JP2007017721A - Pattern forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pattern forming method by which a permanent pattern such as a wiring pattern can be efficiently formed with high definition by enhancing exposure performance without incurring cost increase of apparatus or lowering of exposure speed. <P>SOLUTION: Exposure is performed in such a way that light modulated by a light modulating means forms an image only in a nearly rectangular region of an imaging means including a central part, and that the nearly rectangular exposure region where the image is formed on a surface of a photosensitive layer to be exposed is inclined so that the angle between a minor side direction of the region and a waving direction of the photosensitive layer is made smaller than the angle between a major side direction of the region and the waving direction of the photosensitive layer, accordingly light selectively illuminated onto the region with good optical performance forms an image and the focal position is adjusted to a proper position. As a result, exposure of the photosensitive layer is performed with high definition, and by developing the exposed photosensitive layer, a high-definition pattern is formed. The imaging means comprises a projector lens produced such that a peripheral region is distorted and the distortion of a region including a central part is made less. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a pattern forming method in which light modulated by light modulation means such as a spatial light modulation element is imaged on an exposed surface of a photosensitive layer through an imaging optical system to expose the photosensitive layer.

Conventionally, incident light is modulated on the basis of pattern information (image signal), and light modulation means such as a spatial light modulation means for forming a two-dimensional pattern is provided, and the formed two-dimensional pattern is projected onto a photosensitive material. An exposure apparatus that performs exposure is known.
As the spatial light modulation means, there is known a digital micromirror device (hereinafter referred to as “DMD”) in which a plurality of micromirrors whose tilt angles can be changed are arranged two-dimensionally (for example, 1024 × 756 pixels). (For example, refer to Patent Document 1).

  An exposure apparatus provided with a DMD as a light modulation means includes an image forming means having a projection lens for forming an image of a two-dimensional pattern, and the projection lens is inclined at a predetermined angle among the micromirrors of the DMD. Only the light reflected by the micromirror is imaged on the photosensitive material. That is, exposure using this exposure apparatus is performed such that each pixel forming a two-dimensional pattern projected onto the photosensitive material corresponds to each micromirror.

In a conventional exposure apparatus, a two-dimensional pattern is imaged on a photosensitive material using almost the entire area of the projection lens constituting the imaging means. In this case, it is necessary to suppress curvature of field, astigmatism, distortion, etc. in the entire area of the projection lens, improve telecentricity, and provide high lens optical performance.
However, the manufacture of projection lenses with high lens optical performance over almost the entire surface area requires improvements in component accuracy, better component selection, etc., and large-diameter projections with high lens optical performance over the entire surface region. Since it is difficult to manufacture a lens, a large area cannot be exposed, leading to a reduction in exposure speed.
Therefore, when pattern formation is performed using an exposure apparatus having a projection lens having high lens optical performance in almost the entire surface area, there is a problem that the efficiency of pattern formation is reduced and the cost is increased.

  On the other hand, if the lens optical performance of the projection lens is poor, the beam position accuracy deteriorates.For example, it is necessary to equalize the influence of the deterioration of the position accuracy by a method such as increasing the number of multiple exposures. When pattern formation is performed using an exposure apparatus having an inferior projection lens, there are problems such as a decrease in pattern formation efficiency due to a decrease in exposure speed and a decrease in resolution.

  Therefore, there is still provided a pattern forming method capable of forming a permanent pattern such as a wiring pattern with high definition and efficiency by improving the exposure performance without increasing the cost of the apparatus or reducing the exposure speed. However, the present situation is that further improvement and development is desired.

JP 2001-305663 A

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, the present invention provides a pattern forming method capable of forming a permanent pattern such as a wiring pattern with high definition and efficiency by improving exposure performance without increasing the cost of the apparatus and reducing the exposure speed. The purpose is to provide.

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,
The light from the light irradiating means is received and modulated based on the pattern information. The light modulating means modulates the light from the light irradiating means, and the light modulated by the light modulating means And performing exposure by forming an image on an exposed surface of the photosensitive layer through an adjusting means,
In the exposure, light modulated by the light modulation means is imaged only in a substantially rectangular region including the center of the imaging means,
The substantially rectangular exposure region imaged on the exposed surface of the photosensitive layer has an angle formed by the short side direction and the waviness direction of the photosensitive layer, the long side direction and the waviness direction of the photosensitive layer. The pattern forming method is characterized in that it is performed so as to be smaller than an angle formed by. In the pattern forming method according to <1>, the light modulated by the light modulation unit is imaged on the exposed surface of the photosensitive layer via an imaging unit and a focus adjustment unit. The exposure is performed by. In the exposure, the light modulated by the light modulation means is imaged only in a substantially rectangular area including the central portion of the imaging means, and is formed on the exposed surface of the photosensitive layer. Since the exposure area of the shape is oriented so that the angle formed by the short side direction and the waviness direction of the photosensitive layer is smaller than the angle formed by the long side direction and the waviness direction of the photosensitive layer. The light selectively irradiated on the region with good optical performance is imaged, and the focal position is adjusted to an appropriate position. As a result, the photosensitive layer is exposed with high definition. For example, a high-definition pattern is formed by developing the photosensitive layer thereafter.
<2> The pattern forming method according to <1>, wherein the imaging unit includes a projection lens manufactured by giving distortion to a peripheral region and reducing distortion in a region including a central portion. In the pattern forming method according to <2>, since the imaging unit includes a projection lens manufactured by giving distortion to a peripheral region and reducing distortion of a region including a central portion, By selectively irradiating light onto a region with good optical performance of the projection lens, the optical system of the focus adjustment means can be reduced in size compared with the case where the entire region of the projection lens is used, and modulated. It is possible to adjust the focal position with high accuracy while keeping the focal position of light stable. As a result, the apparatus cost is reduced, and the exposure of the photosensitive layer is performed with extremely high definition.
<3> From <1> to <2 above, wherein the imaging means forms an image of light modulated by the light modulation means in a substantially rectangular region having a long side length of twice or more of the short side length. > The pattern forming method described in the above.

