KR20060111692A - Pattern forming process - Google Patents

Abstract

The object of the present invention is to provide pattern forming processes that may form permanent patterns such as a wiring pattern with high fineness and preciseness, and sufficient efficiency due to suppressing the image deformation formed on pattern forming materials. In order to attain the object, a pattern forming process is provided that comprises modulating a laser beam irradiated from a laser source, compensating the modulated laser beam, and exposing a photosensitive layer by the modulated and compensated laser beam, wherein the photosensitive layer is disposed on a support to form a pattern forming material, the modulating is performed by a laser modulator that comprises plural imaging portions each capable of receiving the laser beam and outputting the modulated laser beam, and the compensating is performed by transmitting the modulated laser beam through plural microlenses each having a non-spherical surface capable of compensating the aberration due to distortion of the output surface of the imaging portion, and the plural microlenses are arranged to a microlens array.

Description

Pattern Formation Method {PATTERN FORMING PROCESS}

The present invention relates to a pattern forming method in which a laser beam modulated by a laser modulator such as a spatial light modulator is formed on a pattern forming material and the pattern forming material is exposed.

BACKGROUND ART Exposure apparatuses which transmit light or laser beam modulated by a spatial light modulator or the like to an imaging optical system to form an optical image on a pattern forming material and expose the pattern forming material are widely known. In general, such an exposure apparatus includes a spatial light modulator having a two-dimensional array of a plurality of drawing units for modulating incident light or a laser beam according to various control signals, a laser source for irradiating a laser beam to the spatial light modulator, and the It consists of an imaging optical system that forms an image from a laser beam modulated by a spatial light modulator onto a pattern forming material (Akito Ishikawa, "Shortening of Research and Application to Massproduction by Maskless Exposure", Electronics Jisso Gijyutsu, Gicho Pulishing & Advertising Co., Ltd., vol. 18, No. 6, pp. 74-79 (2002); Japanese Patent Application Laid-Open No. 2004-1244).

Examples of the spatial light modulator include liquid crystal displays (LCDs), digital micromirror devices (DMDs), and the like. The DMD is a mirror device having, as the drawing unit, a two-dimensional array of a plurality of micromirrors that change half squareness in accordance with a control signal.

In the above exposure apparatus, it is often required to enlarge the image projected on the pattern forming material, and in response to this request, an enlarged imaging optical system is used as the imaging optical system. However, the method of transmitting the modulated light from the spatial light modulator alone to the magnification imaging optical system enlarges the luminous flux from each drawing part of the spatial light modulator, so that the pixel size in the projected pattern is enlarged, so that the sharpness of the pixel. There is a problem that is lowered.

In order to solve this problem, Japanese Patent Laid-Open No. 2004-1244 discloses that a first imaging optical element is disposed in an optical path of a laser beam modulated by the spatial light modulator, and the microstructure is formed on an imaging surface of the first imaging optical element. A lens array is disposed, wherein the microlenses respectively correspond to the imaging portion of the spatial light modulator, and pattern the modulated light in the optical path of the laser beam from the microlens array to form the modulated light on a pattern forming material. There is proposed an enlarged projection in which a second imaging optical element that forms an image on a forming material or a screen is located, and an image is enlarged by the first and second imaging optical elements. In this proposal, the size of the image projected onto the pattern forming material or the screen can be enlarged, while the laser beam from each drawing portion of the spatial light modulator is condensed by the respective microlenses of the array, so that the projected image Grave size or spot size is reduced in focus, and image sharpness is increased.

Moreover, the exposure apparatus which combined the DMD and microlens array as a spatial light modulator is proposed (refer Unexamined-Japanese-Patent No. 2001-305663). In addition, a similar exposure apparatus has also been proposed, in which an opening plate having an opening corresponding to the microlens of the array is arranged at the rear side of the microlens array so that only a laser beam through the microlens passes through the opening (Japanese Patent Laid-Open) See 2001-500628). In these exposure apparatuses, the extinction ratio can be increased by preventing the incidence of the laser beam from adjacent microlenses not corresponding to the respective openings.

However, these proposals use a laser beam focused by the microlenses of the array, so that there is a problem that the image formed on the pattern forming material is deformed. This problem is particularly noticeable when using DMD as a spatial light modulator.

As described above, by suppressing the phase deformation formed on the pattern forming material, a pattern forming method capable of forming fine patterns such as wiring patterns with high precision and efficiency has not yet been provided; In addition, it is a reality that the improvement of the pattern formation method is required.

SUMMARY OF THE INVENTION An object of the present invention is to provide a pattern forming method which can form permanent patterns such as wiring patterns with high precision and efficiency by suppressing phase deformation formed on a pattern forming material.

The above object can be achieved by the present invention. According to the present invention, there is provided a pattern forming method comprising modulating a laser beam irradiated from a laser source, correcting the modulated laser beam, and then exposing the photosensitive layer with the modulated corrected laser beam. Disposed on a support to form a pattern forming material, wherein the modulation is performed by a laser modulator comprising a drawing portion capable of receiving a laser beam and emitting a modulated laser beam, and the correction is caused by distortion of the exit surface of the drawing portion. Provided is a pattern forming method in which a modulated laser beam is transmitted through a plurality of microlenses each having an aspherical surface capable of correcting aberration, and the plurality of microlenses are arranged in a microlens array.

In the pattern forming method, the laser source irradiates the laser beam toward the laser modulator, and the laser beam received by the plurality of the drawing units is modulated by irradiating the laser beam from the drawing unit, and the distortion of the output surface of the drawing unit is distorted. Since the aberration due to is corrected by transmitting the modulated laser beam through the plurality of microlenses, it is possible to effectively control the distortion of the image formed on the pattern forming material. As a result, exposure to the pattern forming material can be made very fine, and a fine pattern can be obtained by developing the photosensitive layer.

