, a pattern forming material and a laminate were prepared, a pattern was formed, and resolution, presence / absence of jaggies, and edge roughness were evaluated. The results are shown in Table 1.
The shortest development time was 10 seconds, and the amount of light energy required to cure the photosensitive layer was 4 mJ / cm ² .

(Comparative Example 1)
In Example 1, except that the exposure was performed without setting and changing each parameter, the pattern forming material and the laminate were prepared and the pattern was formed in the same manner as in Example 1, and the resolution and jaggies were adjusted. Existence and edge roughness were evaluated. The results are shown in Table 1.
The shortest development time was 10 seconds, and the amount of light energy required to cure the photosensitive layer was 3.5 mJ / cm ² .

  From the results shown in Table 1, the patterns of Examples 1 to 5 formed by the pattern forming method of the present invention are suppressed in jaggies, edge roughness is small, and high definition as compared with the pattern of Comparative Example 1. I understood. Moreover, in the exposure process which forms the pattern of Examples 1-5, since the desired pattern was able to be formed, without reducing an exposure speed, the pattern formation method of this invention can form a high-definition pattern efficiently. I understood.

  The pattern formation method of the present invention forms a desired drawing pattern with reduced jaggies on the exposed surface without reducing the exposure speed, thereby making it possible to efficiently and efficiently create a permanent pattern such as a wiring pattern. Since it can be formed, it can be suitably used for forming various patterns that require high-definition exposure, and particularly suitable for forming high-definition wiring patterns.

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 L Laser beam

Claims (34)

After laminating the photosensitive layer in the pattern forming material having the photosensitive layer on the support on the substrate to be processed,
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,
The exposure is
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 pattern forming method is performed by setting at least one of the above and performing modulation control on the pixel part at a predetermined timing based on the pattern information.   The pattern forming method according to claim 1, wherein the light modulation means is a spatial light modulation element.   The pattern formation method according to claim 1, wherein the spatial light modulation element is a digital micromirror device (DMD).   4. 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 pattern forming method according to any one of the above.   5. The pattern forming method according to claim 1, wherein the tilt angle (b) is changed by rotating either the entire exposure head or the light modulating unit by the drawing pixel group rotating unit.   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 pattern formation method in any one.   5. The pattern forming method according to claim 1, wherein the drawing timing changing means changes the drawing timing of the photosensitive element on the exposed surface of the photosensitive layer and adjusts the drawing pitch (c).   5. The pattern forming method according to claim 1, wherein the moving speed changing means 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).   5. The pattern forming method according to claim 1, wherein the phase difference changing unit changes the phase difference of the timing of modulation control of the adjacent pixel parts to change the phase difference (d).   The pattern formation according to any one of claims 1 to 9, 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. Method.   The arrangement pitch (a), the inclination angle (b), the drawing pitch (c), or the phase difference (d) is set according to the inclination angle with respect to the scanning direction of the drawing pattern. A pattern forming method according to any one of the above.   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 at least one of the phase difference (d) is set. 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 pattern forming method according to claim 1, wherein the 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 pattern forming method according to claim 13, 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. The pattern forming method according to claim 13, which 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. The pattern forming method according to claim 13, which is defined as a prohibited 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 The pattern forming method according to claim 13, wherein a correlation with a jaggy shape defined by at least one of the jaggy 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 The pattern forming method according to claim 14, wherein a correlation with a jaggy shape defined by at least one of pitch and jaggy amplitude is obtained.   The pattern forming method according to claim 1, wherein the light irradiation means can synthesize and irradiate two or more lights.   The pattern forming method according to claim 1, wherein the photosensitive layer is developed after the exposure.   21. The pattern forming method according to claim 20, wherein a permanent pattern is formed after the development.   The pattern formation method according to claim 21, wherein the permanent pattern is a wiring pattern, and the formation of the permanent pattern is performed by at least one of an etching process and a plating process.   The pattern formation method according to any one of claims 1 to 22, wherein the photosensitive layer contains a binder, a polymerizable compound, and a photopolymerization initiator.   The pattern forming method according to claim 23, wherein the binder has an acidic group.   The pattern forming method according to any one of claims 23 to 24, wherein the binder is a vinyl copolymer.   The pattern formation method according to any one of claims 23 to 25, wherein an acid value of the binder is 70 to 250 mgKOH / g.   27. The pattern forming method according to claim 23, wherein the polymerizable compound contains a monomer having at least one of a urethane group and an aryl group.   The photopolymerization initiator includes at least one selected from halogenated hydrocarbon derivatives, hexaarylbiimidazoles, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, and metallocenes. 28. The pattern forming method according to any one of the items   The pattern formation method according to any one of claims 1 to 28, wherein the photosensitive layer contains 10 to 90% by mass of a binder and 5 to 90% by mass of a polymerizable compound.   30. The pattern forming method according to claim 1, wherein the photosensitive layer has a thickness of 1 to 100 [mu] m.   The pattern forming method according to claim 1, wherein the support includes a synthetic resin and is transparent.   32. The pattern forming method according to claim 1, wherein the support has an elongated shape.   The pattern forming method according to any one of claims 1 to 32, wherein the pattern forming material is elongated and wound into a roll. The pattern forming method according to claim 1, wherein a protective film is formed on the photosensitive layer in the pattern forming material.