<4> The focus adjusting unit has a wedge-shaped prism pair formed so that the thickness of the light modulated by the light modulating unit in the optical axis direction changes.
From <1>, the focus is adjusted when the light modulated by the light modulation means is imaged on the exposed surface of the photosensitive layer by moving each wedge-shaped prism constituting the wedge-shaped prism pair. <3> The pattern forming method according to any one of the above.
<5> The focus adjusting means includes an optical member constituting the imaging optical system and a piezo element,
Any one of <1> to <3>, wherein the optical member is moved by the piezo element to adjust a focal point when the light modulated by the light modulation unit is imaged on the exposed surface of the photosensitive layer. The pattern forming method according to claim 1. In the pattern forming method according to <5>, the focal point when the light modulated by the light modulation unit is imaged on the exposed surface of the photosensitive layer by moving the optical member by the piezo element. Therefore, a minute displacement in a direction perpendicular to the focal direction can be suppressed, and the focal position can be adjusted with extremely high accuracy while maintaining high beam positional accuracy.

  <6> The imaging means is either a lens that can rotate around the optical axis with respect to the optical axis of the light modulated by the light modulating means, or a lens that can move in a direction perpendicular to the optical axis. The pattern forming method according to any one of <1> to <5>, which is configured.

<7> The pattern forming method according to any one of <1> to <6>, wherein the light modulation means includes n (where n is a natural number of 1 or more) two-dimensionally arranged pixel parts. It is.
<8> The pattern forming method according to any one of <1> to <7>, wherein the light modulation unit is a spatial light modulation element.

<9> The pattern forming method according to any one of <1> to <8>, wherein the light irradiation unit emits laser light emitted from the semiconductor laser element.
<10> The above-mentioned <9>, wherein the light irradiation means is a bundle-shaped fiber light source in which a plurality of optical fibers that enter laser light emitted from a semiconductor laser element from one end and emit incident laser light from the other end are bundled > The pattern forming method according to <1>. In the pattern forming method according to <10>, by using a high-brightness light source having a large light amount per area as a fiber bundle-shaped light source, the etendue can be reduced while improving the optical power. Therefore, the numerical aperture on the light modulation means side can be reduced, and the depth of focus of the imaging optical system can be increased. As a result, the focus shift of the image formed on the exposed surface of the photosensitive layer is suppressed.
<11> The pattern forming method according to any one of <8> to <10>, wherein the light irradiation unit can synthesize and irradiate two or more lights. In the pattern forming material according to <11>, since the light irradiation unit can synthesize and irradiate two or more lights, exposure is performed with exposure light having a deep focal depth. As a result, the exposure of the photosensitive layer is performed with extremely high definition. For example, after that, the photosensitive layer is developed to form an extremely fine pattern.
<12> The light irradiation means collimates and condenses the laser beams emitted from the plurality of lasers, the multimode optical fiber, and the plurality of lasers, and converges them on the incident end face of the multimode optical fiber. It is a pattern formation method in any one of said <8> to <11> which has a light source condensing optical system. In the pattern forming method according to <12>, the light irradiation unit can condense the laser beams emitted from the plurality of lasers by the light source collective optical system and be coupled to the multimode optical fiber. By doing so, exposure is performed with exposure light having a deep focal depth. As a result, the exposure of the photosensitive layer is performed with extremely high definition. For example, after that, the photosensitive layer is developed to form an extremely fine pattern.

<13> The pattern forming method according to any one of <1> to <12>, wherein the photosensitive layer is developed after the exposure.
<14> The pattern forming method according to any one of <1> to <13>, wherein a permanent pattern is formed after development.
<15> The pattern forming method according to <14>, 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.

<16> The pattern forming method according to any one of <1> to <15>, wherein the photosensitive layer includes a binder, a polymerizable compound, and a photopolymerization initiator.
<17> The pattern forming method according to <16>, wherein the binder has an acidic group.
<18> The pattern forming method according to any one of <16> to <17>, wherein the binder is a vinyl copolymer.
<19> The pattern forming method according to any one of <16> to <18>, wherein the binder has an acid value of 70 to 250 mgKOH / g.
<20> The pattern forming method according to any one of <16> to <19>, wherein the polymerizable compound includes a monomer having at least one of a urethane group and an aryl group.
<21> 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 <16> to <20>.
<22> The pattern forming method according to any one of <1> to <21>, wherein the photosensitive layer contains 10 to 90% by mass of a binder and 5 to 90% by mass of a polymerizable compound.
<23> The pattern forming method according to any one of <1> to <22>, wherein the photosensitive layer has a thickness of 1 to 100 μm.

<24> The pattern forming method according to any one of <1> to <23>, wherein the support includes a synthetic resin and is transparent.
<25> The pattern forming method according to any one of <1> to <24>, wherein the support has a long shape.
<26> The pattern forming method according to any one of <1> to <25>, wherein the pattern forming material is long and wound in a roll shape.
<27> The pattern forming method according to any one of <1> to <26>, wherein a protective film is formed on the photosensitive layer in the pattern forming material.

  According to the present invention, conventional problems can be solved, and the permanent pattern such as a wiring pattern can be defined with high definition by improving the exposure performance without increasing the cost of the apparatus or reducing the exposure speed. It is possible to provide a pattern forming method that can be efficiently formed.

(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 exposure step, the light from the light irradiation unit is modulated by the light modulation unit that receives light from the light irradiation unit and modulates the light based on the pattern information, and the light modulated by the light modulation unit , And at least including performing exposure by forming an image on an exposed surface of the photosensitive layer via an imaging unit and a focus adjusting unit,
In the exposure, light modulated by the light modulation means is imaged only in a substantially rectangular region including the center of the imaging means,
The substantially rectangular exposure region imaged on the exposed surface of the photosensitive layer has an angle formed by the short side direction and the waviness direction of the photosensitive layer, the long side direction and the waviness direction of the photosensitive layer. It is directed to be smaller than the angle formed by.

  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 a schematic external view of an exposure apparatus 10 relating to the exposure process of the pattern forming method of the present invention. The exposure apparatus 10 is a flat plate for adsorbing and holding a sheet-like laminate (hereinafter referred to as “photosensitive material 12”) formed by laminating the photosensitive layer of the pattern forming material on a substrate to be processed. The moving stage 14 is provided. Two guides 20 extending along the stage moving direction are installed on the upper surface of the thick plate-shaped installation table 18 supported by the four legs 16. The stage 14 is arranged so that the longitudinal direction thereof faces the stage moving direction, and is supported by the guide 20 so as to be reciprocally movable. Further, the exposure apparatus 10 includes a stage driving device (not shown) that drives the stage 14 along the guide 20.

  A U-shaped gate 22 is installed at the center of the installation table 18 so as to straddle the movement path of the stage 14. Each end of the U-shaped gate 22 is fixed to both side surfaces of the installation base 18. A scanner 24 is installed on one side of the gate 22 and a plurality of sensors 26 for detecting the front and rear ends of the photosensitive material 12 are installed on the other side. The scanner 24 and the sensor 26 are respectively fixed to the gate 22 and installed above the moving path of the stage 14. The scanner 24 and the sensor 26 are electrically connected to a controller (not shown), and operation control is performed by the controller.