Preferably, the aspheric surface is a toric surface. The aspheric toric surface can effectively correct aberrations caused by the distortion of the exit surface of the drawing portion, thereby effectively controlling the distortion of the image formed on the pattern forming material. As a result, exposure to the pattern forming material can be made very fine, and a fine pattern can be obtained by developing the photosensitive layer.

Preferably, the laser modulator may control a part of the plurality of drawing units in accordance with the pattern information. The laser beam can be modulated at high speed by controlling the plurality of drawing units in accordance with the pattern information.

Preferably, the laser modulator is a spatial light modulator, more preferably the spatial light modulator is a digital micromirror device (DMD).

Preferably, the exposure is done by a laser beam transmitted through the aperture array. Exposure by the laser beam transmitted through this aperture array can increase the extinction ratio. As a result, exposure to the pattern forming material can be made very fine, and a fine pattern can be obtained by developing the photosensitive layer.

Preferably, the exposure is performed while relatively moving the laser beam and the photosensitive layer. Exposure can be performed at high speed by performing exposure while moving a laser beam and a photosensitive layer relatively.

Preferably, the post-exposure photosensitive layer is developed, and a post-development permanent pattern is formed.

Preferably, the permanent pattern is a wiring pattern, and by forming the permanent pattern by at least one of an etching process and a plating process, a highly fine wiring pattern can be formed.

Preferably, the laser source may irradiate two or more kinds of lasers together. By irradiating two or more kinds of these lasers, the depth of focus can be deepened and exposed. As a result, exposure to the pattern forming material can be made very fine, and a fine pattern can be obtained by developing the photosensitive layer.

Preferably, the laser source includes a plurality of lasers, a multimode optical fiber, and an aggregation optical system for condensing the laser beams from the plurality of lasers onto the multimode optical fiber. This configuration makes it possible to expose the depth of focus deeply. As a result, exposure to the pattern forming material can be made very fine, and a fine pattern can be obtained by developing the photosensitive layer.

Preferably, the photosensitive layer comprises a binder, a polymerizable compound, and a photopolymerization initiator; Preferably the binder contains acidic groups; Preferably the binder contains a vinyl copolymer; Preferably the acid value of the binder is 70 ~ 250mgKOH / g.

Preferably, the polymerizable compound contains a monomer having at least one of a urethane group and an aryl group.

Preferably, the photopolymerization initiator is a compound selected from the group consisting of halogenated hydrocarbon derivatives, hexaaryl-biimidazole, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, acylphosphine oxides and metallocenes It contains.

Preferably, the said photosensitive layer contains 30-90 mass% of binders, 5-60 mass% of polymeric compounds, and 0.1-30 mass% of a photoinitiator; Preferably the thickness of the photosensitive layer is 1 ~ 100㎛.

Preferably, the support contains a synthetic resin and is transparent; Preferably the support is elongate; Preferably, the pattern forming material is a long shape formed by winding in a roll shape.

Preferably, a protective film is formed on the photosensitive layer of the said pattern forming material.

(Pattern Forming Method)

The pattern forming method according to the present invention includes an exposure step, and another step suitably selected.

Exposure process

In the exposure step, the pattern forming method comprising the step of modulating the laser beam irradiated from the laser source, correcting the modulated laser beam, and then exposing the photosensitive layer with the modulated and corrected laser beam, wherein the photosensitive layer is Disposed on a support to form a pattern forming material, wherein the modulation is performed by a laser modulator including a plurality of drawing portions capable of receiving a laser beam and emitting a modulated laser beam, respectively, and the correction is performed on the exit surface of the drawing portion. A pattern forming method is provided by transmitting a modulated laser beam through a plurality of microlenses each having an aspherical surface for correcting aberration due to distortion, and the plurality of microlenses are arranged in a microlens array.

Laser Modulator

The laser modulator may be appropriately selected depending on the purpose as long as it includes a plurality of drawing parts. Preferred examples of laser modulators include spatial light modulators.

Specific examples of the spatial light modulator include a spatial light modulator in the form of a digital micromirror device (DMD), a micro electro mechanical system (MEMS), a PLZT element, and a liquid crystal satter; Among these, DMD is preferable.

An example of a laser modulator will be described below with reference to the drawings.

DMD 50 is a mirror device having a lattice array of multiple, eg, 1024 × 768, micromirrors 62 on an SRAM cell or memory cell 60, as shown in FIG. 1, where each micromirror is a drawing portion. Act as. The micromirror 62 is supported by the pillar at the top of each drawing part. On the surface of the micromirror, a material having high reflectance such as aluminum is deposited. The reflectivity of the micromirror 62 is at least 90%; For example, the array pitch in the longitudinal direction and the width direction is 13.7 µm, respectively. Further, just below each micromirror 62, an SRAM cell 60 of a silicon gate CMOS manufactured by a conventional semiconductor memory manufacturing method is arranged through pillars including a hinge and a yoke. The mirror device is composed entirely of a monolithic body.

When a digital signal is written into the SRAM cell 60 of the DMD 50, the micromirror 62 supported by the pillar has a diagonal relative to the substrate on which the DMD 50 is disposed, and the angle of rotation is ± α degrees, for example. Tilt within ± 12 degrees. FIG. 2A illustrates a state where + α is also inclined when the micromirror 62 is on, and FIG. 2B illustrates a state where -α is also inclined when the micromirror 62 is off. As shown in FIG. 1, according to the pattern information, each incident laser beam B with respect to the DMD 50 controls the inclination angle of each of the micromirrors 62 in the drawing portion of the DMD 50. As a result, the micromirrors 62 are reflected along the inclined direction of each micromirror 62.

1 shows an example of a partially enlarged state of the DMD 50 in which the micromirror 62 is controlled at -α degrees or + α degrees. The controller 302 connected to the DMD 50 performs on-off control of each micromirror 62. A light absorber (not shown) is arranged in the direction of the laser beam B reflected by the off-state micromirror.

