WO2007007512A1

WO2007007512A1 - Pattern forming method

Info

Publication number: WO2007007512A1
Application number: PCT/JP2006/312095
Authority: WO
Inventors: Masanobu Takashima; Kazuki Komori; Hiromi Ishikawa; Yoji Okazaki; Toshihiko Omori
Original assignee: Fujifilm Corporation
Priority date: 2005-07-07
Filing date: 2006-06-16
Publication date: 2007-01-18
Also published as: CN101218545A; KR20080034124A; TW200710943A; JP2007017722A

Abstract

Provided is a pattern forming method by which a fine pattern can be accurately formed by making a light quantity of each exposure unit uniform while suppressing cost, for exposure using a digital exposure apparatus having an exposure head wherein the exposure units are two-dimensionally distributed. The method at least includes a step wherein a photosensitive layer is irradiated with optical beams emitted from a light irradiation means, through a focusing optical system having a light distribution correcting means, and exposure is performed by irradiating the photosensitive layer with optical beams modulated by a light modulating means. In the pattern forming method, the exposure is performed by permitting light quantities of the optical beams applied on the light modulating means from the light irradiation means in an irradiation area to have distribution, and that the light quantity distribution of the optical beams modulated by the light modulating means is corrected to be uniform on the plane of the photosensitive layer to be exposed.

Description

Specification

Pattern formation method

Technical field

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 a photosensitive layer and the photosensitive layer is exposed.

Background art

[0002] Conventionally, various exposure apparatuses that perform exposure with light modulated in accordance with pattern information (image data) by a spatial light modulation element (SLM) such as a digital micromirror device (DMD) have been proposed. Yes.

[0003] The DMD is a mirror device in which a large number of micromirrors whose reflection surfaces change in response to a control signal are two-dimensionally arranged on a semiconductor substrate such as silicon. In an exposure method using a conventional digital exposure type exposure apparatus using this DMD, for example, a light source for irradiating laser light, a lens system for collimating the laser light irradiated with the light source force, and the lens system Generated according to pattern information or the like using an exposure head including the DMD arranged at a substantially focal position of the lens and a lens system that forms an image of the laser light reflected by the DMD on a scanning surface. Each of the DMD micromirrors is controlled to be turned on and off by a control signal to modulate the laser light, and the modulated laser light (light beam) is set on the stage of the exposure apparatus and moved along the scanning direction. The pattern is scanned and exposed to photosensitive materials such as printed wiring boards and liquid crystal display elements.

In an exposure method using a digital exposure apparatus including an exposure head in which drawing units are two-dimensionally distributed as described above, in order to form a fine pattern with high accuracy, It is important that is uniform.

However, in reality, the light emitted from the exposure head has a lower light intensity at the periphery than at the center of the optical axis due to the factors of each lens system in the exposure head. This is particularly noticeable in systems that irradiate the light collected through the microlens array for each drawing unit.

[0005] To solve this problem, the light intensity distribution (light quantity) of the light emitted from the exposure head is measured, The seeding technique for correcting the light quantity of each drawing unit to be uniform by controlling the drive so that the drive timing of each picture element portion of the spatial light modulator is changed according to the light intensity distribution has already been developed. The applicant has proposed (see, for example, Patent Documents 1 and 2).

However, in the techniques of Patent Documents 1 and 2 described above, the load applied to the drive control unit of the spatial light modulation element increases to affect the processing speed, and such an exposure apparatus is In some cases, the electrical circuit configuration and processing software become complicated, leading to an increase in cost. The cost of the electrical control system accounts for a large percentage of the overall cost of the device, so a new technology that can reduce the load on the control system is desired to reduce the cost.

[0007] Therefore, in exposure using a digital exposure apparatus including an exposure head in which drawing units are two-dimensionally distributed, the light amount of each drawing unit distributed two-dimensionally is made uniform while suppressing costs. However, a pattern forming method capable of forming a fine pattern with high accuracy has not been provided yet, and further improvement and development are desired at present.

Patent Document 1: Japanese Patent Application Laid-Open No. 2005-22248

Patent Document 2: # 112005-22249

Disclosure of the invention

Problems to be solved by the invention

[0009] The present invention has been made in view of the current situation, and it is an object of the present invention to solve the above-described problems and achieve the following objects. That is, according to the present invention, the amount of light of each drawing unit distributed two-dimensionally is made uniform while reducing the cost for exposure using a digital exposure apparatus having an exposure head in which the drawing unit is distributed two-dimensionally. Thus, an object of the present invention is to provide a pattern forming method capable of forming a fine pattern with high accuracy.

Means for solving the problem

[0010] Means for solving the above-described problems are as follows. That is,

<1> After laminating the photosensitive layer in a pattern forming material having a photosensitive layer on a support on a substrate to be processed,

The photosensitive layer has n (where n is a natural number of 1 or more) two-dimensionally arranged pixel parts, and the light modulation state is changed for each of the pixel parts according to pattern information. Light modulation hand Irradiating the light beam emitted from the light irradiating means via a condensing optical system having a light distribution correcting means, and irradiating with the light beam modulated by the light modulating means,

The exposure gives a distribution of the amount of light within the irradiation region of the light beam irradiated from the light irradiation unit to the light modulation unit, and the light amount distribution force of the light beam modulated by the light modulation unit. The pattern forming method is characterized in that the correction is performed so as to be uniform on the exposed surface. In the pattern forming method according to <1>, the light amount in the irradiation region of the light beam irradiated to the light modulation unit is distributed by the condensing optical system having the light amount distribution correction unit. Since the light quantity distribution on the exposure surface of the light beam modulated by the light modulation means is corrected to be uniform, the light quantity of each drawing unit is corrected to be uniform in the picture element unit, and high accuracy is achieved. Exposure. For example, a high-definition pattern is then formed by developing the photosensitive layer.

<2> The pattern forming method according to <1>, wherein the light modulation unit is configured to irradiate the light modulation unit with the light beam emitted from the light irradiation unit as a light beam having a distribution in the angle of the principal ray by a condensing optical system. In the pattern forming method according to <2>, the light beam emitted from the light irradiation unit is irradiated to the light modulation unit by the condensing optical system as a light beam having a distribution in the chief ray angle. Therefore, a distribution is given to the amount of light within the irradiation region of the light beam irradiated to the light modulation means. As a result, the light quantity distribution on the exposure surface is made uniform, and extremely high-precision exposure is performed. For example, after that, the photosensitive layer is developed to form a very fine pattern.

<3> Light irradiation means force The pattern forming method according to <1>, wherein the emitted light beam is irradiated to the light modulation means as telecentric light by a condensing optical system. In the pattern forming method according to <3>, since the light beam emitted from the light irradiation unit is irradiated to the light modulation unit as telecentric light by the condensing optical system, the light modulation unit The telecentricity of the light applied to the light and the uniformity of the light quantity distribution on the exposure surface of the light modulated by the light modulation means can be achieved, and extremely high-precision exposure is performed. For example, by developing the photosensitive layer thereafter, extremely high definition Pattern is formed.

<4> A first optical lens that has an aspherical shape in which the condensing optical system decreases in lens power as it moves away from the optical axis center force, and an aspherical shape in which the lens power increases as it moves away from the optical axis center The pattern forming method according to <3>, further including: a light distribution correcting unit including a second optical lens having In the pattern forming method according to <4>, the condensing optical system has an aspherical shape (such as a convex lens for condensing a parallel incident beam) such that the lens power becomes smaller as the optical axis central force is also separated. And a second optical lens having an aspherical shape (such as a concave lens that diverges a parallel incident beam) such that the lens power increases as the distance from the optical axis center increases. Since the light distribution correcting means is provided, a situation is realized in which the light passing through the center of the first optical lens is stronger than the light passing through the periphery of the first optical lens. In addition, a telecentric optical system is realized by reversing the change in lens power along the optical axis between the first optical lens and the second optical lens. As a result, the light amount distribution of the light beam emitted from the telecentric optical system has a higher distribution density in the peripheral portion with respect to the center of the optical axis, the light amount distribution on the exposure surface is made uniform, and extremely accurate exposure is possible. Done. For example, by developing the photosensitive layer thereafter, an extremely fine pattern is formed.

<5> From the above <1>, the condensing optical system increases the amount of light in the peripheral portion rather than the central portion within the irradiation region of the light beam irradiated from the light irradiation means to the light modulation means. <4> The pattern forming method according to any one of <4>. In the pattern forming method according to <5>, the condensing optical system is arranged in a peripheral portion rather than a central portion in an irradiation region of a light beam irradiated from the light irradiation unit to the light modulation unit. In order to increase the amount of light, in the irradiation region of the light beam irradiated to the light modulation means, the amount of light in the peripheral portion that is lower than the central portion is increased by the condensing optical system, and light use efficiency in exposure is improved.

<6> Light modulation means force The pattern forming method according to any one of <1> to <5>, which is a spatial light modulation element.

<7> The pattern forming method according to <6>, wherein the spatial light modulator is a digital 'micromirror' device (DMD). <8> The pattern forming method according to any one of <1> to <7>, wherein the photosensitive layer is developed after exposure.

<9> The pattern forming method according to any one of <1> to <8>, wherein a permanent pattern is formed after development.

<10> The pattern forming method according to <9>, 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.

<11> The pattern forming method according to any one of <1>, <10>, <10>, wherein the light irradiation means 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 pattern forming material is exposed with extremely high definition. For example, by developing the photosensitive layer thereafter, a very high-definition pattern is formed.

<12> The light irradiating means collimates and condenses the laser beams irradiated with the plurality of lasers, the multimode optical fiber, and the plurality of laser forces, respectively, on the incident end face of the multimode optical fiber. The pattern forming method according to any one of <1>, <1 1>, and the like, including a light source condensing optical system for convergence. In the pattern forming method according to <12>, laser beams emitted from the plurality of lasers are condensed by the light source condensing optical system by the light irradiation unit, and the multimode optical fiber By focusing on the incident end face of the bar, a light beam with high brightness and deep focal depth can be obtained. As a result, the pattern forming material is exposed with extremely high definition. For example, after that, the photosensitive layer is developed to form a very fine pattern.