  The stage 14 is provided with an exposure surface measurement sensor 28 for detecting the amount of laser light emitted from the scanner 24 to the exposed surface of the photosensitive material 12 when the exposure by the scanner 24 is started. The exposure surface measurement sensor 28 is extended in the direction orthogonal to the stage moving direction at the end of the exposure surface side of the installation surface of the photosensitive material 12 in the stage 14.

FIG. 2 is a schematic external view of the scanner 24.
As shown in FIG. 2, the scanner 24 includes, for example, ten exposure heads 30 arranged in a substantially matrix of 2 rows and 5 columns.
Each exposure head 30 includes a DMD that is a spatial modulation element as the light modulation unit, and projects a two-dimensional pattern formed by the DMD onto the photosensitive material 12.
An exposure area 32 indicates a projection area when a two-dimensional pattern emitted from each exposure head is projected onto the photosensitive material 12. As the stage 14 moves, a strip-shaped exposed region 34 by the exposure head 30 is formed on the photosensitive material 12.

<< Exposure head >>
3 is a conceptual diagram for explaining a schematic configuration of the exposure head 30, and FIG. 7 is a diagram for explaining optical elements constituting the exposure head 30 along the optical path of laser light propagating through the exposure head 30. As shown in FIG. It is.
The exposure head 30 includes a light source unit 60, a DMD irradiation optical system 70, a DMD 80, an imaging optical system 50 as the imaging means, and a wedge-shaped prism pair 54 as the focusing means. Configured.

  As shown in FIG. 4, the light source unit 60 includes a plurality of (for example, 14) LD modules 40, and one end of a first multimode optical fiber 41 is coupled to each LD module 40. A second multimode optical fiber 68 having a smaller cladding diameter than that of the first multimode optical fiber is coupled to the other end of the first multimode optical fiber 41.

  As shown in detail in FIG. 5, seven ends of the second multimode optical fiber 68 opposite to the first multimode optical fiber 41 are arranged along the direction orthogonal to the scanning direction, and they are arranged in two rows. Thus, the laser emitting unit 66 is configured.

  As shown in FIG. 5, the laser emitting portion 66 constituted by the end portion of the second multimode optical fiber 64 is sandwiched and fixed between two support plates 65 having a flat surface. Moreover, it is desirable that a transparent protective plate such as glass is disposed on the light emitting end face of the second multimode optical fiber 64 for protection. The light exit end face of the second multimode optical fiber 68 is likely to collect dust and easily deteriorate due to its high light density, but by arranging the protective plate as described above, it prevents dust from adhering to the end face, Moreover, deterioration can be delayed.

  The LD module 40 is composed of a combined laser light source shown in FIG. The combined laser light source includes a plurality of (for example, seven) semiconductor laser elements LD chips LD1, LD2, LD3, LD4, LD5, LD6, and LD7 arranged and fixed on the heat block 400, and LD chips LD1 to LD1. The collimator lenses 401, 402, 403, 404, 405, 406 and 407 provided corresponding to each of the LDs 7, one condensing lens 90, and one first multimode optical fiber 41 are configured. Yes. The number of semiconductor laser elements is not limited to seven, and other numbers may be adopted. Further, instead of the seven collimator lenses 401 to 407 as described above, a collimator lens array in which these lenses are integrated may be used.

  The LD chips LD1 to LD7 are chip-like lateral multimode or single mode GaN-based semiconductor laser elements, all oscillation wavelengths are common (for example, about 405 [nm]), and maximum outputs are all common (for example, 100 [mW] for a multimode laser and 30 [mW] for a single mode laser. If the wavelength range is 350 [nm] to 450 [nm], semiconductor laser elements having oscillation wavelengths other than the above 405 [nm] may be used as the LD chips LD1 to LD7.

In this way, each laser beam emitted from the plurality of LD chips LD1 to LD7 is incident on one first multi-mode optical fiber 41 and multiplexed, and further, the amount of light per area is large as a fiber bundle-shaped light source. By using a high brightness light source, the Etendue can be reduced while improving the optical power.
Accordingly, the spatial light modulation by the spatial light modulator only in the region including the central portion of the imaging means can suppress the illumination NA value even if the illumination area for the illuminated object (light modulator) is reduced. it can. Thereby, even when the imaging optical system is disposed on the downstream side of the illumination object, the depth of focus of the imaging optical system can be increased, and the focus deviation of the formed exposure image can be suppressed. The effect is obtained.
The detailed relationship between etendue and depth of focus is described in Japanese Patent Laid-Open No. 2005-018013.

  In the above description, the case where the light emitted from the light irradiation unit is configured by combining the plurality of LD chips LD1 to LD7 has been described. However, the semiconductor laser element and one end of the optical fiber are connected to each other without combining. The optical fiber having a smaller cladding diameter than that of the optical fiber may be coupled to the other end of the optical fiber. In this case, it is preferable to use a multimode high-power laser as the semiconductor laser element, and a high-intensity light source can be realized by using such a high-power laser.

As shown in FIG. 7, the DMD irradiation optical system 70 includes a collimator lens 71, micro fly's eye lenses 72 and 73, a field lens 74, a mirror 75, and a prism 76.
The collimator lens 71 is a lens for making the plurality of laser beams emitted from the laser beam emitting unit 61 into a substantially parallel beam.
The micro fly's eye lenses 72 and 73 are formed by arranging a large number of microlens cells vertically and horizontally, and are lenses for uniformizing the light quantity distribution of the laser light applied to the DMD 80. The laser light that has passed through the micro fly's eye lenses 72 and 73 passes through the field lens 74, is reflected by the mirror 75, and enters the prism 76.
The prism 76 is a TIR prism (total reflection prism) and totally reflects the laser light reflected by the mirror 75 toward the DMD 80. Details of the DMD 80 will be described later.
The DMD irradiation optical system 70 may include a rod integrator as a means for uniformizing the light amount distribution.