Preferably, the DMD 50 is inclined slightly with its short side at a predetermined angle with respect to the sub-scanning direction, for example, 0.1 to 5 degrees. 3A shows the scanning trajectory of the reflection laser image or the exposure beam 53 by each micromirror when the DMD 50 is not inclined; 3B shows the scanning trajectory of the reflection laser image or the exposure beam 53 by each micromirror when the DMD 50 is inclined.

In the DMD 50, a plurality of micromirrors, for example, 1024 micromirrors are arranged in the longitudinal direction to form an array, and a plurality of arrays, for example, 756 are arranged in the short direction. Thus, by tilting the DMD 50 as shown in FIG. 3B, the scan trace of the exposure beam 53 or the pitch P ₂ of the scan line from each micromirror does not incline the DMD 50, or Since the pitch P ₁ of the scan line is reduced, the resolution can be significantly improved. On the other hand, since the inclination angle of the DMD 50 is small, the scanning direction W ₂ when the DMD 50 is inclined and the scanning direction W ₁ when the DMD 50 is not inclined are substantially the same.

Hereinafter, a method for accelerating the modulation speed of the laser modulator (hereinafter referred to as "high speed modulation") will be described.

Preferably, the laser modulator can control less than " n " arbitrary drawing units continuously arranged among the drawing units according to the pattern information (an integer of " n " 2 or more). The data processing speed of the laser modulator has a limitation, and the modulation rate per line is determined in proportion to the number of drawing units used, so that the modulation rate per line can be increased by simply using " n " drawing units arranged in succession. Can increase.

The high speed modulation will be described below with reference to the drawings.

When the laser beam B is irradiated from the fiber array laser source 66 to the DMD 50, the laser beam reflected when the micromirror of the DMD 50 is on is patterned by the lens system 54, 58 by the lens system 54, 58. It is imaged on 150. In this way, the laser beam irradiated from the fiber array laser source 66 is turned on or off by the respective drawing portions, so that the pattern forming material 150 is approximately equal to the number of writing portions used for the DMD 50. The unit or the exposure area 168 is exposed. In addition, when the pattern forming material 150 is moved with the stage 152 at a constant speed, the pattern forming material 150 is sub-scanned by the scanner 162 in a direction opposite to the stage moving direction, so that each exposure is performed. A band-shaped exposure area 170 is formed corresponding to the head 166.

In this example, as shown in Figs. 4A and 4B, in the DMD 50, 1024 arrays of micromirrors are arranged in the main-scan direction and 768 arrays in the sub-scanning direction. Of these micromirrors, a portion of the micromirror, such as 1024 × 256, may be controlled by the controller 302.

In this control, as shown in Fig. 4A, a micromirror array disposed at the center of the DMD 50 may be used; Alternatively, as shown in FIG. 4B, a micromirror array disposed at the edge of the DMD 50 may be used. In addition, when the micromirror is partially damaged, the micromirror used may be appropriately changed depending on the situation, such as using an undamaged micromirror.

The data processing speed of the DMD 50 is limited, and since the modulation speed per line is determined in proportion to the number of drawing units used, the modulation speed per line is increased by using some micromirror arrays. In addition, when exposure is performed continuously with respect to an exposure surface in proportion to an exposure head, it is not necessary to use all drawing parts in a sub-scanning direction.

When the sub-scanning of the pattern forming material 150 is finished by the scanner 162 and the rear end of the pattern forming material 150 is detected by the sensor 164, the stage 152 is gated along the guide 158. Returning to the origin at the most upstream side of 160, the stage 152 is again moved along the guide 158 at a constant speed from the upstream side to the downstream side of the gate 160.

For example, using 384 arrays of 768 micromirror arrays, the modulation rate can be twice as fast as when using all 768 arrays; In addition, using 256 of the 768 micromirror arrays, the modulation rate can be three times faster than using all 768 arrays.

As described above, when the DMD 50 is equipped with 1,024 micromirror arrays in the main-scan direction and 768 micromirror arrays in the sub-scan direction, the entire micromirror is controlled by controlling and driving some micromirror arrays. Compared to controlling and driving an array, the modulation rate per line is faster.

In addition to controlling and driving some micromirror arrays, a long DMD in which a plurality of micromirrors are arranged on a substrate in a two-dimensional array in the case where the angle of each reflecting surface can be changed according to various control signals The modulation rate can be increased, and the substrate is longer in a predetermined direction than its vertical direction.

It is preferable to perform the exposure while moving the exposure laser and the photosensitive layer relatively; It is more preferable to use the exposure together with the high speed modulation because the exposure can be performed at high speed in a short time.

As shown in Fig. 5, the entire surface of the pattern forming material 150 may be exposed by one scan of the scanner 162 in the X direction; Alternatively, as shown in FIGS. 6A and 6B, the scanner 162 scans the pattern forming material 150 in the X direction, and then moves the scanner 162 one step in the Y direction and then scans in the X direction. The entire surface of the pattern forming material 150 may be exposed by repeating the exposure. In this example, the scanner 162 includes 18 exposure heads 166; Each exposure head includes the laser source and the laser modulator.

The exposure is performed on a partial region of the photosensitive layer, whereby the partial region is cured, and then a pattern is formed by removing uncured regions other than the partial cured region in a developing step described later.

Next, an example of the pattern forming apparatus including the laser modulator will be described with reference to the drawings.

The pattern forming apparatus including the laser modulator includes a flat stage 152 that adsorbs and holds a sheet-shaped pattern forming material 150 on its surface.

On the upper surface of the thick plate-shaped table 156 supported by the four leg portions 154, two guides 158 extending along the stage moving direction are arranged. The stage 152 is disposed such that its longitudinal direction is directed toward the stage moving direction, and is supported in a mutually movable manner by the guide 158. The pattern forming apparatus is provided with a driving device (not shown) for driving the stage 152 along the guide 158.