<13> The pattern forming method according to any one of <1> to <12>, wherein the photosensitive layer contains a binder, a polymerizable compound, and a photopolymerization initiator.

<14> Binder strength The pattern forming method according to 13 above, which has an acidic group.

<15> Any of the above 13> Karaku 14> wherein the binder is a vinyl copolymer. The pattern forming method according to claim 1.

<16> The binder according to any one of <13> and <15>, wherein the binder includes a copolymer, and the copolymer has structural units derived from at least one of styrene and a styrene derivative. It is a pattern forming material.

<17> The pattern forming material according to any one of <13> to <16>, wherein the glass transition temperature (Tg) force of the binder is 80 ° C or more.

<18> The pattern forming method according to any one of <13>, <17>, wherein the binder has an acid value of 70 to 250 mgKOHZg.

<19> The pattern forming method according to any one of <13> to <18>, wherein the polymerizable compound contains a monomer having at least one of a urethane group and an aryl group.

<20> The photopolymerization initiator is a halogenated hydrocarbon derivative, hexarylbiimidazole, oxime derivative, organic peroxide, thio compound, ketone compound, aromatic onium salt, The pattern forming method according to any one of the above items 13> Karaku 18>, which includes at least one selected from Sensen.

<21> The pattern forming method according to any one of <1> to <20>, wherein the photosensitive layer contains 10 to 90% by mass of a noinder and 5 to 90% by mass of a polymerizable compound.

<22> The pattern forming method according to any one of <1> to <21>, wherein the photosensitive layer has a thickness of 1 to 100111.

<23> Support strength The pattern forming method according to any one of the above items <1> to <22>, which contains a synthetic resin and is transparent.

<24> The pattern forming method according to any one of <1>, <23>, wherein the support has a long shape.

<25> Pattern forming material force The pattern forming method according to any one of the above-mentioned <1> force <24>, which is long and wound in a roll shape.

<26> The pattern forming method according to any one of <1> to <25>, wherein a protective film is formed on the photosensitive layer in the pattern forming material. The invention's effect

[0017] According to the present invention, the conventional problems can be solved, and the exposure can be performed while using a digital exposure apparatus including an exposure head in which drawing units are two-dimensionally distributed, while reducing the cost. A pattern forming method capable of forming a fine pattern with high accuracy can be provided by equalizing the amount of light of each drawing unit distributed in a uniform manner.

Brief Description of Drawings

FIG. 1 is a schematic block diagram showing an optical system of an exposure head provided in an exposure apparatus used in the color filter manufacturing method of the present invention.

[FIG. 2] FIG. 2 is an example of a partially enlarged view showing the configuration of a digital micromirror device (DMD).

FIG. 3A is an explanatory diagram for explaining the operation of the DMD shown in FIG.

FIG. 3B is an explanatory diagram for explaining the operation of the DMD shown in FIG.

FIG. 4A is a perspective view showing a configuration of a fiber array light source.

FIG. 4B is a plan view showing an array of light emitting points in the laser emitting section of FIG. 4A.

FIG. 5 is a plan view showing a configuration of a combined laser light source.

FIG. 6 is a plan view showing a configuration of a laser module.

FIG. 7 is a side view showing the configuration of the laser module shown in FIG.

FIG. 8 is a partial side view showing the configuration of the laser module shown in FIG.

[FIG. 9A] FIG. 9A is a schematic diagram schematically showing the inclination of the chief ray of laser light irradiated on the DMD.

[FIG. 9B] FIG. 9B is a graph showing the distribution of chief ray angles of laser light irradiated on the DMD.

[FIG. 10] FIG. 10 shows a case where a laser beam having a chief ray angle distribution corresponding to the chief ray angle distribution (1) of the laser beam emitted onto the DMD shown in FIG. The graph (2) showing the light intensity distribution of the image, the graph (3) showing the light transmission characteristics between the DMD and the microlens array, and performing image exposure with the laser light adjusted as shown in the graph (3). FIG. 14 is a graph (4) showing a state where the light amount distribution in the exposure area is made uniform and corrected.

FIG. 11A is a block diagram showing a telecentric optical system, and shows a second embodiment of the present invention. It is a block diagram which shows the telecentric optical system which has the aspherical lens which concerns on a form.

FIG. 11B is a configuration diagram showing a telecentric optical system, and is a configuration diagram showing a telecentric optical system having a spherical lens as a base of the telecentric optical system in FIG. 11A.

BEST MODE FOR CARRYING OUT THE INVENTION

[0019] (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.

[0020] The exposure step includes n (where n is a natural number of 1 or more) two-dimensionally arranged pixel parts, and the light modulation state is changed for each of the pixel parts according to pattern information. The light modulation means to be changed is irradiated with a light beam emitted from the light irradiation means via a condensing optical system having a light distribution correction means, and the light beam modulated by the light modulation means is irradiated for exposure. Including at least

The exposure gives a distribution of the amount of light within the irradiation region of the light beam irradiated from the light irradiation unit to the light modulation unit, and the light amount distribution force of the light beam modulated by the light modulation unit. The correction is performed so as to be uniform on the exposed surface.

[0021] A method for providing a distribution of the amount of light in the irradiation region of the light beam irradiated from the light irradiation unit to the light modulation unit can be appropriately selected according to the purpose without any particular limitation. For example, the first embodiment in which a light beam emitted from the light irradiating means is irradiated to the light modulating means as a light beam having a distribution in the principal ray angle by the condensing optical system, and the light There is a second embodiment in which a light beam emitted from an irradiating means is irradiated to the light modulating means as telecentric light by the condensing optical system.

An example of an exposure apparatus relating to the exposure process of the pattern forming method of the present invention will be described below with reference to the drawings. The exposure method in the exposure process will be clarified through the description of the exposure apparatus.

[First Embodiment]

<Schematic configuration of exposure system> FIG. 1 shows a schematic configuration of an exposure head 100 provided in the exposure apparatus according to the first embodiment.

As shown in FIG. 1, the exposure head 100 may represent an incident light beam as a pixel part (hereinafter referred to as “pixel”) according to pattern information (hereinafter also referred to as “image data”). ) As a light modulation means to modulate every time, a digital 'micromirror' device (DMD) 50 of a spatial light modulation element is provided. The DMD 50 is connected to a controller (not shown) having a data processing unit and a mirror drive control unit.

Based on the input pattern information (image data), the data processing unit of the controller generates a control signal for driving and controlling each micromirror of the DMD 50 which is a pixel part (pixel) based on the input pattern information (image data). The mirror drive control unit controls the angle of the reflection surface of each micromirror of the DMD 50 based on the control signal generated by the image data processing unit.

The control of the angle of the reflecting surface will be described later.

[0024] On the light incident side of the DMD 50, a fiber array light source 112 having a laser emission portion in which emission ends (light emission points) of optical fibers are arranged in a line along a predetermined direction are emitted from the fiber array light source 112. The condensing optical system 114 that corrects the laser beam that has been corrected and collects the light on the DMD, and the mirrors 122 and 124 that reflect the laser light transmitted through the condensing optical system 114 toward the DMD 50 are arranged in this order.

[0025] The condensing optical system 114 includes a pair of combination lenses 116 that condense the laser light emitted from the fiber array light source 112, and a rod that corrects the light amount distribution of the collected laser light to be uniform. It comprises an integrator 118 and a condensing lens 120 that condenses the laser light whose light intensity distribution has been corrected on the DMD.

Since the rod integrator 118 guides the light while totally reflecting the light inside the integrator, the rod integrator 118 can correct the laser light so that the light quantity distribution is uniform.

On the other hand, a projection optical system is provided on the light reflection side of the DMD 50.

The projection optical system projects a light source image onto a photosensitive material (laminated body in which the photosensitive layer in the pattern forming material is laminated on a substrate to be processed) 134 on the exposure surface of the DMD 50 on the light reflection side. In order to do this, the optical members for exposure of the lens system 126, the microlens array 128, and the objective lens system 130 are arranged in order toward the DMD50 side force photosensitive material 134. It is configured.

Here, as shown in FIG. 1, the lens system 126 and the objective lens system 130 are configured as a magnifying optical system in which a plurality of lenses (such as a convex lens and a concave lens) are combined, and are reflected by the DMD 50. By expanding the cross-sectional area of the light beam (light beam), the area of the exposure area on the photosensitive material 134 by the light beam reflected by the DMD 50 is expanded to a predetermined size.

Note that the photosensitive material 134 is disposed at the rear focal position of the objective lens system 130.

[0028] As shown in FIG. 1, the microlens array 128 includes a plurality of one-to-one correspondences with each micromirror 62 (see FIG. 2) of the DMD 50 that reflects the laser light emitted from the fiber array light source 112. The microlenses 132 are two-dimensionally arranged and integrally molded into a rectangular flat plate shape. Each microlens 132 is on the optical axis of each laser beam transmitted through the lens system 126. Each is arranged.

The microlens array 128 can be formed, for example, by molding a resin or optical glass.

[0029] One-light modulation means

As shown in FIG. 2, the DMD 50 as an example of the light modulation means is configured such that a micromirror 62 is supported on a SRAM cell (memory cell) 60 by a support column. This is a mirror device configured by arranging a large number (for example, 600 × 800) of micromirrors constituting a portion (also referred to as “pixel” or “pixel”) in a grid pattern.

Each pixel is provided with a micro mirror 62 supported by a support column at the top, and a material having high reflectivity such as aluminum is deposited on the surface of the microphone opening mirror 62. Note that the reflectivity of the micromirror 62 is 90% or more.

In addition, a silicon gate CMOS SRAM cell 60 manufactured in a normal semiconductor memory manufacturing line is disposed directly below the micromirror 62 via a support including a hinge and a yoke. (Integrated type).