-Imaging means-
-Imaging optics-
The image forming optical system 50 is an image forming means for forming an image on the photosensitive material 12 and projecting a two-dimensional pattern formed by modulating the laser light from the light irradiation means by the DMD 80. As shown in FIG. 7, the imaging optical system 50 includes a first projection lens 51, a second projection lens 52, a microlens array 55, and an aperture array 59.
The two-dimensional pattern formed by being reflected by each micromirror that constitutes the DMD 80 is transmitted through the first projection lens 51 and enlarged and imaged by a predetermined magnification (for example, three times). Here, the light beam La transmitted through the first projection lens 51 is individually condensed by each microlens 55 a of the microlens array 55 disposed in the vicinity of the image forming position by the first projection lens 51. The individually condensed light beams pass through the aperture 59a to form an image. The two-dimensional pattern imaged through the microlens array 55 and the aperture array 59 is transmitted through the second projection lens 52 and further magnified to a predetermined magnification (for example, 1.67 times), and the wedge-shaped prism pair 54. And is imaged on the photosensitive material 12. Finally, the two-dimensional pattern formed by the DMD 80 is magnified at a magnification (for example, 3 × 1.67 × = 5 times) obtained by multiplying the magnifications of the first projection lens 51 and the second projection lens 52, respectively. And projected onto the photosensitive material 12.
Note that the imaging optical system 50 is not necessarily provided with the second projection lens 52.

8A and 8B are plan views showing a projection lens 300 that constitutes the first projection lens 51 and the second projection lens 52. FIG.
In order to improve the exposure performance of the exposure apparatus, a projection lens having high lens optical performance (suppression of field curvature, astigmatism, distortion, etc., high telecentricity) is required. However, an attempt to improve lens optical performance over the entire area of the projection lens leads to an increase in the cost of the lens, which makes it difficult to manufacture a large-diameter lens. On the other hand, in recent years, it has been clarified that it is possible to manufacture a projection lens by intentionally distorting a predetermined region in order to improve lens optical performance in an arbitrary region of the projection lens.

  Therefore, for example, by giving distortion to the peripheral portion of the projection lens and reducing the distortion of the central portion, the lens optical performance in the region including the central portion of the projection lens is improved, and further, in the region including the central portion. The two-dimensional pattern formed by the DMD 80 can be transmitted and imaged. Specifically, as shown in FIG. 8A, a region 320 that is a peripheral region of the projection lens 300 is given a characteristic that the field curvature is large, and the region 330 has a large distortion, and the region including the central portion of the projection lens 300 correspondingly. The lens optical performance can be improved by reducing the distortion of the lens.

However, as shown in FIG. 8A, for example, when the two-dimensional pattern formed by the DMD 80 is irradiated and transmitted through the region 310 of the projection lens 300, a part of the two-dimensional pattern has a large curvature of field and distortion. Since the region including the characteristic is transmitted, the two-dimensional pattern needs to be irradiated to the region 340 having good lens optical performance in the projection lens 300.
Therefore, in order to select a region 340 with good lens optical performance of the projection lens 300 and irradiate a two-dimensional pattern, for example, projection is performed in the direction of arrow A shown in FIG. 8B around the optical axis of the light of the two-dimensional pattern. It is preferable to rotate the lens 300. By this rotation, the region 340 with good lens optical performance can coincide with the region 310 irradiated with the two-dimensional pattern, and the two-dimensional pattern can be transmitted through the region 340 with good lens optical performance.
In this way, by forming an image by transmitting a two-dimensional pattern in a region having good lens optical performance, the image quality when the two-dimensional pattern is projected onto the photosensitive material 12 can be improved.

  In addition, when a large-diameter projection lens is used, it is difficult to manufacture if an attempt is made to obtain sufficient lens optical performance in the entire area of the projection lens, but the lens can be placed in an arbitrary area such as a peripheral area of the large-diameter projection lens. By imparting distortion and reducing lens distortion in the region including the central portion, high lens optical performance can be obtained. By using such a large-diameter projection lens, the exposure area can be expanded and the exposure speed can be increased.

  In order to form an image of the light reflected from the DMD 80 in a partial region including the central portion of the projection lens, a two-dimensional pattern formed by the DMD 80 is like a region 310 shown in FIGS. 8A and 8B. It is desirable that the pattern has a substantially rectangular pattern in which the length of the long side is twice or more than the length of the short side. This will be described in detail in the description of DMD described later.

In order to selectively irradiate the two-dimensional pattern on the region 340 with good lens optical performance of the projection lens 300, the imaging optical system 50 is preferably configured to be rotatable about the optical axis of the light of the two-dimensional pattern. .
9 is a schematic side sectional view of a lens barrel 400 including the imaging optical system 50, and a lower diagram in FIG. 9 is a schematic plan view of the lens barrel 400 viewed from the direction of arrow B in the upper diagram. .
The lens barrel 400 has a flange-like flange 410 on the side surface. A screw through-hole 412 is formed in the flange 410 for each α [°]. A female screw hole (not shown) is also formed in the bracket 420 corresponding to the screw through hole 412 for each α [°], and a screw (not shown) is inserted into the screw through hole 412 of the flange 410 so that the bracket 420 The flange 410 and the bracket 420 are fixed by screwing into the corresponding female screw holes. With this structure, the lens barrel 400 can be fixed at an arbitrary angular position by rotating by α [°] around the optical axes of the first projection lens 51 and the second projection lens 52. Further, when fixing the flange 410 and the bracket 420 with screws, the screws may be inserted into all the screw through holes 412 of the screw through holes 412 and screwed into the corresponding female screw holes of the bracket 420, For example, a screw may be inserted into two screw through holes 412 located on the diagonal line and screwed into corresponding female screw holes of the bracket 420.

  When the lens barrel 400 is rotated, both the first projection lens 51 and the second projection lens 52 are rotated. Then, the flange 410 and the bracket 420 are fixed at the rotational position showing the best exposure performance while measuring the exposure performance such as the focus and image quality (resolution) of the two-dimensional pattern projected on the photosensitive material 12.

  In this way, the first projection lens 51 and the second projection lens 52 are rotated by rotating the lens barrel 400 around the optical axis of the light of the two-dimensional pattern, and the first projection lens 51 and the second projection lens 52 are rotated. In the constituting projection lens, the region with good lens optical performance can be matched with the irradiation region of the two-dimensional pattern formed by the light modulation means.

In addition, you may comprise the projection lens which comprises the 1st projection lens 51 and the 2nd projection lens 52 so that it can rotate independently for every projection lens.
The lens barrel 400 may be configured to be movable in the direction perpendicular to the optical axis of the two-dimensional pattern, and the first projection lens 51 and the second projection lens 52 may be arranged in the direction perpendicular to the optical axis of the two-dimensional pattern. You may comprise so that each projection lens to comprise can be moved independently.