The gate 160 is provided at the center of the table 156 so that the gate 160 crosses the path of the stage 152. Each end of the gate 160 is fixed to both sides of the table 156. A scanner 162 is installed at one side of the gate 160, and a plurality of (eg, two) detection sensors 164 for sensing the front and rear ends of the pattern forming material 150 at the other side of the gate 160. Is installed. The scanner 162 and the detection sensor 164 may be attached to the gate 160, respectively, and are fixedly positioned above the path of the stage 152. The scanner 162 and sensor 164 are connected to a controller (not shown) that controls them.

As shown in FIGS. 8 and 9B, the scanner 162 includes a plurality of (eg, 14) exposure heads 166 arranged in a substantially matrix shape of “m rows × n columns” (eg, 3 × 5). Equipped with. In this example, four exposure heads 166 are arranged in the third row in consideration of the width of the pattern forming material 150. "m""n" specified in the exposure head in the column of the row will be referred to below as exposure head 166 _mn.

The exposure area 168 by the exposure head 166 is a rectangle having short sides in the sub-scanning direction. Therefore, the exposure area 170 is formed on the band-shaped exposure forming material 150 corresponding to each exposure head 166 as the stage 152 moves. In addition, the specific exposure area | region corresponding to the exposure head of m-th nth column is represented by exposure area _168mn below.

9A and 9B, each of the exposure heads in each row is spaced in the line direction such that the band-shaped exposure area 170 is arranged without space in the direction orthogonal to the sub-scanning direction. Long side) x (natural number); twice in this example). Therefore, the non-exposed areas between the exposure area 168 ₁₁ and the exposure area 168 ₁₂ of the first row can be exposed by the exposure area 168 ₂₁ of the second row and the exposure area 168 ₃₁ of the third row.

Each of the exposure heads 166 _{11 to} 166 _mn is a digital micromirror device (DMD) 50 (US Texas Instrunemts Inc) as a laser modulator or a spatial light modulator for modulating the incident laser beam according to pattern information as shown in FIGS. 10 and 11. Product). Each DMD 50 is connected to the controller 302 provided with a data processing part and a mirror drive part as shown in FIG. The data processor of the controller 302 generates a control signal for controlling and driving each of the micromirrors in the area to be controlled for each of the exposure heads 166 based on the input pattern information. The area to be controlled will be described later. The mirror drive-control unit controls the reflection surface angle of each micromirror of the DMD 50 for each exposure head 166 based on the control signal generated by the pattern information processing unit. Control of the reflection surface angle will be described later.

The fiber array laser source 66, the fiber array laser source, having a laser irradiation section arranged in an array along the direction corresponding to the long side direction of the exposure area 168 at the laser incidence side of the DMD 50 at the emitting end or the light emitting point. A lens system 67 for correcting the laser beam from 66 and condensing it on the DMD, and a mirror 69 for reflecting the laser beam through the lens system 67 toward the DMD 50 are arranged in this order. . 10 schematically shows the lens system 67.

As shown in Fig. 11, the lens system 67 includes a condenser lens 71 for condensing the laser beam B for illumination from the fiber array laser source 66, and inserted into the optical path of the laser beam that has passed through the condenser lens 71. A rod-shaped optical coupler (hereinafter referred to as " rod coupler ") 72 and an imaging lens 74 disposed in front of the rod coupler 72 or on the mirror 69 side. The condenser lens 71, the rod coupler 72, and the imaging lens 74 enter the laser beam irradiated from the fiber array laser source 66 into the DMD 50 as a light beam of a substantially parallel beam having a uniform cross-sectional intensity. . The shape and action of this rod coupler 72 will be described later in detail.

The laser beam B irradiated from the lens system 67 is reflected by the mirror 69 and is irradiated to the DMD 50 through the total reflection prism 70 (not shown in FIG. 10).

On the reflection side of the DMD 50, an imaging system 151 is formed which forms the laser beam B reflected by the DMD 50 on the pattern forming material 150. As shown in FIG. 11, the imaging system 151 includes a first imaging system of the lens systems 52 and 54, a second imaging system of the lens systems 57 and 58, and a microlens array 55 inserted between the imaging systems. And an opening array 59 are provided.

Each of the drawing portions of the DMD 50 respectively corresponds to a plurality of microlenses 55a arranged in two dimensions to form the microlens array 55. In this example, since the micromirrors of 1024 columns x 256 rows of the 1024 columns x 768 rows of the DMD 50 are driven, the pitch of the microlenses 55a in which 1024 columns x 256 rows of the microlenses are correspondingly arranged is in the row direction. And 41 mu m for both the column direction. The microlens 55a has, for example, a focal length of 0.19 mm, a numerical aperture NA of 0.11, and is formed of optical glass BK7. The shape of the microlenses will be described later. The beam diameter of the laser beam B at the position of the microlens 55a is 41 mu m.

The opening array 59 is formed of a plurality of openings 59a in which each microlens 55a of the microlens array 55 respectively corresponds. The diameter of the opening 59a is 10 micrometers, for example.

The first imaging system forms an image on the microlens array 55 as a three-fold enlarged image of the DMD 50. The second imaging system is an image magnified 1.6 times through the microlens array 55 to image and project onto the pattern forming material 150. Therefore, the image by the DMD 50 is imaged and projected on the pattern forming material 150 as the image 4.8 times enlarged.

On the other hand, a prism pair 73 is provided between the second imaging system and the pattern forming material 150 and is moved on the pattern forming material 150 by an operation of moving the prism pair 73 in the vertical direction. The upper focus of can be adjusted. In Fig. 11, the pattern forming material 150 is supplied in sub-scanning in the direction of the arrow F. Figs.

The drawing unit may be appropriately selected according to the purpose as long as it can receive the laser beam from the laser source or the laser irradiation means and can emit the laser beam; For example, when the pattern formed by the pattern forming method according to the present invention is an image pattern, the drawing portion is a pixel, or when the laser modulator includes a DMD, the drawing portion is a micromirror.

A plurality of drawing units included in the laser modulator may be appropriately selected according to the purpose.

The arrangement of the drawing portions of the laser modulator can be appropriately selected according to the purpose; It is preferable that the drawing units are arranged two-dimensionally, and more preferably arranged in a grid pattern.