[0030] When a digital signal is written to the SRAM cell 60 of the DMD50, the microphone mirror 62 supported by the support is ±± degrees (eg ± 10 °) with respect to the substrate side on which the DMD50 is placed with the diagonal line as the center. ) Tilted within the range. Figure 3A shows micromirror 62 in the on state + shows a state tilted to α degrees, and Fig. 3 (b) shows a state tilted to α degrees when the micromirror 62 is in the OFF state. Therefore, by controlling the tilt of the micro mirror 62 in each pixel of the DMD 50 according to the image signal as shown in FIG. 2, the light incident on the DMD 50 is reflected in the tilt direction of each micro mirror 62. .

FIG. 2 shows an example of a state in which a part of the DMD 50 is enlarged and the micromirror 62 is controlled to be + α degrees or α degrees. On / off control of each micromirror 62 is performed by a controller (not shown) connected to the DMD 50. A light absorber (not shown) is arranged in the direction in which the light beam is reflected by the micromirror 62 in the off state.

[0032] Single light irradiation means

The fiber array light source 112 as an example of the light irradiating means includes a plurality of (25 in the figure) laser modules 64 as shown in FIG. 4A. Each laser module 64 includes a multimode optical fiber _30. One end of each is joined. The other end of the multimode optical fiber 30 is coupled with an optical fiber 31 having the same core diameter as the multimode optical fiber 30 and a cladding diameter smaller than the multimode optical fiber 30. As shown in FIG. A plurality of rows (three rows in the figure) of emission end portions (light emission points) of the laser emission portion 68 are arranged along a predetermined direction.

[0033] The multimode optical fiber 30 and the optical fiber 31 may be any of a step index optical fiber, a graded index optical fiber, and a composite optical fiber. For example, a step index type optical fiber manufactured by Mitsubishi Cable Industries, Ltd. can be used.

In the present embodiment, the multimode optical fiber 30 and the optical fiber 31 are step index optical fibers, and the multimode optical fiber 30 has a cladding diameter = 125 m, a core diameter = 50 / ζ πι, NA = 0.2, the transmittance of the incident end face coating is 99.5% or more, and the optical fiber 31 has a cladding diameter = 60 m, a core diameter = 50 m, and NA = 0.2.

However, the cladding diameter of the optical fiber 31 is not limited to 60 m. The optical fiber used in conventional fiber light sources has a cladding diameter of 125 m. The smaller the cladding diameter, the deeper the depth of focus, so the cladding diameter of multimode optical fibers is 80 m or less. 60 μm or less is more preferable, and 40 μm or less is more preferable.

On the other hand, since the core diameter needs to be at least 3 to 4 / ζ πι, the cladding diameter of the optical fiber 31 is preferably 10 m or more.

[0035] The laser module 64 is configured by a combined laser light source (fiber light source) shown in FIG. This combined laser light source is composed of a plurality of (for example, 7) chip-shaped lateral multimode or single mode GaN semiconductor lasers L Dl, LD2, LD3, LD4, LD5, LD6 and LD7, collimator lenses 11, 12, 13, 14, 15, 16, and 17 provided corresponding to each of the GaN-based semiconductor lasers LD1 to LD7, one condenser lens 20, and 1 It is composed of a multi-mode optical fiber 30 and a force. The number of semiconductor lasers is not limited to seven. For example, a multimode optical fiber with a cladding diameter of 60 / ζ πι, a core diameter of 50 πι, and NA = 0.2 can receive as many as 20 semiconductor laser beams. And the number of optical fibers can be further reduced.

[0036] The GaN semiconductor lasers LD1 to LD7 all have the same oscillation wavelength (for example, 405 nm), and all the maximum outputs are also common (for example, 100 mW for the multimode laser and 30 mW for the single mode laser). As the GaN-based semiconductor lasers LD1 to LD7, lasers having an oscillation wavelength other than the above-described 405 nm in a wavelength range of 350 nm to 450 nm may be used.

A suitable wavelength range will be described later.

[0037] As shown in Figs. 6 and 7, the combined laser light source is housed in a box-shaped package 40 having an upper opening together with other optical elements. The package 40 is provided with a package lid 41 created so as to close the opening thereof. After the degassing process, a sealing gas is introduced, and the opening of the knock 40 is closed by the package lid 41, whereby the package 40 and the package 40 are packaged. The combined laser light source is hermetically sealed in a closed space (sealed space) formed by the cage lid 41.

[0038] A base plate 42 is fixed to the bottom surface of the package 40. On the top surface of the base plate 42, the heat block 10, a condensing lens holder 45 for holding the light source condensing lens 20, and a multimode are provided. Attached with fiber holder 46 that holds the incident end of optical fiber 30 It has been. The exit end of the multimode optical fiber 30 is drawn out of the package through an opening formed in the wall surface of the package 40.

[0039] A collimator lens holder 44 is attached to the side of the heat block 10.

The collimator lenses 11 to 17 are held. An opening is formed in the lateral wall surface of the package 40, and wiring 47 for supplying a driving current to the GaN-based semiconductor lasers LD1 to LD7 is drawn out of the package through the opening.

In FIG. 6, in order to avoid complication of the drawing, only the GaN semiconductor laser LD 7 among the plurality of GaN semiconductor lasers is numbered, and the collimator lens 17 among the plurality of collimator lenses is assigned. Only numbered.

FIG. 8 shows the front shape of the mounting portion of the collimator lenses 11 to 17. Each of the collimator lenses 11 to 17 is a plane parallel to a region including the optical axis of a circular lens having an aspheric surface. It is formed into a shape that has been cut long and thin. The elongated collimator lens can be formed, for example, by molding resin or optical glass. The collimator lenses 11 to 17 are closely arranged in the arrangement direction of the light emitting points so that the length direction is orthogonal to the arrangement direction of the light emitting points of the GaN-based semiconductor lasers LD1 to LD7 (left and right direction in FIG. 8).

On the other hand, each of the GaN-based semiconductor lasers LD1 to LD7 includes an active layer having an emission width of 2 μm, and the divergence angles in a direction parallel to the active layer and in a direction perpendicular thereto are, for example, 10 ° and 30 °, respectively. Lasers that emit laser beams B1 to B7 are used. These GaN-based semiconductor lasers LD1 to LD7 are arranged so that the light emitting points are arranged in a line in a direction parallel to the active layer.

[0043] Accordingly, the laser beams B1 to B7 emitted by the respective light emission point forces are expanded in the direction in which the divergence angle is large with respect to the elongated collimator lenses 11 to 17 as described above. The incident light enters in a state where the direction with a small angle coincides with the width direction (direction perpendicular to the length direction). That is, the collimator lenses 11 to 17 have a width of 1. lmm and a length of 4.6 mm, and the horizontal and vertical beam diameters of the laser beams B1 to B7 incident on them are 0.9 mm and 2 respectively. 6mm. Each of the collimator lenses 11 to 17 has a focal length. The distance f is 3 mm, NA is 0.6, and the lens arrangement pitch is 1.25 mm.

1

[0044] The light source condensing lens 20 is obtained by cutting an area including the optical axis of a circular lens having an aspherical surface into a long and narrow plane parallel to the arrangement direction of the collimator lenses 11 to 17, that is, perpendicular to the length in the horizontal direction. It is formed in a short shape in any direction. The light source condenser lens 20 has a focal length f = 23 mm and NA = 0.2. Similarly to the collimator lens, the light source condenser lens 20 is also an example.

2

For example, it is formed by molding a resin or optical glass.

In the fiber array light source 112 configured in this way, the laser beams B1, B2, B3, B4, B5 emitted in the force divergent light states of the Ga N-based semiconductor lasers LD1 to LD7 constituting the combined laser light source , B6, and B7 are collimated by the corresponding collimator lenses 11-17. The collimated laser beams B1 to B7 are collected by the light source condenser lens 20 and converge on the incident end face of the core 30a of the multimode optical fiber 30.

The collimator lenses 11 to 17 and the light source condenser lens 20 constitute a light source condensing optical system, and the light source condensing optical system and the multimode optical fiber 30 constitute a multiplexing optical system.

That is, the laser beams B1 to B7 condensed as described above by the light source condenser lens 20 enter the core 30a of the multimode optical fiber 30 and propagate through the optical fiber, and merge with the single laser beam B. The light is emitted from the optical fiber 31 coupled to the output end of the multimode optical fiber 30.

[0047] In each laser module, when the laser beam B1 ~: B7 coupling efficiency to the multimode optical fiber 30 is 0.85 and each output of the GaN-based semiconductor lasers LD1 ~ LD7 is 30mW (single mode laser is used) In this case, a combined laser beam B with an output of 180 mW (= 30 mWX 0.85 X 7) can be obtained for each of the optical fibers 31 arranged in an array. Therefore, the output from the laser emitting section 68 in which 25 optical fibers 31 are arranged in an array is about 4.5 W (= 180 mW × 25).

[0048] In the laser emitting section 68 of the fiber array light source 112, light emission points with high luminance are arranged along the main traveling direction as described above. Conventional fiber light sources that combine laser light from a single semiconductor laser into a single optical fiber have low output, so it was not possible to obtain the desired output without arranging multiple rows. Combined laser light used in the form of Since the source has a high output, the desired output can be obtained even with a small number of columns, for example one column.

[0049] For example, in a conventional fiber light source in which a semiconductor laser and an optical fiber are coupled on a one-to-one basis, a laser with an output of about 30 mW (milliwatt) is usually used as a semiconductor laser, and a core diameter is used as an optical fiber. Multimode optical fiber with 50 m, clad diameter 125 m, NA (numerical aperture) of 0.2 can be used, and 225 multimode optical fibers can be obtained if an output of about 4.5 W (watt) is to be obtained. (15 X 15) must bundled, the area of the light emitting region 3. 6 mm ² because it is (1. 9m m X l. 9mm ), the luminance at laser emitting portion 68 1. 25 (WZmm ^2), The luminance per optical fiber is 10 (WZmm ² ).