-Light modulation means-
The light modulation means is not particularly limited as long as it can form two-dimensional pattern light based on pattern information (image signal), and can be appropriately selected according to the purpose. , N is a natural number greater than or equal to 1), and those having a picture element portion arranged in a two-dimensional shape. Among these, a spatial light modulator is preferable, and specifically, DMD is preferable.
Hereinafter, the case where DMD is used as the light modulation means will be described.

A schematic perspective view of the DMD 80 is shown in FIG. The DMD 80 is a spatial light modulation unit that spatially modulates light incident from the DMD irradiation optical system 70 based on pattern information (image signal) to form a two-dimensional pattern.
The DMD 80 has micromirrors 81 as pixel parts (pixels) arranged in a number of n (for example, 1024 × 757) two-dimensionally. Further, the DMD 80 is connected to a controller (not shown) having a data processing unit and a mirror drive control unit.
The data processing unit generates a control signal for controlling the driving of each micromirror 81 arranged in the DMD 80 based on the pattern information (image signal).
The mirror drive control unit controls the angle of the reflection surface of each micromirror 81 of the DMD 80 based on the control signal generated by the data processing unit.
The light reflected by the micromirror 81 inclined at a predetermined angle out of the light irradiated on the DMD 81 by the data processing unit and the mirror drive control unit being inclined at a predetermined angle by the reflection surface of the micromirror 81. Becomes a two-dimensional pattern and enters the imaging optical system 50.

  By the way, as described above, the first projection lens 51 and the second projection lens 52 give distortion to the peripheral portions of the projection lenses constituting the first projection lens 51 and the second projection lens 52, and reduce distortion at the center. Thus, the lens optical performance of the region including the central portion of the projection lens is improved, and the two-dimensional pattern is transmitted through the region including the central portion to form an image. In order to image the two-dimensional pattern in a part of the region including the central portion of the projection lens in this way, the two-dimensional pattern formed by the DMD 80 has a long side length like a region 310 shown in FIG. 8B. Is a substantially rectangular pattern that is at least twice as long as the length of the short side. In order to form such a substantially rectangular two-dimensional pattern, a part of the micromirrors 81 of the DMD 80 is driven and controlled so that the length of the side is two times longer than the length of the short side. Is preferably formed.

The substantially rectangular two-dimensional pattern will be described in detail with reference to FIGS. 11A and 11B.
In the DMD 80, for example, a micromirror 81 having 1024 pixels in the main scanning direction at the time of exposure, that is, the row direction, and 756 pixels in the sub-scanning direction at the time of exposure, that is, the column direction, is two-dimensionally arranged. A 1024 × 240 pixel two-dimensional pattern is formed by using some of the micromirrors 81 (for example, 240 pixels) among the 756 pixels arranged in the column direction.
Here, among the micromirrors 81 arranged in the column direction, the number of micromirrors 81 to be used is desirably about 1/2 to 1/5 of the number of micromirrors 81 arranged in the row direction.

Further, for all the micromirrors constituting the DMD 80, a micromirror that occupies the center of the DMD 80 may be used as in the region 80C shown in FIG. 11A, and the DMD 80 may be used as in the region 80T shown in FIG. 11B. You may use the micromirror which occupies the edge part vicinity of.
Furthermore, when a defect occurs in the micromirror being used, the micromirror region to be used may be appropriately changed depending on the situation, for example, by using a micromirror region in which no defect has occurred. .

In this way, in the micromirror 81 constituting the DMD 80, by using a part of the micromirrors 81 arranged in the column direction, the length of the long side is substantially rectangular, which is longer than the length of the short side. A two-dimensional pattern can be formed, and it becomes easy to irradiate only the region having high lens optical performance of the projection lens constituting the first projection lens 51 and the second projection lens 52.
In addition, since the data processing speed of the DMD 80 is proportional to the number of micromirrors 81 to be controlled (number of pixels), the data processing speed can be reduced by using some of the micromirrors 81 arranged in the column direction. The exposure speed can be increased.
Further, by reducing the two-dimensional pattern formed by the DMD 80, the microlens array 55 in which the microlenses corresponding to the micromirrors 81 are arranged in an array can be reduced in size. Since the microlens array is an expensive optical member, the cost of the exposure apparatus can be reduced.

  Note that, in order to form a substantially rectangular two-dimensional pattern in which the length of the long side is longer than the length of the short side, a part of the micromirrors 81 arranged in the column direction in the DMD 80 is used. However, a DMD in which the number of micromirrors in the long side direction is twice or more than the number of micromirrors in the short side direction may be used in advance.

-Focus adjustment means-
--Wedge type prism pair--
FIG. 12 is a side view showing the configuration of the wedge-shaped prism pair 54, and FIG. 13 is a schematic perspective view showing the wedge-shaped prism pair 54.
The wedge-shaped prism pair 54 is a focus adjusting means for adjusting the focal point when the two-dimensional pattern is imaged by changing the optical path length of the light of the two-dimensional pattern.
The wedge prism pair 54 includes wedge prisms 540A and 540B, base prism holders 541A and 541B for fixing the wedge prisms 540A and 540B, and a slide base 542A and a slide base disposed at both ends of the base prism holder 541A. The slide unit 545 includes a slider 542 </ b> B that moves on 542 </ b> A, and a drive unit 546 that moves the slide unit 545. For the wedge-shaped prism pair 54, as shown in FIG. 13, a parallel flat plate made of a transparent material such as glass or acrylic is cut along a plane Hk that is inclined with respect to the parallel planes H11 and H22 of the parallel plate. A pair of wedge prisms A and B obtained by doing so can be used as the wedge prisms 540A and 540B.

  The wedge-shaped prisms 540A and 540B shown in FIG. 12 are fixed to the base prism holders 541A and 541B via an air layer 550 having a width t (for example, 10 [um]). In addition, linear sliding is possible by a combination of the slide base 542A and the slider 542B, and the drive unit 546 moves the positions of the wedge prisms 540A and 540B to each other so that the width t of the air layer 550 does not change. Move relatively in the direction (direction of arrow u in the figure). By the movement of the slide portion 545, the thickness of the wedge-shaped prism pair 54 in the optical axis direction (the thickness obtained by removing the width t of the air layer 550 from the thickness of the plane parallel plate) is changed. That is, the optical path length of the light forming the two-dimensional pattern is changed by the wedge-shaped prism pair 54.

As described above, by arranging the wedge-shaped prism pair 54 between the second projection lens 52 and the photosensitive material 12, the optical path length of the light of the two-dimensional pattern can be easily adjusted.
Therefore, as compared with the prior art, the focus adjustment when the two-dimensional pattern imaged by the second projection lens 52 is imaged on the photosensitive material 12 can be performed easily and in a short time.