Microlens Array

The microlens array may be appropriately selected according to the purpose, but the microlenses should have an aspherical surface capable of correcting aberrations caused by distortion of the irradiation surface of the drawing portion.

The aspherical surface may be appropriately selected depending on the purpose; For example, the aspherical surface is preferably a toric surface.

Hereinafter, the microlens array, the aperture array, and the imaging system will be described with reference to the drawings.

FIG. 13A shows the DMD 50, the laser source 144 for irradiating the laser beam to the DMD 50, the lens system or imaging optical system 454 and 458 for enlarging and imaging the laser beam reflected by the DMD 50, and the DMD. A microlens array 472 in which a plurality of microlenses 474 corresponding to each drawing unit of 50 is arranged, and an opening in which a plurality of openings 478 corresponding to each microlens of the microlens array 472 are cast. The exposure head provided with the lens system or the imaging systems 480 and 482 which form an array and the number of laser beams to the exposure surface 56 through the number is shown.

14 shows planarity data for the reflecting surface of the micromirror 62 of the DMD 50. In Fig. 14, the contour lines represent the same respective heights of the reflecting surfaces; The pitch of the contour is 5 nm. In Fig. 14, the X direction and the Y direction are two diagonal directions of the micromirror 62, and the micromirror 62 rotates around a rotation axis extending in the Y direction. 15A and 15B show the height displacement of the micromirror 62 along the X and Y directions, respectively.

As shown in Figs. 14 and 15A and 15B, distortion exists in the reflecting surface of the micromirror 62, in particular, in one diagonal direction (Y direction) in which the distortion in one diagonal direction (Y direction) is different from the central part of the mirror. Greater than distortion. Therefore, it may cause a problem that the shape at the position where the laser beam B is focused by the microlens 55a of the microlens array 55 is distorted.

In order to prevent such a problem, the microlens 55a of the microlens array 55 has a special shape different from the prior art as will be described later.

16A and 16B show the front shape and the side shape of the entire microlens array 55 in detail. 16A and 16B, each part of the microlens array is indicated in units of mm. In the pattern forming method according to the present invention, as described above, the micromirror of 1024 columns x 256 rows of the DMD 50 is driven; The microlens array 55 correspondingly consists of 1024 arrays in the longitudinal direction and 256 arrays in the width direction. In Fig. 16A, the position of each microlens is indicated by the "j" th column and the "k" th row.

17A and 17B show front and side shapes of one microlens 55a of the microlens array 55, respectively. 17A shows the contour of the microlens 55a. The cross section of each microlens 55a on the irradiation side has an aspherical surface shape for correcting aberration due to distortion of the reflecting surface of the micromirror 62. Specifically, the microlens 55a is a toric lens; The radius of curvature Rx of the optical X direction Rx is -0.125 mm, and the radius of curvature Ry of the optical Y direction R is -0.1 mm.

Therefore, the condensing state of the laser beam B in the cross section parallel to the X direction and the Y direction is as shown in Figs. 18A and 18B, respectively. That is, when the X direction and the Y direction are compared, the radius of curvature of the microlens 55a in the Y direction is smaller and the focal length is shorter.

19A, 19B, 19C, and 19D show simulations of the beam diameter near the focal point of the microlens 55a in the above-described shape. As a contrast, Figures 20A, 20B, 20C and 20D show the same simulation for microlens 55a with Rx = Ry = -0.1 mm. The value of z in the figure indicates the evaluation position in the focal direction of the microlens 55a as a distance from the beam irradiation surface of the microlens 55a.

The surface shape of the microlens 55a in the simulation can be calculated by the following formula.

In the above formula, Cx means the radius of curvature in the X direction (= 1 / Rx), Cy means the radius of curvature in the Y direction (= 1 / Ry), X means the distance from the optical axis O in the X direction And Y is the distance from the optical axis O with respect to the Y direction.

Comparing Figs. 19A to 19D and 20A to 20D, in the pattern forming method according to the present invention, the focal length in the cross section parallel to the Y direction is toric as the microlens 55a shorter than the focal length in the cross section parallel to the X direction. By using the lens, it can be seen that the distortion of the beam shape in the vicinity of the condensing position is reduced. Therefore, the image can be exposed to the pattern forming material 150 more clearly without distortion. Further, it can be seen that in the embodiment of the present invention shown in Figs. 19A to 19D, the area having a small beam diameter is wider, that is, the depth of focus is larger.

On the other hand, in the case where the magnitude of the distortion in the center portion appears in the center portion of the micromirror 62 as opposed to the above, if the focal length in the cross section parallel to the X direction is smaller than the focal length in the cross section parallel to the Y direction, The image may be exposed to the pattern forming material 150 more clearly and without distortion.

The opening array 59 disposed near the condensing position of the microlens array 55 is configured such that each opening 59a receives only the laser beam through its corresponding microlens 55a. In other words, the opening array 59 provides respective openings which can prevent light from being incident from the adjacent microlenses 55a and increase the extinction ratio.

Originally, the smaller the diameter of the opening 59 formed for this purpose can provide the effect of reducing the distortion of the beam shape at the condensing position of the microlens 55a. However, this configuration inevitably increases the amount of light blocked by the opening array 59, resulting in a decrease in light quantity efficiency. On the contrary, since the aspherical microlens 55a does not block light, the light quantity efficiency is also maintained high.

In the pattern formation method according to the present invention, the microlenses 55a may be aspherical or secondary shapes such as quadratic or sixth order. The use of higher-order aspherical surfaces can further increase the accuracy of the beam shape.

In the above-mentioned aspect, the cross section of the irradiation side of the microlens 55a is aspherical or toric; Or it can be composed of one of the cross-section as a spherical surface and the other surface as a mold surface can cause the same effect in the actual loss.