In contrast, in the present embodiment, as described above, an output of about 4.5 W can be obtained with 25 multimode optical fibers, and the area of the light emitting region at the laser emitting portion 68 is 0.2 mm. ² (0.18 mm × l. 13 mm), the luminance at the laser emitting portion 68 is 22.5 (W / mm ² ), which is about 18 times higher than the conventional luminance. In addition, the luminance per optical fiber is 90 (WZmm ² ), which makes it possible to increase the luminance by about 9 times.

[0051] As the semiconductor laser constituting the combined laser light source, a blue laser having an oscillation wavelength near 400 nm is preferable. Directional force using blue laser Microlens array 1 A condensing beam of each microlens 132 of 28 can be narrowed down.

[0052] Condensing optical system having light distribution correcting means

In the exposure head 100 of the present embodiment, which is the first embodiment, the condensing optical system 114 described above is an exposure surface of the exposure beam modulated by the DMD 50 separately from the light amount distribution correction function provided in the rod integrator 118. In order to evenly correct the light intensity distribution with higher accuracy, the laser light emitted to the DMD 50 has a predetermined distribution of the light intensity within the irradiation area, in detail, the laser incident from the fiber array light source 112 It has the function of emitting laser light with a predetermined distribution of chief ray angles to the light and irradiating the DMD 50.

Here, an example of irradiating the DMD 50 with laser light having a distribution in the chief ray angle will be described with reference to FIG. The principal ray (principal ray / chief ray) is a ray that passes through the center of the entrance pupil (or aperture stop) in the object space in the optical system (a ray that exists without vignetting even when the aperture stop is minimized). In the broad sense, it is the ray at the center of the oblique ray bundle. Used in the meaning of the person.

FIG. 9A is a diagram schematically showing the inclination of the chief ray of the laser light irradiated on the DMD 50. As shown in Fig. 9A, in the laser beam LB irradiated to a specific position P on the DMD 50, when the chief ray of the laser beam LB tilts to the minus (-) side, as shown by the arrow PR The chief ray tilts in the direction approaching the optical axis (optical axis center) X of the laser beam, and in the case of tilting to the plus (+) side, the direction moving away from the optical axis X of the laser beam as indicated by the arrow + PR Lean to.

FIG. 9B shows a state in which the chief ray angle is distributed according to the distance from the optical axis center in the illumination area on the laser beam power DMD 50 emitted from the condensing optical system 114 of the present embodiment. It is the figure which showed the example irradiated. As shown in Fig. 9B, the chief ray angle distribution of the laser beam irradiated to the illumination area (laser beam irradiation area) on DMD50 is parallel to the optical axis without tilting the chief ray at the center of the optical axis of the laser beam. The chief ray gradually tilts to the + side and gradually tilts as it goes from the optical axis center to the periphery of the illumination area, and when the predetermined distance YA is reached, the chief ray moves to the + side. The tilt angle becomes maximum (maximum tilt angle A), and after a predetermined distance YA, the tilt angle of the chief ray toward the + side gradually decreases, and when it reaches the peripheral edge of the illumination area, it is the same as the center of the optical axis. The distribution is such that the inclination of the light beam disappears.

By providing such a distribution of the chief ray angles of the laser light, the light density in the periphery of the DMD50 is increased compared to the center of the optical axis, that is, in the center of the optical axis. In comparison, the laser light having a higher brightness in the peripheral portion is irradiated.

[0056] In the case where the chief ray angle of the laser beam has the above-described distribution, the size of the distribution amount determined by the maximum tilt angle A of the chief ray is equal to or greater than the light amount reduction amount in the peripheral portion. In addition, the telecentricity (parallelism between the principal ray and the optical axis) of the exposure beam required on the exposure surface is preferably set to an amount that satisfies the amount.

In the case of the exposure head 100 of the present embodiment, the reduction in the amount of light at the periphery of the exposure beam on the exposure surface is mainly caused by the microlens array 128 (see FIG. 1) of the projection optical system disposed on the light reflection side of the DMD 50. Therefore, it is desirable to set the size of the distribution amount to be greater than or equal to the amount of light reduction in the peripheral portion caused by the microlens array 128, for example.

In addition, for the predetermined distance YA, the light amount reduction amount and the light amount reduction region (light 9B, in the example shown in Fig. 9B, if the distance from the optical axis center to the peripheral edge of the illumination area (the outer edge of DMD50) is YS, YS>YA> YSZ2 is set.

[0057] <Operation of exposure apparatus>

The operation of the exposure apparatus will be described.

In this exposure apparatus, when image data is input to a controller (not shown), the controller controls the drive of each micromirror 62 of the DMD 50 provided in the exposure head 100 based on the input image data. And based on the generated control signal! Control the angle of the reflection surface of each micromirror 62 of DMD50.

[0058] Illumination light emitted from the fiber array light source 112 to the DMD 50 via the condensing optical system 114

(Laser light) is reflected and modulated in a predetermined direction according to the angle of the reflection surface of each micromirror 62, and the modulated light beam is expanded by the lens system 126 and provided in the microlens array 128. Each of the beams 132 is incident and collected. The condensed light beam is imaged on the exposure surface of the photosensitive material 134 by the objective lens system 130. In this way, the laser light emitted from the fiber array light source 112 is turned off for each pixel ( Then, the photosensitive material 134 is exposed in a pixel unit (exposure area) of approximately the same number as the number of used pixels of the DMD 36.

[0059] Normally, the light amount (light intensity) distribution of this light beam is lower in the peripheral portion than in the central portion of the optical axis due to factors of the lens system, but the exposure head 100 of the present embodiment includes A rod integrator 118 is provided in the condensing optical system 114 arranged on the optical path on the light incident side of the DMD 50 in order to make the light distribution of the laser light emitted from the fiber array light source 112 uniform and irradiate the DMD 50. .

However, with this rod integrator 118 as well, in the system in which each drawing unit is condensed by the microlens array 128 as in the present embodiment, the light intensity at the peripheral portion with respect to the central portion of the optical axis is significantly reduced, and the image can be obtained with higher accuracy. When performing exposure, it is difficult to correct the light intensity distribution to the required accuracy. In order to improve the correction accuracy of this light quantity distribution, it is possible to lengthen the rod integrator 118. Since the rod integrator 118 is an extremely expensive optical component, the cost of the apparatus increases, and the exposure head 100 Has become larger There is a demerit.

In contrast, in the exposure head 100 of the present embodiment, as described above, the laser light incident on the condensing optical system 114 from the fiber array light source 112 is as shown in (1) of FIG. In addition, the laser beam is emitted from the condensing optical system 114 and irradiated to the DMD 50 as a laser beam having a distribution in the angle of the chief ray and having a higher brightness in the peripheral area than the center of the optical axis. As shown in (2) of FIG. 10, the light amount distribution in the light irradiation region increases the light amount in the peripheral portion as compared with the center of the optical axis. Therefore, as shown in (3) in FIG. 10, the microlens array 128 having a characteristic of reducing the amount of transmitted light as the light beam modulated for each pixel by the DMD 50 goes to the periphery of the optical axis central force. When the light is transmitted and irradiated on the exposure surface of the photosensitive material 134, the light amount distribution of the light beam on the exposure surface is corrected to be uniform as shown in (4) of FIG.

[0061] As described above, in the exposure apparatus of the first embodiment, the light quantity of each drawing unit is corrected so as to be uniform in a plurality of two-dimensionally distributed pixel units, and high-accuracy image exposure is performed. It can be carried out.

Even when using a combination of drive control technologies that change the drive timing of each micromirror 62 of the DMD 50 according to the light intensity distribution, the DMD 50 is corrected in advance so that the light intensity of each drawing unit is uniform. This reduces the load on the drive controller and reduces the effect on processing speed, simplifies the electrical circuit configuration and processing software, and reduces costs.

[0062] In addition, if the light amount distribution correcting unit includes the optical system (the condensing optical system 114) used in the present embodiment, the above-described unit for correcting the light amount distribution can be realized with a simple and inexpensive configuration.

[0063] [Second Embodiment]

In the second embodiment, in the exposure head 100 of the exposure apparatus according to the first embodiment described above, the concentrating optical system 114 includes a telecentric lens having an aspheric lens as the light distribution correcting means. By providing an optical system, this is a technique for equalizing the light amount distribution of the light beam on the exposure surface as in the first embodiment.

In the exposure head according to the second embodiment, for example, the light distribution is provided in the condensing optical system 114. As a correcting means, there is provided a telecentric optical system 150 constituted by a pair of plano-convex lenses 152 and 154 as shown in FIG. 11A. The telecentric optical system 150 is, for example, a rod integrator 118 and a condensing lens. Located between the lenses 120.

The plano-convex lenses 152 and 154 are aspherical lenses whose convex surfaces are formed in an aspheric shape, and the lens power decreases as the distance from the optical axis center increases (convex lenses that collect parallel incident beams). A first optical lens having an aspheric shape (such as a concave lens that diverges a parallel incident beam) such that the lens power increases as the distance from the center of the optical axis increases. It is a combination of lenses.

[0066] The plano-convex lens 152 disposed on the laser beam incident side (fiber array light source 112 side) is such that the surface shape of the incident surface S2 increases as the radius of curvature increases from the optical axis (optical axis center) X. It is a spherical surface, in other words, an aspherical surface whose curvature decreases with increasing distance from the optical axis X, and the exit surface S3 is planar.

In addition, the plano-convex lens 154 arranged on the laser beam emission side (DMD50 side) has an aspheric surface in which the incident surface S4 has a flat surface and the surface shape of the output surface S5 decreases as the radius of curvature increases from the optical axis X In other words, it is an aspheric surface whose curvature increases with distance from the optical axis X.

[0067] Table 1 below shows an example of lens data of the telecentric optical system 150 according to the present embodiment, and Table 2 shows an example of aspherical data of the entrance surface S2 and the exit surface S5 according to the embodiment. .

[0068] [Table 1]

[0069] [Table 2] Aspheric surface

Surface number S2 S5

A -0.0001 2 0.00003 The above aspheric data is represented by a coefficient in the following equation (1) representing the aspheric shape.