  As shown in FIG. 14, the wedge-shaped prism pair 54 is disposed between the microlens array 55 and the second projection lens 52, thereby changing the optical path length of the light of the two-dimensional pattern. The focus of the pattern may be adjusted.

  Although the case where the wedge-shaped prism pair 54 is used as the focus adjusting means has been described, the focus adjusting means is not limited to this, and the position of the projection lens constituting the imaging optical system 50 is not changed. Any focus adjustment means with high beam position accuracy for performing focus adjustment may be used.

--Focus adjustment means using optical member and piezo element constituting imaging optical system--
As the focus adjusting means, for example, as shown in FIGS. 15A, 15B, 16A, and 16B, a microlens array 55 that is an optical member constituting an imaging optical system is focused using a piezo element 600. Focus adjustment may be performed by moving in the direction (the direction of arrow X in the figure).
By using the piezo element 600, it is possible to perform minute movement in the focus direction while suppressing displacement in the direction perpendicular to the focus direction of the microlens array 55, so that focus adjustment is performed while maintaining stable beam position accuracy. It can be carried out.

<Exposure method>
An exposure method using the above-described exposure apparatus 10 will be described.
FIG. 17A is a perspective view schematically showing the positional relationship between the photosensitive material 12 and the DMD 80. As shown in FIG. 2, the exposure apparatus 10 has been described as including ten exposure heads 30 having DMDs 80. However, in FIGS. 17A and 17B, the exposure apparatus 10 is simplified and shown and described with a focus on only one DMD 80. To do.

As shown in FIG. 17A, when the micromirror 81 occupying the region 80T is used for all the micromirrors 81 of the DMD 80, the photosensitive material 12 is placed with the short side direction of the region 80T facing the waviness direction of the photosensitive material 12. It is preferable to expose the photosensitive material 12 while moving it in the waviness direction (with the short side direction of the region 80T directed to the moving direction of the photosensitive material 12). That is, the exposure is performed so that the substantially rectangular exposure region formed by the region 80T and imaged on the exposed surface of the photosensitive material is substantially parallel to the short side direction and the waviness direction of the photosensitive layer. Preferably it is done.
In FIG. 17A, an exposure area 81 is an exposure area when a two-dimensional pattern is formed using all the micromirrors 81 of the DMD 80, and the exposure area 81T is 2 using the micromirror 81 that occupies the region 80T in the DMD81. This is an exposure area when a dimensional pattern is formed.

FIG. 17B is an enlarged side view showing a portion surrounded by a broken-line frame P in FIG. 17A. As shown in FIG. 17B, when a two-dimensional pattern is formed using all the micromirrors 81 of the DMD 80, the maximum depth difference with respect to the photosensitive material 12 in the exposure area 81 (the maximum of the surface of the photosensitive material 12 in the exposure area 81). The difference in height is d2.
On the other hand, when the micromirror 81 occupying the region 80T is used in the DMD 80, the maximum depth difference with respect to the photosensitive material 12 in the exposure area 81T is d1.
As shown in FIG. 17B, d1 <d2, and the smaller the depth difference, the smaller the degree of undulation of the photosensitive material 12 in the two-dimensional pattern than when the depth difference is large. Therefore, the focal position of the two-dimensional pattern can be adjusted to a more appropriate position.

  Further, when the exposure of one frame is completed and the photosensitive material 12 is moved by moving the stage 14 in the scanning direction, the position of the exposure area 81T is changed, and the degree of undulation of the photosensitive material 12 in the exposure area 81T is changed. Therefore, although the focal position also changes, the focal position is adjusted immediately by the focus adjustment by the wedge prism pair 54. Therefore, exposure having a long focal depth corresponding to the undulation of the photosensitive material 12 can be performed.

Thus, in the micromirrors 81 constituting the DMD 80, when a part of the micromirrors 81 arranged in the column direction is used to form a substantially rectangular two-dimensional pattern, the two-dimensional pattern By performing exposure with the short side direction facing the waviness direction of the photosensitive material 12, the degree of waviness of the photosensitive material 12 in the exposure area 81T can be reduced.
For this reason, the focal position of the two-dimensional pattern can be adjusted to an appropriate position, and the focal depth of the exposure apparatus 10 can be apparently increased as compared with the conventional exposure apparatus, and as a result, the exposure image quality can be improved. High-definition pattern exposure is performed.

As shown in FIG. 2, the exposure head 30 is actually attached to the scanner 24 so that the pixel row direction of the DMD 80 forms a predetermined set inclination angle with the scanning direction. Therefore, the exposure area 32 (corresponding to the exposure area 81T in FIG. 17) by each exposure head 30 is a rectangular area inclined with respect to the scanning direction.
In order to minimize the degree of influence due to the waviness of the photosensitive material 12 in the exposure area 81T, it is ideal that the short side direction of the exposure area 81T and the waviness direction of the photosensitive material 12 are perfectly matched. Even if the area 81T has the predetermined set inclination angle, if the short side direction of the exposure area 81T is oriented in the waviness direction of the photosensitive material 12 from the long side direction, that is, on the exposed surface of the photosensitive material. The angle formed by the short side direction and the waviness direction of the photosensitive layer in the substantially rectangular exposure region to be imaged is smaller than the angle formed by the long side direction and the waviness direction of the photosensitive layer. It only has to be suitable.

  As described above, the exposure in the pattern forming method of the present invention imparts distortion to the peripheral area of the projection lens constituting the imaging means, and reduces the distortion of the area including the central part, thereby reducing the central part. By using an exposure apparatus equipped with an imaging means that improves the optical performance of the included area, the spatially light-modulated light is imaged by imaging the spatially light-modulated light in the area with good optical performance. The image quality when projected on the material can be improved.

  Also, by giving lens distortion to any area such as the peripheral area of the projection lens and reducing the lens distortion in the area including the central part, even a large aperture projection lens can have high lens optical performance. This increases the exposure area and increases the exposure speed.

  The image forming means in the exposure apparatus can rotate around the optical axis of the spatial light modulated exposure light, or can move in the direction perpendicular to the optical axis, thereby forming a projection constituting the image forming means. The region with good optical performance of the lens is selectively irradiated with light subjected to spatial light modulation.

  Further, by using only a region having a good lens performance including the central portion by giving lens distortion to the peripheral region or the like of the projection lens, the optical system of the focus adjusting means can be used compared to the case where the entire region of the projection lens is used. As a result, high-definition exposure is performed by an exposure apparatus that realizes a highly accurate stable holding and moving mechanism. Further, the focal position is adjusted with high accuracy while keeping the optical position of the spatially modulated exposure light stable.