In addition, in the above-described form, the microlenses 55a of the microlens array 55 are aspherical for compensating aberration due to distortion of the reflecting surface of the micromirror 62; Alternatively, by providing each microlens of the microlens array having a reflectance distribution for correcting aberration due to distortion of the reflecting surface of the micromirror 62, substantially the same effect can be caused.

22A and 22B show an example of such a microlens 115a. 22A and 22B show the front or rear side of the microlens 115a, respectively. The overall shape of the microlens 115a is a flat plate shape as shown in Figs. 22A and 22B. X and Y directions in Figs. 22A and 22B have the same meanings as described above.

23A and 23B schematically show a state in which the laser beam B is focused by the microlens 115a in cross sections parallel to the X and Y directions, respectively. This microlens 115a exhibits a refractive index distribution in which the refractive index distribution gradually increases in the outward direction from the optical axis O; The dotted lines in Figs. 23A and 23B show positions at which the refractive index decreases by a predetermined level from the optical axis O. As shown in Figs. 23A and 23B, when comparing the cross section parallel to the X direction and the cross section parallel to the Y direction, the latter changes abruptly and the focal length becomes shorter. Therefore, the microlens array having such a refractive index distribution can provide the same effect as the microlens array 55 described above.

In addition, a microlens having an aspherical surface as shown in FIGS. 17 and 18 provides such a refractive index distribution, so that both the surface shape and the refractive index distribution can correct aberrations due to distortion of the reflecting surface of the micromirror 62.

In the above-described aspect, the aberration caused by the distortion of the reflecting surface of the micromirror 62 of the DMD 50 is corrected; Similarly, in the pattern forming process according to the present invention using a spatial light modulator other than DMD, if distortion appears on the surface of the drawing portion of the spatial light modulator, the aberration caused by the distortion can be corrected to prevent distortion of the beam shape. Can be.

The imaging optical system mentioned above is demonstrated below.

In the exposure head, when the laser beam is irradiated from the laser source 144, the cross-sectional area of the light beam reflected by the DMD 50 in one direction is enlarged several times, for example, twice the lens systems 454 and 458. The magnified laser beam is condensed by each microlens of the microlens array 472 corresponding to each drawing of the DMD 50 and then passes through the corresponding opening 476 of the aperture array 476. The laser beam passing through the opening is formed on the exposure surface 56 by the lens systems 480 and 482.

In the imaging optical system, the laser beam reflected by the DMD 50 is magnified by the magnification lenses 454 and 458 several times, and is projected onto the exposure surface 56, thereby widening the entire image area. When the microlens array 472 and the aperture array 476 are not arranged, as shown in FIG. 13B, one drawing portion size or spot size of each beam spot BS projected on the exposure surface 56 is shown. Is enlarged according to the size of the exposure area 468, so that the MRF (Modulation Transfer Function) characteristic representing the sharpness of the exposure area 468 is deteriorated.

On the other hand, when the microlens array 472 and the aperture array 476 are arranged, the laser beam reflected by the DMD 50 is the angle of the DMD 50 by each microlens of the microlens array 472. The light is condensed corresponding to the drawing part. Accordingly, as shown in FIG. 13C, even when the exposure area is enlarged, the spot size of each beam spot BS can be reduced to a predetermined size, for example, 10 μm × 10 μm, thereby preventing deterioration of MTF characteristics. Highly accurate exposure can be performed. On the other hand, the inclination of the exposure area 468 is caused by the DMD 50 which is inclined to remove the space between the drawing portions.

In addition, even when the beam becomes thick due to the aberration of the microlens, the beam shape can be shaped so as to form a spot on the exposure surface 56 with a certain size by the opening, and the array of openings formed corresponding to each drawing portion. By passing the beam through, crosstalk between adjacent drawing portions can be prevented.

Further, by using the high luminance laser source as the laser source 144, the inclination angle of the light beam incident on the microlenses of the microlens array 472 from the lens 458 is reduced, so that partial incidence of the light beam of the adjacent drawing portion is incident. Can be prevented, that is, a high extinction ratio can be achieved.

Other optical systems

In the pattern formation method which concerns on this invention, you may use together with the optical system suitably selected from the conventional optical system, For example, the optical system which correct | amends light quantity distribution can further be used.

The optical system for correcting the light quantity distribution changes the luminous flux width at each exit side so that the ratio of the luminous flux width at the periphery to the luminous flux width at the center close to the optical axis is higher at the exit side than the incidence side, so that the parallel luminous flux from the laser source is irradiated to the DMD. In doing so, the amount of light distribution on the irradiated surface is corrected to become substantially uniform. Hereinafter, an optical system for correcting the light amount distribution will be described with reference to the drawings.

First, as shown in FIG. 24A, the case where the total luminous flux widths H0 and H1 between the incident light beam and the outgoing light beam are the same for the optical system will be described. In Fig. 24A, portions 51 and 52 denote virtually the entrance and exit planes in the optical system for correcting the light amount distribution.

In the optical system for correcting the light quantity distribution, it is assumed that the luminous flux width h0 of the luminous flux incident on the central portion close to the optical axis Z1 and the luminous flux width h1 of the luminous flux incident on the peripheral portion are the same (h0 = h1). The optical system for correcting the light quantity distribution provides a laser beam having the same luminous flux h0 and h1 at the incidence side, thereby expanding the luminous flux width h0 for the incident luminous flux at the center, and conversely for the incident luminous flux at the periphery. It serves to reduce the light beam width h1. That is, the optical system affects the output light beam width h10 at the center portion and the light beam width h11 at the peripheral portion such that h11 <h10. Expressed as a ratio of luminous flux width, the (emission luminous flux width at the periphery) / (the luminous flux width at the center) is smaller than the incidence ratio, that is, [h11 / h10] is (h1 / h0 = 1) or (h11 / h10 <1) Is less than

By changing the light beam width, it is possible to supply the light beam of the central portion having a high light quantity to the peripheral portion having low light quantity; The light amount distribution is almost uniform in the exposure surface without degrading the utilization efficiency. The degree of homogenization is 30% or less, for example, 20% or less of light quantity nonuniformity in an effective area.