[0070] [Equation 1] hVR

+ Ah formula (1)

1 + 1−h ² / R ^{2 In the} above formula (1), each coefficient is defined as follows.

z: Length of perpendicular line (mm) drawn from a point on the aspheric surface at a height h from the optical axis to the tangent plane (plane perpendicular to the optical axis) of the apex of the aspheric surface

h: Distance from optical axis (mm) (h ² = x ² + y)

R: radius of curvature (curvature: 1ZR)

A: Aspheric data

With the above configuration, in the exposure apparatus of the second embodiment, as shown in FIG. 11A, the laser beam LB2 emitted from the plano-convex lens 152 has a longer focal length as it moves away from the optical axis X. Become. Therefore, when the laser beam LB2 reaches the incident surface S4 of the plano-convex lens 154, the direction of the light that has passed near the center tends to move away from the optical axis X compared to the light that has passed through the periphery of the plano-convex lens 152. Becomes stronger. As a result, the brightness of light is higher in the periphery than in the vicinity of the center of the lens. Also, the plano-convex lens 154 is opposite to the plano-convex lens 152, and the focal length becomes shorter as the distance from the optical axis X increases. Therefore, combining these two plano-convex lenses 152, 154 forms a telecentric optical system. Can do.

As a result, the light quantity distribution of the laser beam LB3 emitted from the telecentric optical system 150 having the plano-convex lenses 152 and 154 in parallel is increased in the distribution density of the peripheral portion with respect to the optical axis center. In the DMD 50 irradiated with the laser beam LB3, the amount of light in the peripheral portion is increased from the central portion (optical axis center) of the laser light irradiation region. FIG. 11B shows a ray diagram of the telecentric optical system 160 of the spherical lens system, which is the base of the telecentric optical system 150 of the present embodiment that is an aspherical lens system.

In this telecentric optical system 160, the incident surface of the plano-convex lens 162 arranged on the incident side of the laser beam (LB1) is a spherical surface, and the emitting surface of the laser beam (the emitting surface of the plano-convex lens 164 arranged on the output side of the LB3 is spherical) Therefore, in this telecentric optical system 160, the light quantity distribution of the laser beam LB3 ′ emitted from the emission surface is almost evenly distributed around the optical axis central force as shown in FIG. 11B. It becomes.

As described above, the aspherical lens system (telecentric optical system 150) of the second embodiment can also be seen from a comparison with the light amount distribution when the above spherical lens system (telecentric optical system 160) is used. In addition, the light amount distribution of the emitted laser light has a higher distribution density in the peripheral portion with respect to the optical axis center, and the light amount in the peripheral portion is increased than the optical axis center.

Therefore, as in the first embodiment, the light beam modulated by the DMD 50 passes through the microphone aperture lens array 128, so that even if the light amount in the peripheral portion with respect to the central portion of the optical axis is reduced, exposure is performed. The surface is irradiated with a light beam that has been corrected so that the light quantity distribution is uniform, and an exposure apparatus equipped with the telecentric optical system 150 can perform high-accuracy image exposure.

In addition, as described above, the laser light emitted from the telecentric optical system 150 is emitted as telecentric light and applied to the DMD 50, so that the telecentricity of the laser light applied to the DMD 50 and the DMD 50 are modulated. In addition, it is possible to achieve both the uniformity of the light distribution on the exposed surface of the light beam.

[0076] Similarly to the first embodiment, the second embodiment is also a light amount distribution correcting means including a condensing optical system having two pairs of plano-convex lenses 152, 154 (telecentric optical system). If so, the means for correcting the light quantity distribution described above can be realized with a simple configuration.

[0077] In the second embodiment, the telecentric optical system 150 is used to increase the amount of light in the peripheral portion of the laser light, so that a reduction in light use efficiency in exposure can be suppressed. This also makes it possible to reduce the output of the laser light emitted from the fiber array light source 112, thereby extending the life of the fiber array light source 112 and suppressing contamination of the optical system with high-intensity light. Can also be planned. In addition, fiber array light source 112 and optical system It is also possible to reduce the number of maintenance operations, which reduces the maintenance cost of the exposure equipment.

As described above, the exposure process has been described in detail according to the first and second embodiments, but the present invention is not limited thereto, and various other modes can be implemented within the scope of the present invention. It is.

For example, in the exposure apparatus, an exposure head provided with a DMD as a spatial modulation element has been described as the light modulation unit. However, in addition to such a reflective spatial light modulation element, a transparent spatial light is used. A modulation element (LCD) can also be used. For example, MEMS (Micro Electro Mechanical Systems) type Spatial Light Modulator (SLM), optical element (PLZT element) that modulates transmitted light by electro-optic effect, liquid crystal light shutter (FLC) It is also possible to use a spatial light modulator other than the MEMS type, such as a liquid crystal shutter array. MEMS is a collective term for micro-sized sensors, actuators, and control circuits using micro-machining technology based on the IC manufacturing process, and a micro system integrated with a control circuit. It means a spatial light modulator driven by electromechanical action using force. In addition, it is possible to use two or more Grating Light Valves (GLV) configured in two dimensions.

In a configuration using these reflective spatial light modulator (GLV) and transmissive spatial light modulator (LCD), a lamp or the like can be used as a light source in addition to the laser light source described above.

[0080] Further, as the light modulation means, a fiber array light source having a plurality of combined laser light sources, a single semiconductor laser power having one light emitting point, and a single optical fiber for emitting incident laser light A fiber array light source that is an array of fiber light sources equipped with a light source in which a plurality of light emitting points are arranged in a two-dimensional shape (for example, an LD array, an organic EL array, etc.) can be applied.

[0081] <Laminate>

The exposure target 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. It can be selected appropriately. As the laminate, for example, A layer other than the photosensitive layer in the pattern forming material is laminated.

[0082] <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.

[0083] The photosensitive layer can be appropriately selected from known pattern forming materials that are not particularly limited, and includes, for example, a needle, a polymerizable compound, and a photopolymerization initiator. Those containing other appropriately selected components are preferred.

Further, the number of laminated photosensitive layers can be appropriately selected according to the purpose without any particular limitation. For example, it may be one layer or two or more layers.

[0084] <<Binder>>

For example, the noder is preferably swellable in an alkaline aqueous solution, 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.

[0085] The acidic group is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among these, a carboxyxenore group is preferable. .

Examples of the binder having a carboxyl group include a vinyl copolymer having a carboxyl group, polyurethane resin, polyamic acid resin, and modified epoxy resin. Among these, solubility in a coating solvent, Viewpoints such as solubility in alkaline developer, suitability for synthesis, and ease of adjustment of film properties. Vinyl copolymers having a carboxyl group are preferred. From the viewpoint of developability, a copolymer of at least one of styrene and a styrene derivative is also preferable.

[0086] The vinyl copolymer having a carboxyl group can be obtained by copolymerization with at least (1) a vinyl monomer having a carboxyl group, and (2) a monomer copolymerizable therewith. Specific examples of these monomers include the compounds described in paragraph numbers [0164] to [0205] of JP-A-2005-258431. [0087] The content of the binder in the photosensitive layer is not particularly limited. A force that can be appropriately selected according to the purpose. For example, 10 to 90% by mass is preferable, and 20 to 80% by mass is more preferable. 40-80 mass% is especially preferable.

If the content is less than 10% by mass, the alkali developability and the adhesion to a printed wiring board forming substrate (for example, a copper-clad laminate) may be deteriorated. The stability against image time and the strength of the cured film (tent film) may be reduced. The above content may be the total content of the binder and the polymer binder used in combination as necessary.

[0088] 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 purpose. For example, the pattern forming material 80 ° C or higher is preferable, 100 ° C or higher is more preferable, and 120 ° C or higher is particularly preferable, from the viewpoint of suppressing tack and edge fusion and improving the peelability of the support. preferable.

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.

[0089] The Noinda one acid value, especially the force limit Ru can be appropriately selected depending on the Nag purpose for example, preferably 70~250mgKOHZg force ^{s, 90~200mgKOH} / g and more preferred signaling 100～180MgKOH / g is particularly preferred.

If the acid value is less than 70 mg KOHZg, developability may be insufficient or resolution may be inferior, and permanent patterns such as wiring patterns may not be obtained in high definition. At least the developer resistance and adhesion of the turn may be poor, and a permanent pattern such as a wiring pattern may not be obtained with high definition.

[0090] <Polymerizable compound>

The polymerizable compound is not particularly limited and may be appropriately selected according to the purpose. For example, a monomer or oligomer having at least one of a urethane group and an aryl group is preferably exemplified. These preferably have two or more polymerizable groups.

[0091] Examples of the polymerizable group include an ethylenically unsaturated bond (for example, (meth) atariloy). Group, (meth) acrylamide group, styryl group, beryl group such as butyl ester and butyl ether, aryl group such as valyl ether gally ester), polymerizable cyclic ether group (for example, epoxy group, oxetane group, etc.) Among these, ethylenically unsaturated bonds are preferred.

[0092] Monomer having urethane group

The monomer having a urethane group is not particularly limited as long as it has a urethane group, and can be appropriately selected according to the purpose. For example, paragraph numbers [0210] to [0210] of the publication of JP-A-2005-258431 [0262] and the like.

[0093] Monomers having aryl groups

The monomer having an aryl group is not particularly limited as long as it has an aryl group, and can be appropriately selected according to the purpose. For example, a polyhydric alcohol compound having an aryl group, a polyvalent amine compound. And esters or amides of unsaturated carboxylic acids with at least any of the above compounds and polyamino alcoholic compounds.

Specific examples include the compounds described in paragraphs [0264] to [0271] of JP-A-2005-258431.

[0094] Other polymerizable monomers

In the pattern forming method of the present invention, a polymerizable monomer other than the monomer containing a 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.

[0095] Examples of the polymerizable monomer other than the monomer containing a urethane group and the monomer containing an aromatic ring include an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, And an amide of an unsaturated carboxylic acid and a polyvalent amine compound.

Specific examples include the compounds described in paragraph numbers [0273] to [0284] of JP-A-2005-258431.