  In addition, when concentrating spatially light-modulated light on a small spot through the microlens array, the expensive microlens array can be reduced in size, so that a microlens array with higher pitch accuracy and lower cost can be employed. . Furthermore, by using a piezo element as the focus adjustment means, it is possible to suppress a minute displacement in a direction perpendicular to the focus direction, and to adjust the focus position with high accuracy while maintaining high beam position accuracy.

  Also, each laser beam emitted from a plurality of semiconductor laser elements is incident on one optical fiber and combined, and a high-intensity light irradiation means with a large light amount per area is used as a fiber bundle light source. Thus, the Etendue can be reduced while improving the optical power, and the numerical aperture (NA) on the DMD side can be reduced. Thus, the numerical aperture on the DMD side can be reduced even when spatial light modulation is performed by the spatial light modulation means only in a substantially rectangular area including the central portion of the imaging means, and the imaging optical system Even when is disposed downstream of the illumination object, the depth of focus of the imaging optical system can be increased, and the focus deviation of the imaged exposure image is suppressed.

  Further, when the imaging means forms an image of the exposure light that has been spatially light-modulated in a substantially rectangular region whose long side is twice or more the length of the short side and projects it onto the photosensitive material, The angle between the short side direction and the waviness direction of the photosensitive layer of the substantially rectangular exposure region imaged on the exposed surface of the photosensitive material is the long side direction and the waviness direction of the photosensitive layer. By performing exposure so that the angle is smaller than the angle formed, the degree of swell of the photosensitive material in the projection area of the projected spatial light modulated exposure light can be reduced, and the focus of the spatial light modulated light is reduced. The position can be adjusted. Thereby, the depth of focus can be apparently increased as compared with the conventional exposure apparatus, and the resolution (exposure image quality) can be improved.

<Laminated body>
The subject of the exposure is not particularly limited as long as it is a photosensitive layer in a laminate formed by laminating the photosensitive layer in a pattern forming material having a photosensitive layer on a support on a 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 sensitivity and storage stability of the photosensitive layer, and 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 using the following exposure apparatus, and the resolution and etching property were evaluated by the following methods. The results are shown in Table 1.
In the exposure, the angle formed between the short side direction and the waviness direction of the photosensitive layer of the substantially rectangular exposure region imaged on the exposed surface of the photosensitive layer is the long side direction and the photosensitive layer. The angle was made smaller than the angle formed by the waviness direction of the layer.

<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 >>
An exposure apparatus 10 whose outline of the appearance is shown in FIG. 1 was used. The configuration of the exposure head of the exposure apparatus is as shown in FIG. 7. Specifically, the combined laser light source shown in FIGS. 4 to 6 as the light irradiation means and the light modulation means as shown in FIG. In the DMD shown in the figure, as shown in FIG. 11, only 1024 × 240 columns of 756 micromirror rows in which 1024 micromirrors are arranged in the main scanning direction are arranged in the sub-scanning direction. It has a DMD controlled to be driven, an imaging optical system composed of the projection lens shown in FIGS. 8A and 8B and the lens barrel shown in FIG. 9, and a wedge-shaped prism pair shown in FIGS. An exposure apparatus provided with an exposure head.

The lens barrel 400 shown in FIG. 9 is rotated to measure the exposure performance such as the focus and image quality of the two-dimensional pattern projected on the exposed surface of the photosensitive layer, and at the rotational position showing the best exposure performance. The lens barrel flange 410 and the bracket 420 were fixed, and the direction of the projection lens was fixed.
Furthermore, when the exposure of one frame is completed and the photosensitive layer (laminated body) moves by moving the stage in the scanning direction, the degree of waviness of the photosensitive layer in the exposure area changes. Focus adjustment was performed.

(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.

<Etching property>
Using the laminated body having the pattern formed in the measurement of the resolution, an iron chloride etchant (ferric chloride-containing etching solution, 40 ° Baume, liquid temperature 40) is formed on the exposed copper-clad laminate in the laminated body. C.) was sprayed at 0.25 MPa for 36 seconds to dissolve and remove the exposed copper layer not covered with the hardened layer. Next, the formed pattern was removed by spraying a 2% by mass sodium hydroxide aqueous solution, and a printed wiring board having a copper layer wiring pattern as the permanent pattern on the surface was produced. The wiring pattern on the printed wiring board was observed with an optical microscope, and the minimum line width of the wiring pattern was measured. A smaller minimum line width means that a finer wiring pattern can be obtained and the etching property is better. The results are shown in Table 1.

(Example 2)
In Example 1, except that the exposure apparatus was changed to that described below, a pattern was formed in the same manner as in Example 1, and the resolution and etching property were evaluated. The results are shown in Table 1.

<< Exposure equipment >>
In the exposure apparatus used in Example 1, instead of the wedge-shaped prism pair, an exposure apparatus provided with a focus adjusting unit composed of a combination of a piezo element and a microlens array shown in FIGS. The focus was adjusted by performing a minute movement in the focus direction while suppressing displacement of the microlens array in the direction perpendicular to the focus direction by the piezo element.

(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 and etching property 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 and etching property 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 and etching property 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, a pattern forming material and a laminate are used in the same manner as in Example 1 except that an exposure head having a configuration not including (or not operating) a wedge-shaped prism pair as a focus adjusting unit is used. Were prepared, patterns were formed, and resolution and etching properties were evaluated. The results are shown in Table 1.
The amount of light energy required for curing the photosensitive layer was 3.5 mJ / cm ² .

(Comparative Example 2)
In the exposure apparatus of Example 1, a pattern forming material and a laminate are prepared in the same manner as in Example 1 except that image formation by the projection lens is performed on the entire surface of the projection lens, and a pattern is formed. The etching property was evaluated. The results are shown in Table 1.
The amount of light energy required for curing the photosensitive layer was 3.5 mJ / cm ² .

(Comparative Example 3)
In Example 1, except that the exposure was performed without adjusting the direction of the substantially rectangular exposure region imaged on the exposed surface of the photosensitive layer, the pattern forming material, and A laminated body was prepared, a pattern was formed, and resolution and etching property were evaluated. The results are shown in Table 1.
The amount of light energy required for curing the photosensitive layer was 3.5 mJ / cm ² .