Even when the luminous flux widths on the incidence side and the outgoing side are entirely changed, the effects and effects of the optical system for correcting the light quantity distribution are the same as shown in Figs. 24A, 24B and 24C.

FIG. 24B shows the case where the entire bundle of light beams H0 is reduced to the bundle of light beams H2 and emitted (H0> H2). Also in this case, in the optical system for correcting the light quantity distribution, the light beam width h10 at the incidence side is the same as the light beam width h1 at the exit side, and the light beam width h10 at the center portion is larger than the peripheral portion at the exit side. There is a tendency to process so that the luminous flux width h11 becomes smaller in the center portion. In consideration of the reduction ratio of the luminous flux, the optical system functions to reduce the reduction ratio of the incident light flux at the center portion compared to the peripheral portion and to increase the reduction ratio of the incident light flux at the peripheral portion relative to the center portion. Also in this case, (the output luminous flux width in the peripheral part) / (the output luminous flux width in the center part) is smaller than the incidence ratio, that is, [H11 / H10] is smaller than (h1 / h0 = 1) or ((h11 / h10) <1). small.

24C illustrates the case where the total luminous flux width H0 on the incidence side is extended to the width H3 to emit (H0 <H3). Even in this case, the optical system for correcting the light quantity distribution has a laser beam having the same light beam width h0 as the light beam width h1 at the incidence side, and a light beam width h10 at the center portion at the exit side is larger than the periphery portion. There is a tendency to process so that the luminous flux width h11 is smaller than the center portion. Considering the magnification of the luminous flux, the optical system works to increase the magnification of the incident light flux at the center portion compared to the peripheral portion and to reduce the magnification of the incident light flux at the peripheral portion relative to the center portion. Also in this case, (the output light beam width at the peripheral part) / (the output light beam width at the center part) is smaller than the incidence ratio, that is, [H11 / H10] is smaller than (h1 / h0 = 1) or (h11 / h10 <1).

In this way, the optical system for correcting the light quantity distribution changes the luminous flux width at each emission position, and the (emission luminous flux width in the peripheral portion) / (emission luminous flux width in the center portion) at the emission side is reduced compared to the incident side; The laser beam having the same luminous flux width is a laser beam in which the luminous flux width at the center portion is larger than the peripheral portion at the exit side and the luminous flux width at the peripheral portion is smaller than the central portion. By this action, the luminous flux of the central part can be supplied to the periphery, so that the light quantity distribution is almost uniform in the luminous flux section without lowering the utilization efficiency of the entire optical system.

Specific lens data of the pair of combination lenses used in the optical system for correcting the light amount distribution are exemplified below. In this example, as described above, lens data in the case where the light quantity distribution in the cross section of the exiting light flux exhibits a Gaussian distribution as in the case where the laser source is a laser array will be described. When one semiconductor laser is connected to the incidence end portion of the single mode optical fiber, the light quantity distribution of the incident light beam from the optical fiber shows a Gaussian distribution. Further, the pattern forming method according to the present invention can be applied to the case where the amount of light near the center is significantly larger than the amount of light around the periphery, such as when the core diameter of the multimode optical fiber is reduced to form a single mode optical fiber.

Table 1 summarizes the basic lens data.

Primary lens data Si (face number) ri (curvature radius) di (planar distance) Ni (reflectivity) 01 02 03 04 Aspheric ∞ ∞ Aspheric 5.000 50.000 7.000 1.52811 1.52811

As can be seen from Table 1, a pair of combination lenses consists of two aspherical lenses of rotational symmetry. A first surface of the incidence side of the first lens disposed on the light incidence side; A second surface opposite the light exit side; A third surface of the incident side of the second lens disposed on the light exiting side; The opposite surface of the light exit side is defined as a fourth surface. The first and fourth surfaces are aspherical.

In Table 1, "Si (plane number)" represents the "i" th surface (i = 1-4), "ri (curvature radius)" shows the radius of curvature of the "i" th surface, and di (surface Distance) represents the distance between planes between the "i" th plane and the "i + 1" th plane. The unit of di (planar distance) is millimeter (mm). Ni (refractive index) represents the refractive index with respect to the wavelength of 405 nm of the optical element containing an "i" th surface.

Table 2 summarizes the aspheric data of the first and fourth surfaces.

The aspherical data may be represented by coefficients of the following formula (A) representing an aspherical shape.

In said Formula (A), a coefficient is defined as follows.

Z: length of the waterline (mm) extending from the point on the aspherical surface at the height ρ from the optical axis to the tangent plane of the aspheric vertex or a plane perpendicular to the optical axis

ρ: distance from the optical axis (mm)

K: Cone Factor

C: paraxial curvature (1 / r, r: paraxial curvature radius)

ai: aspherical coefficient of the difference "i" (i = 3 to 10)

Fig. 26 shows the light amount distribution of the illumination light obtained by the pair of combined lenses shown in Tables 1 and 2 above. The horizontal axis represents distance from the optical axis, and the vertical axis represents light quantity ratio (%). Fig. 25 shows light intensity distribution (Gaussian distribution) of uncorrected illumination light. As can be seen from Figs. 25 and 26, by the optical system for correcting the light amount distribution, an almost uniform light amount distribution can be obtained which significantly exceeds that for which no correction has been performed, so that a uniform laser can be obtained without lowering the light utilization efficiency. Uniform exposure can be achieved by the beam.

Light irradiation means or laser source

The light irradiation means can be appropriately selected according to the purpose; Examples include ultra high pressure mercury lamps, xenon lamps, carbon arc lamps, halogen lamps, fluorescent lamps, LEDs, semiconductor lasers and other known laser sources, and also combinations of two or more of these means. Among these means, a means capable of irradiating two or more kinds of light or laser beams is preferable.