[0096] The content of the polymerizable compound in the photosensitive layer is preferably, for example, 5 to 90% by mass.

15 to 60% by mass is more preferable. 20 to 50% by mass is particularly preferable.

When the content is 5% by mass, the strength of the tent film may be reduced. Exceeding this may cause deterioration of edge fusion during storage (exudation of roll end force).

In addition, the content of the polyfunctional monomer having two or more polymerizable groups in the polymerizable compound is preferably 5 to: LOO mass% is preferable 20 to: LOO mass% is more preferable 40 to: LOO mass % Is particularly preferred.

[0097] << Photoinitiator >>

The photopolymerization initiator can be appropriately selected from known photopolymerization initiators that are not particularly limited as long as it has the ability to initiate the polymerization of the polymerizable compound. Those that have photosensitivity to visible light may have some effect with photo-excited sensitizers, and may be active agents that generate active radicals. Cationic polymerization is performed depending on the type of monomer. It may be an initiator that initiates. The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a wavelength range of about 300 to 800 nm. The wavelength ί to 330-500mn force is particularly preferred!

[0098] Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), hexarylbiimidazole, oxime derivatives, organic peroxides. Products, thio compounds, ketone compounds, aromatic onium salts, meta-octenes, and the like. Among these, from the viewpoints of the sensitivity and storage stability of the photosensitive layer and the adhesion between the photosensitive layer and the printed wiring board forming substrate, a halogenated hydrocarbon having a triazine skeleton, an oxime derivative, a ketone compound, Hexaarylbiimidazole compounds are preferred.

Specific examples of the preferable photopolymerization initiator include the compounds described in paragraph numbers [0288] to [0309] of JP-A-2005-258431.

[0099] The content of the photopolymerization initiator in the photosensitive layer is preferably 0.1 to 30% by mass.

-20% by mass is more preferred 0.5-15% by mass is particularly preferred.

[0100] <<Other ingredients>>

Examples of the other components include compounds described in paragraph numbers [03 12] to [0336] of JP-A-2005-258431. Contains these ingredients as appropriate From this, it is possible to adjust properties such as stability, photographic properties, print-out properties, and film properties of the target pattern forming material.

[0101] The thickness of the photosensitive layer is not particularly limited, and can be appropriately selected according to the purpose. However, if it is omitted, 1 to: LOO μm force S, preferably 2 to 50 μm force S 4-30 μm force S is particularly preferable.

[0102] [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.

[0103] The solvent of the photosensitive resin composition solution is not particularly limited and may be appropriately selected according to the purpose. For example, methanol, ethanol, n propanol, isopropanol, n-butanol, sec butanol , Alcohols such as n-hexanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisoptyl ketone; ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, propionic acid Esters such as ethyl, dimethyl phthalate, ethyl benzoate, and methoxypropyl acetate; aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene; carbon tetrachloride, trichloroethylene, black mouth form, 1, 1, 1— Trichloroethane, methylene chloride, monochrome benzene, etc. Halogenated hydrocarbons; ethers such as tetrahydrofuran, ethinoreethenole, ethyleneglycololemethylenoleethenole, ethyleneglycololemonoethylether, 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethylsulfoxide, Examples include sulfolane. These may be used alone or in combination of two or more. In addition, a known surfactant may be added.

Next, the photosensitive resin composition solution is applied on a support and dried to form a photosensitive layer, whereby a pattern forming material can be produced.

The method for applying the photosensitive resin composition solution is not particularly limited, and can be appropriately selected according to the purpose. For example, spray method, roll coating method, spin coating method, slit coating method, etatrusion Coating method, curtain coating method, die coating method, gravure Various coating methods such as a 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 ratio of use, etc., but are usually 60 to 110 ° C. for 30 seconds to 15 minutes.

[0105] <<Support>>

The support is not particularly limited, and can be appropriately selected according to the purpose. However, it is preferable that the photosensitive layer is peelable and has good light transmittance. Further, the surface is smooth. It is more preferable that the property is good.

[0106] The support is preferably made of a synthetic resin and transparent, for example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic. Alkyl ester, poly (meth) acrylate ester copolymer, polychlorinated butyl, polybulal alcohol, polycarbonate, polystyrene, cellophane, polysalt-vinylidene copolymer, polyamide, polyimide, salt-vinyl '' Various plastic films such as butyl acetate copolymer, polytetrafluoroethylene, polytrifluoroethylene, cellulose-based film, nylon film and the like can be mentioned, and among these, polyethylene terephthalate is particularly preferable. These may be used alone or in combination of two or more.

[0107] The thickness of the support is not particularly limited, and can be appropriately selected according to the purpose. However, if it is omitted, 2 to 150 μm force S, preferably 5 to: LOO μm force S Preferably, 8 to 50 μm force S is particularly preferable.

[0108] The shape of the support is not particularly limited, and can be appropriately selected according to the purpose, but is preferably long. The length of the long support is not particularly limited, and examples thereof include those having a length of 10 to 20, OOOm.

[0109] 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, polyethylene, paper laminated with polypropylene, and the like. Among these, a polyethylene film and a polypropylene film are preferable.

The thickness of the protective film is not particularly limited and can be appropriately selected according to the purpose. For example, 5 to: LOO μm force S is preferable, 8 to 50 μm force S is more preferable, and 10 to 30 μm force S is particularly preferable.

When the protective film is used, it is preferable that the adhesive force A of the photosensitive layer and the support and the adhesive force B of the photosensitive layer and the protective film satisfy the relationship of adhesive force A> adhesive force B.

[0110] Examples of the combination of the support and the protective film (support Z protective film) include, for example, polyethylene terephthalate Z polypropylene, polyethylene terephthalate Z polyethylene, polychlorinated bur Z cellophane, polyimide Z polypropylene, polyethylene terephthalate. z Examples include polyethylene terephthalate. In addition, the above-described adhesive force relationship can be satisfied by surface-treating at least one of the support and the 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, glossy treatment, One discharge irradiation treatment, active plasma irradiation treatment, laser beam irradiation treatment and the like can be mentioned.

[0111] The coefficient of static friction between the support and the protective film is preferably 0.3 to 1.4, more preferably 0.5 to 1.2 force! / !.

If the coefficient of static friction is less than 0.3, slipping may occur excessively, so that a deviation may occur when the roll is formed, and if it exceeds 1.4, it is difficult to wind in a good roll. Sometimes.

[0112] The pattern forming material is preferably stored, for example, by winding it around a cylindrical core and winding it into a long roll. The length of the long pattern forming material is not particularly limited. For example, a range force of 10-20,000 m can be appropriately selected. In addition, slitting may be performed to make it easy for the user to use, and a long body in the range of 100 to 1,000 m may be rolled. In this case, it is preferable that the support is scraped off 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 the packaging has low moisture permeability. I prefer to use materials. [0113] 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 polybutyl alcohol is formed on the surface of the protective film. The undercoat layer is formed by applying the polymer coating solution to the surface of the protective film and then drying at 30 to 150 ° C (particularly 50 to 120 ° C) for 1 to 30 minutes. Can do. In addition to the photosensitive layer, the support, and the protective film, it may have a layer such as a release layer, an adhesive layer, a light absorption layer, and a surface protective layer.

[0114] <Substrate to be treated>

The substrate to be treated (hereinafter sometimes referred to as “substrate”) can be appropriately selected from known materials having no particular limitation, from those having high surface smoothness to those having an uneven surface. Specifically, a plate-like substrate (substrate) is preferable. Known printed wiring board forming substrates (for example, copper-clad laminates), glass plates (for example, soda glass plates), synthetic oil-repellent films , Paper, metal plate and the like.

[0115] The substrate can be used by forming a laminated body in 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.

[0116] The pattern forming material can be widely used for pattern formation of printed wiring boards, color filters, pillar materials, rib materials, spacers, display members such as partition walls, holograms, micromachines, and proofs. In particular, it can be suitably used in the pattern forming method of the present invention.

[0117] [Other processes]

As the other steps, there is a force that can be appropriately selected from known pattern formation steps without particular limitations. Examples thereof include a development step, an etching step, and a plating step. These may be used alone or in combination of two or more.

In the development step, the photosensitive layer is exposed by the exposure step, and the photosensitive layer is exposed. After the region is cured, the uncured region is removed and developed to form a pattern.

[0118] The method for removing the uncured region is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a method for removing using a developer.

[0119] The developer is not particularly limited and may be appropriately selected according to the purpose. Examples thereof include an alkaline aqueous solution, an aqueous developer, an organic solvent, etc. Among these, a weak alkaline aqueous solution is used. preferable. Examples of the base 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, and phosphoric acid. Sodium, potassium phosphate, sodium pyrophosphate, potassium pyrophosphate, borax, etc.

[0120] The pH of the weakly alkaline aqueous solution is more preferably, for example, about 9 to about 8 to 12, preferably L1. Examples of the weak alkaline aqueous solution include 0.1 to 5% by mass of sodium carbonate aqueous solution or potassium carbonate aqueous solution.

The temperature of the developer may be appropriately selected according to the developability of the photosensitive layer. For example, the temperature is preferably about 25 ° C. to 40 ° C.

[0121] The developer is a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.) In order to accelerate development, an organic solvent (for example, alcohols, ketones, esters, ethers, amides, latatones, etc.) may be used in combination. The developer may be an aqueous developer obtained by mixing water or an alkaline aqueous solution and an organic solvent, or may be an organic solvent alone.

[0122] The etching step can be performed by a method appropriately selected from among known etching methods.

The etching solution used for the etching treatment can be appropriately selected according to the purpose without any particular limitation. For example, when the metal layer is formed of copper, a cupric chloride solution, Ferric solution, alkaline etching solution, hydrogen peroxide-based etching solution, etc. A ferric solution is preferred.

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.

The permanent pattern is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include a wiring pattern.

[0123] 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, and Watt bath (nickel sulfate-salt nickel nickel) plating.

And nickel plating such as nickel sulfamate, and gold plating such as hard gold plating and soft gold plating.