  From the results in Table 1, it was found that the wiring patterns of Examples 1 to 5 were high-definition and excellent in etching properties as compared with the wiring patterns of Comparative Examples 1 to 3. In addition, by using a projection lens with a lens distortion in the peripheral area and reducing the lens distortion in the area including the center, and using an exposure head equipped with a lens barrel that can rotate the projection lens, It has been found that high-definition exposure can be realized at low cost, and that the focal length can be adjusted easily and in a short time by providing a wedge-shaped prism pair, so that efficient exposure can be achieved.

  The pattern forming method of the present invention can form a permanent pattern such as a wiring pattern with high definition and efficiency by improving exposure performance without increasing the cost of the apparatus or reducing the exposure speed. Therefore, it can be suitably used for forming various patterns that require high-definition exposure, and can be particularly suitably used for forming high-definition wiring patterns.

FIG. 1 is a schematic external view of the exposure apparatus. FIG. 2 is a schematic external view of the scanner. FIG. 3 is a diagram showing the internal configuration of the exposure head. FIG. 4 is a diagram illustrating a configuration of a light source unit as a light irradiation unit. FIG. 5 is a diagram showing the configuration of the laser emitting portion in the light irradiation means. FIG. 6 is a diagram showing the configuration of the LD module in the light irradiation means. FIG. 7 is an explanatory diagram of optical elements constituting the exposure head. FIG. 8A is a plan view showing a projection lens. FIG. 8B is a plan view showing the projection lens. FIG. 9 is a schematic side sectional view of a lens barrel including an imaging optical system and a schematic plan view of the lens barrel. FIG. 10 is a schematic perspective view of a DMD which is a light modulation means. FIG. 11A is an explanatory diagram of a use region of a micromirror that constitutes a DMD. FIG. 11B is an explanatory diagram of a use region of a micromirror that constitutes a DMD. FIG. 12 is a side view showing the configuration of a wedge-shaped prism pair that is a focus adjusting means. FIG. 13 is a schematic perspective view of a wedge-shaped prism pair which is a focus adjusting means. FIG. 14 is an explanatory diagram of optical elements constituting the exposure head. FIG. 15A is a diagram illustrating a configuration of a microlens array including a piezo element, which is another example of the focus adjusting unit. FIG. 15B is a diagram illustrating a configuration of a microlens array including a piezo element, which is another example of the focus adjusting unit. FIG. 16A is a diagram illustrating a configuration of a microlens array including a piezo element, which is another example of the focus adjusting unit. FIG. 16B is a diagram illustrating a configuration of a microlens array including a piezo element, which is another example of the focus adjusting unit. FIG. 17A is a perspective view schematically showing the positional relationship between the photosensitive material and the DMD. FIG. 17B is a side view schematically showing the positional relationship between the photosensitive material and the DMD.

Explanation of symbols

10 Exposure Device 30 Exposure Head 80 DMD
50 imaging optical system 51 first projection lens 52 second projection lens 54 wedge-shaped prism pair 12 photosensitive material

Claims (25)

After laminating the photosensitive layer in the pattern forming material having the photosensitive layer on the support on the substrate to be processed,
The light from the light irradiating means is received and modulated based on the pattern information. The light modulating means modulates the light from the light irradiating means, and the light modulated by the light modulating means And performing exposure by forming an image on an exposed surface of the photosensitive layer through an adjusting means,
In the exposure, light modulated by the light modulation means is imaged only in a substantially rectangular region including the center of the imaging means,
The substantially rectangular exposure region imaged on the exposed surface of the photosensitive layer has an angle formed by the short side direction and the waviness direction of the photosensitive layer, the long side direction and the waviness direction of the photosensitive layer. A pattern forming method characterized in that the pattern forming method is performed so as to be smaller than an angle formed by.   The pattern forming method according to claim 1, wherein the image forming unit forms an image of light modulated by the light modulation unit in a substantially rectangular region whose long side is twice or more the length of the short side. The focus adjustment means has a wedge-shaped prism pair formed so that the thickness in the optical axis direction of the light modulated by the light modulation means changes,
3. The focal point when the light modulated by the light modulating means is imaged on the exposed surface of a photosensitive layer is adjusted by moving each wedge-shaped prism constituting the wedge-shaped prism pair. The pattern formation method in any one of. The focus adjusting means has an optical member constituting the imaging optical system and a piezo element,
3. The focal point when the light modulated by the light modulating unit is imaged on the exposed surface of the photosensitive layer is adjusted by moving the optical member by the piezo element. Pattern forming method.   The imaging means is composed of either a lens that can rotate around the optical axis with respect to the optical axis of the light modulated by the light modulating means, or a lens that can move in a direction perpendicular to the optical axis. The pattern forming method according to any one of claims 1 to 4.   6. The pattern forming method according to claim 1, wherein the light modulation means is a spatial light modulation element.   7. The pattern forming method according to claim 1, wherein the light irradiation means emits laser light emitted from the semiconductor laser element.   8. The bundle-shaped fiber light source according to claim 7, wherein the light irradiating means is a bundled fiber light source in which a plurality of optical fibers that enter the laser light emitted from the semiconductor laser element from one end and emit the incident laser light from the other end are bundled. Pattern forming method.   The pattern forming method according to claim 7, wherein the light irradiation means can synthesize and irradiate two or more lights.   The light irradiation means condenses the laser beams emitted from the plurality of lasers, the multimode optical fiber, and the lasers by collimating them, and converges them on the incident end face of the multimode optical fiber. The pattern forming method according to claim 7, further comprising an optical system.   The pattern forming method according to claim 1, wherein the photosensitive layer is developed after the exposure.   The pattern forming method according to claim 1, wherein a permanent pattern is formed after the development.   The pattern formation method according to claim 12, 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 in any one of Claim 1 to 13 in which a photosensitive layer contains a binder, a polymeric compound, and a photoinitiator.   The pattern forming method according to claim 14, wherein the binder has an acidic group.   The pattern forming method according to claim 14, wherein the binder is a vinyl copolymer.   The pattern formation method according to any one of claims 14 to 16, wherein an acid value of the binder is 70 to 250 mgKOH / g.   The pattern forming method according to claim 14, 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. 20. The pattern forming method according to any one of items 19 to 19.   The pattern formation method according to any one of claims 1 to 19, wherein the photosensitive layer contains 10 to 90% by mass of a binder and 5 to 90% by mass of a polymerizable compound.   The pattern forming method according to claim 1, wherein the photosensitive layer has a thickness of 1 to 100 μm.   The pattern forming method according to claim 1, wherein the support includes a synthetic resin and is transparent.   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 23, 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.