A permanent pattern can be formed on the surface of the substrate by removing the pattern after performing a plating process in the plating process, and further removing unnecessary portions by an etching process or the like as necessary.

[0124] The pattern forming method of the present invention reduces variations in resolution and density unevenness of the pattern formed on the exposed surface of the pattern forming material, and suppresses distortion of an image to be formed. Since the pattern can be formed with high definition and efficiency, it can be suitably used for forming various patterns that require high-definition exposure, and particularly suitable for forming high-definition wiring patterns. Can be used.

[Manufacturing Method of 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, a method for producing a printed wiring board using the pattern forming method of the present invention will be described.

[0126] In particular, as a method for producing a printed wiring board having a hole portion such as a through hole or a via hole, (1) the pattern forming material is formed on a printed wiring board forming substrate having a hole portion as the base. A photosensitive layer is laminated in a positional relationship to be on the substrate side to form a laminate, and (2) a wiring pattern forming region is formed from the side of the laminate opposite to the substrate. Light irradiation to the area and hole formation area! (3) The photosensitive layer is cured, (3) the support in the pattern forming material is removed from the laminate, and (4) the photosensitive layer in the laminate is developed, and the uncured portion in the laminate is removed. A pattern can be formed by removing.

[0127] The removal of the support in (3) may be performed between (1) and (2) instead of between (2) and (4). Good.

[0128] 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, Semi-additive method and full additive method)). Among these, the subtractive method is preferable in order to form a printed wiring board with industrially advantageous tenting. 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, the copper thin film portion is further etched after the peeling to produce a desired printed wiring board. can do. A multilayer printed wiring board can also be manufactured in the same manner as the printed wiring board manufacturing method.

[0129] Next, a method for producing a printed wiring board having through holes using the pattern forming material will be further described.

[0130] 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 laminated 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. And press-bonding using a pressure roller (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. The lamination temperature of the pattern forming material is not particularly limited, and examples thereof include room temperature (15 to 30 ° C.) or under heating (30 to 180 ° C.). Among these, under heating (60 to 140 ° C.) C) is preferred. The roll pressure of the pressure-bonding roll is not particularly limited. For example, 0.1 to 1 MPa is preferable. The speed of the pressure-bonding is particularly preferably 1 to 3 mZ without limitation.

Alternatively, the printed wiring board forming substrate may be preheated or laminated under reduced pressure.

[0132] In addition to the method of laminating and forming the photosensitive layer in the pattern forming material on the printed wiring board forming substrate, the laminated body is formed for producing a photosensitive layer of the pattern forming material. The method may be such that the photosensitive resin composition 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, if necessary (for example, when the light transmittance of the support is insufficient), the support may be peeled off and force exposure may be performed.

[0134] At this point, the support is still peeled! /. In this case, the support is peeled off from the laminate (support peeling step).

[0135] Next, the uncured region of the photosensitive layer on the printed wiring board forming substrate is dissolved and removed with an appropriate developer, and the cured layer for forming the wiring pattern and the curing for protecting the metal layer of the through hole are performed. A layer pattern is formed to expose the metal layer on the surface of the printed wiring board forming substrate (development process).

[0136] Further, after development, if necessary, post-heating treatment or post-exposure processing may be performed to further accelerate the curing reaction of the cured portion. 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 coating of the through hole prevents the etching solution from entering the through hole and corroding the metal plating in the through hole. Will remain in the prescribed shape. Thereby, a wiring pattern is formed on the printed wiring board forming substrate.

[0138] The etching solution is not particularly limited and may be appropriately selected depending on the purpose. For example, when the metal layer is formed of copper, a cupric chloride solution, a salty ferric solution, an alkaline etching solution, a hydrogen peroxide-based etching solution, and the like can be mentioned. Among these, a salty ferric solution is preferable from the viewpoint of etching factor.

Next, the cured layer is removed from the printed wiring board forming substrate as a peeled piece with a strong alkaline aqueous solution or the like (cured product removing step).

The base component in the strong alkaline aqueous solution is not particularly limited, and examples thereof include sodium hydroxide and potassium hydroxide.

The pH of the strong alkaline aqueous solution is more preferably about 13-14, for example, preferably about 12-14.

The strong alkaline aqueous solution is not particularly limited, and examples thereof include 1 to 10% by mass of sodium hydroxide aqueous solution or potassium hydroxide aqueous solution.

[0140] The printed wiring board may be a multilayer printed wiring board.

Note that the pattern forming material may be used in a Meki process that is performed only by the etching 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 monochloride-nickel) plating, nickel plating such as nickel sulfamate, Examples include hard gold plating and gold plating such as soft gold plating. Example

[0141] Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto.

[0142] (Example 1)

Manufacturing of pattern forming materials

A photosensitive resin composition solution having the following composition is applied to a 20 μm-thick polyethylene terephthalate film as the support and dried to form a 15-m-thick photosensitive layer. Manufactured.

[Composition of photosensitive resin composition solution]

'Methacrylic acid Z Methyl metatalylate Z Styrene copolymer (Copolymer composition (mass ratio):

29/19/52, mass average molecular weight: 60,000, acid value 189) 11.8 parts by mass Polymerizable monomer represented by the following structural formula (1) 5.6 mass

Hexamethylene diisocyanate and pentaethylene oxide monometaataryl

1Z2 molar ratio adduct 5.0 parts by mass

'Dodecapropylene glycol dialkyl relay 0.56 parts by mass

'N Methyl Ataridon 0.11 parts by mass

■ 2, 2 screw (o black mouth ferrule) 1, 4, A 'tetraphenyl ruby

Dazonole 2. 17 parts by mass

'2-Mercaptobenzimidazole 0.23 parts by mass

'Malachite green oxalate 0.02 parts by mass

'Royco Crystal Violet 0.26 parts by weight

'Methyl ethyl ketone 40 parts by mass

-Methoxy 2-propanol 20 parts by mass

[Chemical 1]

CH ₃ CH-,

H _? OC— CO ~ iO— CH ₂ CH ₂ "0--0 ~ (CH ₂ CH ₂ O ^ CO OCH ₂ Structural formula (1)

However, in Structural Formula (1), m + n represents 10.

On the photosensitive layer of the pattern forming material, 20 μm-thick polyethylene phenol was laminated as the protective film.

Next, while removing the protective film of the pattern forming material from the surface of the copper-clad laminate (no through-hole, copper thickness 12 m) that has been polished, washed with water and dried as the substrate, The photosensitive layer is pressed with a laminator (MODEL8B-720-PH, manufactured by Taisei Laminator Co., Ltd.) so as to be in contact with the copper-clad laminate, and the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film A laminate in which (support) was laminated in this order was prepared.

The crimping conditions were a crimping roll temperature of 105 ° C, a crimping roll pressure of 0.3 MPa, and a laminating speed of lmZ. [0146] The photosensitive layer of the pattern forming material in the prepared laminate is exposed using the following apparatus, and (a) resolution, (b) edge roughness, and (c) etchability are obtained by the following methods. evaluated. The results are shown in Table 3.

[0147] <(a) Resolution>

(1) Measuring method of shortest development time

The laminate strength is peeled off, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. is sprayed at a pressure of 0.15 MPa over the entire surface of the photosensitive layer on the copper clad laminate, Spray start force The time required for the photosensitive layer on the copper clad laminate to be dissolved and removed was measured, and this was taken as the shortest development time.

As a result, the shortest development time was 10 seconds.

[0148] (2) Sensitivity measurement

From the support side to the photosensitive layer of the pattern forming material in the prepared laminate, from the lmj / cm ² to lOOmj / cm ^{2 at} intervals of 2 ^1/2 times using the exposure apparatus described below. A part of the photosensitive layer was cured by irradiating light having different light energy amounts. After standing at room temperature for 10 minutes, the support was peeled off from the laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C was sprayed to a spray pressure of 0.15 MPa over the entire surface of the photosensitive layer on the copper clad laminate. Then, spraying was performed twice as long as the shortest development time determined in the above (1), and the uncured area was dissolved and removed, and the thickness of the remaining cured area was measured. Next, a sensitivity curve was obtained by plotting the relationship between the light irradiation amount and the thickness of the hardened layer. From the sensitivity curve, the amount of light energy when the thickness of the cured region was 15 m, 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 required to cure the photosensitive layer was 3.5 mj / cm (?).

[0149] <<Exposure equipment>>

4A to 8 as the light irradiating means and the DMD schematically shown in FIG. 2 as the light modulating means, in which 1024 micromirrors are arranged in the main scanning direction. Micromirror array force The exposure head having the DMD controlled to drive only 1024 X 256 arrays out of 768 arrays arranged in the sub-scanning direction and the optical system shown in FIG. The exposure apparatus provided was used.

[0150] In the exposure head, the condensing optical system has a predetermined distribution in the angle of the chief ray with respect to the laser light incident on the fiber array light source, separately from the light amount distribution correction function provided in the rod integrator 118. In addition, the light intensity distribution amount is set to be equal to or greater than the peripheral light amount reduction caused by the microlens array, and the optical axis shown in Fig. 9B is provided. The predetermined distance YA from the center was set to YS> YA> YSZ2, where YS is the distance from the center of the optical axis to the peripheral edge of the illumination area (the outer periphery of the DMD).

[0151] (3) Resolution measurement

The laminate was produced under the same method and conditions as in the method (1) for evaluating the shortest development time, and allowed to stand at room temperature (23 ° C., 55% RH) for 10 minutes. From the polyethylene terephthalate film (support) of the obtained laminate, using the above-mentioned exposure equipment, exposure of each line width in 1 μm increments from 10 μm to 50 μm line width with line Z space = 1Z1 I do. 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. Spray the entire surface of the photosensitive layer on the copper-clad laminate with a 1% by weight sodium carbonate aqueous solution at 30 ° C at a spray pressure of 0.15 MPa for twice the minimum development time determined in (1) above. Dissolve the area. The surface of the copper clad laminate with a cured resin pattern thus obtained is observed with an optical microscope, and there is no abnormality in the cured resin pattern line, such as scumming or misalignment, and the smallest line that can form a space. The width was measured and used as the resolution. The smaller the numerical value, the better the resolution.

[0152] <(b) Edge roughness>

Using the exposure apparatus, the laminated body is irradiated and exposed so that a horizontal line pattern perpendicular to the scanning direction of the exposure head is formed, and a part of the photosensitive layer is exposed to the resolution. A pattern was formed in the same manner as in (3) in the measurement. Of the obtained patterns, any five points on a line with a line width of 30 / zm were observed using a laser microscope (VK-950 0, manufactured by Keyence Corporation; objective lens 50x), and the edges in the field of view were observed. Out of position The absolute value of the difference between the most swollen part (mountain peak) and the most constricted part (valley bottom) was calculated, and the average value of the five observed points was calculated as the edge roughness. The edge roughness is preferably as the value is small, since it exhibits good performance. The results are shown in Table 3.

[0153] <(c) Etchability>

Using the laminate having the pattern formed in the measurement of the resolution, on the surface of the exposed copper-clad laminate in the laminate, a salted pig iron etchant (ferric chloride-containing etching solution, 40 ° Baume, Etching was performed by spraying at a liquid temperature of 40 ° C at 0.25 MPa for 36 seconds to dissolve and remove the exposed copper layer not covered with the hardened layer. Subsequently, the formed pattern was removed by spraying a 2% by mass aqueous solution of sodium hydroxide and sodium hydroxide, and a printed wiring board having a copper layer wiring pattern as the permanent pattern on the surface was prepared. 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 3.

[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 (a) resolution, (b) edge roughness, and (c) etchability were evaluated. The results are shown in Table 3.

[0155] <<Exposure equipment>>

4A to 8 as the light irradiating means and the DMD schematically shown in FIG. 2 as the light modulating means, in which 1024 micromirrors are arranged in the main scanning direction. Micromirror column force An exposure apparatus having an exposure head having a DMD controlled to drive only 1024 X 256 columns out of 768 arrays arranged in the sub-scanning direction and the optical system shown in FIG. Was used. Between the rod integrator 118 and the condenser lens 120 of the exposure head shown in FIG. 1, as a light distribution correcting means, a telecentric lens composed of a pair of plano-convex lenses 152 and 154 as shown in FIG. 11A. An optical system 150 is provided.

[0156] The plano-convex lens 152 disposed on the laser beam incident side (fiber array light source 112 side) The surface shape of the incident surface S2 is an aspheric surface whose radius of curvature increases as it moves away from the optical axis (optical axis center) X, in other words, an aspheric surface that decreases as the radius of curvature increases away from the optical axis X. It is flat.

[0157] By using this exposure apparatus, the light intensity distribution of the laser beam emitted from the telecentric optical system 150 after being collimated becomes higher in the peripheral density with respect to the center of the optical axis. In the irradiated DMD 50, the amount of light in the peripheral portion is increased from the central portion (optical axis center) of the laser light irradiation region. Thereafter, the laser beam passes through the microlens array 128 to cause a reduction in the amount of light in the peripheral portion with respect to the central portion of the optical axis, and the exposure surface is irradiated with the light beam corrected so that the light amount distribution is uniform.

[Example 3]

In Example 1, a 1Z2 molar addition product of hexamethylene diisocyanate and pentaethylene oxide monomethaacrylate in the photosensitive resin composition solution is represented by the following structural formula (2). A pattern forming material and a laminate were prepared in the same manner as in Example 1 except that the compound was replaced with the above compound. A pattern was formed, and (a) resolution, (b) edge roughness, and (c) etching property were evaluated. . The results are shown in Table 3.

The shortest development time was 10 seconds, and the amount of photoenergy required to cure the photosensitive layer was 3.5 mjZcm ² .

[0159] [Chemical 2]

,,

Structural formula (2)

[Example 4]

In Example 1, a 1Z2 molar ratio adduct of hexamethylene diisocyanate and tetraethylene oxide monomethaacrylate in the photosensitive resin composition solution is represented by the following structural formula (3). A pattern forming material and a laminate were prepared in the same manner as in Example 1 except that the compound was changed to a non-turned material, and (a) resolution, (b) edge roughness, and (c) etching property were evaluated. I was worth it. The results are shown in Table 3.

[0161] [Chemical 3]

Et— -cc H OC H _? CH, OCON H- 1 CH,), -NHCO 0- (CH, CH _? 0} _(i CO ~), 3.)

[0162] (Example 5)

In Example 1, methacrylic acid Z methyl metatalylate Z styrene copolymer (copolymer composition (mass ratio): 29Z19Z52, mass average molecular weight: 60,000, acid value 189) was converted to methyl metatalylate Z styrene. Example 1 except that Z benzyl metatalate Z methacrylic acid copolymer (copolymer composition (mass ratio): 8/30/37/25, mass average molecular weight: 60,000, acid value 163) In the same manner as above, a pattern forming material and a laminate were prepared, a pattern was formed, and (a) resolution, (b) edge roughness, and (c) etching property were evaluated. The results are shown in Table 3.

The shortest development time is 10 seconds, and the light energy required to cure the photosensitive layer is approximately 4 mj / cm (?

[0163] (Comparative Example 1)

In the exposure apparatus of Example 1, a pattern forming material and a laminate were prepared in the same manner as in Example 1 except that an exposure head having a configuration that does not include a light distribution correction unit in the condensing optical system was prepared. And (a) resolution, (b) edge roughness, and (c) etchability were evaluated. The results are shown in Table 3.

The amount of light energy required to cure the photosensitive layer was 3.5 miZcm ²

[0164] (Comparative Example 2)

In the exposure apparatus of Embodiment 2, the light collecting optical system is not equipped with light distribution correction means! Except for using the exposure head with the configuration, the pattern forming material and the laminate were prepared in the same manner as in Example 2. It was prepared to form a pattern, and (a) resolution, (b) edge roughness, and (c) etching property were evaluated. The results are shown in Table 3.

[0165] [Table 3]

[0166] From the results of Table 3, compared to the wiring patterns of Comparative Examples 1 and 2, the wiring patterns of Examples 1 to 5 using the exposure head equipped with the light distribution correcting means are high-definition, and the edge roughness is used. In addition, it was also strong that it was excellent in etching property. Furthermore, by using an exposure head equipped with light distribution correction means, it was possible to realize high-definition exposure at low cost and to perform efficient exposure.

Industrial applicability

[0167] The pattern forming method of the present invention provides a light amount of each drawing unit that is two-dimensionally distributed while suppressing costs in exposure using a digital exposure apparatus including an exposure head in which drawing units are two-dimensionally distributed. By making the pattern uniform, it is possible to provide a pattern forming method capable of forming a fine pattern with high precision, and therefore, it can be suitably used for forming various patterns that require high-definition exposure. In particular, it can be suitably used for forming a high-definition wiring pattern.

Claims

The scope of the claims

[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 photosensitive layer has n (where n is a natural number of 1 or more) two-dimensionally arranged pixel parts, and the light modulation state is changed for each of the pixel parts according to pattern information. The light modulation means is irradiated with a light beam emitted from the light irradiation means via a condensing optical system having a light distribution correction means, and exposure is performed by irradiating the light beam modulated by the light modulation means. Including at least

The exposure gives a distribution of the amount of light within the irradiation region of the light beam irradiated from the light irradiation unit to the light modulation unit, and the light amount distribution force of the light beam modulated by the light modulation unit. A pattern forming method, wherein the correction is performed so as to be uniform on the exposed surface.

2. The pattern forming method according to claim 1, wherein the light modulating unit irradiates the light modulating unit with the light beam emitted from the light irradiating unit as a light beam having a distribution in the angle of the principal ray by the condensing optical system.

[3] The pattern forming method according to [1], wherein the emitted light beam is irradiated to the light modulation means as telecentric light by a condensing optical system.

[4] A first optical lens having an aspherical shape in which the condensing optical system decreases in lens power as it moves away from the optical axis center, and an aspherical shape in which the lens power increases as it moves away from the optical axis center The pattern forming method according to claim 3, further comprising: a light distribution correction unit including a second optical lens having

[5] The condensing optical system according to any one of claims 1 to 4, wherein the condensing optical system increases the amount of light in the peripheral portion rather than the central portion in the irradiation region of the light beam irradiated from the light irradiation means to the light modulation means. Pattern forming method.

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 any one of claims 1 to 6, wherein the photosensitive layer is developed after the exposure.

[8] The permanent pattern is formed after the development is performed. Pattern forming method.

The pattern forming method according to claim 8, 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 forming method according to claim 1, wherein:

A light irradiating means collects a plurality of lasers, a multimode optical fiber, and a laser beam irradiated from each of the plurality of lasers into parallel light and collects the light, and converges it on the incident end face of the multimode optical fiber. The pattern formation method according to claim 1, further comprising: an optical optical system.

12. The pattern forming method according to claim 1, wherein the photosensitive layer contains a binder, a polymerizable compound, and a photopolymerization initiator.

13. The pattern forming method according to claim 12, wherein the binder has an acidic group.

The pattern forming method according to any one of claims 12 to 13, wherein the pattern is a bull copolymer.

The pattern forming method according to claim 12, wherein an acid value of the binder is 70 to 250 mg KOHZg.

16. The pattern forming method according to claim 12, wherein the polymerizable compound contains a monomer having at least one of a urethane group and an aryl group.

The photopolymerization initiator is also selected from halogenated hydrocarbon derivatives, hexarylbiimidazole, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, and metallocenes. The pattern forming method according to claim 12, comprising at least one selected from the group consisting of:

18. The pattern forming method according to claim 1, 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: LOO m.

The support according to any one of claims 1 to 19, wherein the support contains a synthetic resin and is transparent. Pattern forming method.

21. The pattern forming method according to claim 1, wherein the support has a long shape.

[22] The pattern forming method according to any one of claims 1 to 21, wherein the pattern forming material has a long shape and is wound in a roll shape.

[23] The pattern forming method according to any one of [1] to [22], wherein a protective film is formed on the photosensitive layer in the non-turn forming material.