Examples of the light or laser beam irradiated from the light irradiation means or the laser source include UV rays, visible rays, X-rays, laser beams, and the like. Among these, a laser beam is preferable, More preferably, it is what contains 2 or more types of laser beams (Hereinafter, it may be called a "multiplexing laser.").

300-1500 nm is preferable, as for the wavelength of the said UV ray and visible light, 320-800 nm is more preferable, 330 nm-650 nm are the most preferable.

The wavelength of the laser beam is preferably 200 to 1500 nm, more preferably 300 to 800 nm, still more preferably 330 nm to 500 nm, and most preferably 400 nm to 450 nm.

As said haptic laser irradiation means, the means provided with the several laser irradiation apparatus, the multimode optical fiber, and the condensing optical system which collects each laser beam and couples them to a multimode optical fiber is illustrated preferably.

In the following, the harmonic laser irradiation means or the fiber array laser source will be described with reference to the drawings.

The fiber array laser source 66 includes a plurality (for example, 14) laser modules 64 as shown in Fig. 27A. One end of the multimode optical fiber 30 is coupled to each laser module 64. At the other end of each multimode optical fiber 30, an optical fiber 31 whose core diameter is the same as the multimode optical fiber 30 and whose clad diameter is smaller than the multimode optical fiber 30 is combined. As specifically shown in Fig. 27B, at the other end of the multimode optical fiber 30, the ends of the multimode optical fiber 31 are arranged at seven ends along the main-scanning direction orthogonal to the sub-scanning direction. The two ends are arranged in two rows to form the laser emission unit 68.

The laser output unit 68, which is composed of the ends of the multimode optical fiber 31, is fixed by interposing between two flat support plates 65 as shown in Fig. 27B. Preferably, a transparent protective plate such as a glass plate is disposed on the exit end face of the multimode optical fiber 31 to protect the light exit end face. The emission cross section of the multi-mode optical fiber 31 is easy to collect and deteriorate easily because of high optical density; The protective plate as described above can delay the deterioration by preventing dust from adhering to the end face.

In this example, in order to arrange the optical fibers 31 having a small clad diameter in an array without a space, the multi-mode optical fibers 30 are laminated between two multi-mode optical fibers 30 joined to a portion having a large clad diameter. The output end of the optical fiber 31 coupled to the stacked multimode optical fiber 30 is interposed between the two output ends of the optical fiber 31 coupled to the two multimode optical fibers 30 which are joined at a large clad diameter portion. do.

Such an optical fiber may be manufactured by coaxially coupling an optical fiber 31 having a length of 1 to 30 cm and a small clad diameter to the tip portion of the laser beam exit side of the multi-mode optical fiber 30 having a large clad diameter as shown in FIG. have. The two optical fibers are combined such that the incident cross section of the optical fiber 31 is fused so that the central axis of the two optical fibers coincides with the exit cross section of the multimode optical fiber 30. As described above, the diameter of the core 31a of the optical fiber 31 is equal to the diameter of the core 30a of the multimode optical fiber 30.

In addition, a short optical fiber manufactured by fusing an optical fiber having a short length and a large clad diameter to an optical fiber having a small clad diameter may be coupled to the exit end of the multimode optical fiber through a ferrol or an optical connector. By being coupled in a detachable manner through a connector or the like, it is possible to facilitate replacement of the output end even when the optical fiber having a small clad diameter is partially broken, thereby advantageously reducing the maintenance cost of the exposure head. In some cases, the optical fiber 31 is referred to as the "emission end" of the multimode optical fiber 30.

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, Mitsubishi Cable Industries Ltd. You can use the product's step index fiber. One of the best forms according to the present invention is that the multimode optical fiber 30 and the optical fiber 31 are step index type optical fibers; In the multimode optical fiber 30, the cladding diameter is 125 mu m, the core diameter is 50 mu m, the NA is 0.2 and the transmittance is 99.5% or more (in the coating on the incident cross section); In the optical fiber 31, the cladding diameter is 60 mu m, the core diameter is 50 mu m, and NA is 0.2.

In general, the laser beam in the infrared region increases the propagation loss when the cladding diameter of the optical fiber is reduced. Thus, the appropriate cladding diameter is determined according to the wavelength band of the laser beam. However, the shorter the wavelength, the smaller the propagation loss; For example, in a laser beam having a wavelength of 405 nm irradiated from a GaN semiconductor laser, the thickness of the clad (clad diameter-core diameter) / 2 is about 1/2 of the thickness of the clad when conventionally propagating infrared light having a wavelength of 800 nm, or Alternatively, even when approximately 1/4 of the cladding thickness at the time of propagating infrared light having a wavelength of 1.5 µm for communication, propagation loss hardly increases. Therefore, the cladding diameter can be reduced to about 60 mu m.

Needless to say, the cladding diameter of the optical fiber 31 is not limited to 60 mu m. The cladding diameter of the optical fiber used in the conventional fiber array laser source is 125 탆; The smaller the clad diameter, the deeper the depth of focus; 80 micrometers or less are preferable, as for the clad diameter of a multimode optical fiber, 60 micrometers or less are more preferable, and 40 micrometers or less are more preferable. On the other hand, since the core diameter is approximately at least 3 to 4 µm, the clad diameter of the optical fiber 31 is preferably 10 µm or more.

The laser module 64 is composed of a harmonic laser source or a fiber array laser source shown in FIG. The multiplexing laser source is arranged on the heating block 10 to fix a plurality of fixed (e.g., seven) multimode or single mode GaN semiconductor lasers (LD1, LD2, LD3, LD4, LD5, LD6 and LD7) and collimators. Lens 11, 12, 13, 14, 15, 16 and 17, one condenser lens 20, and one multimode optical fiber 30. Needless to say, the number of semiconductor lasers is not limited to seven. For example, in a multimode optical fiber having a cladding diameter of 60 µm, a core diameter of 50 µm and a NA of 0.2, about 20 semiconductor lasers can be incident, thereby reducing the number of optical fibers while realizing the required amount of light of the exposure head. You can.

GaN semiconductor lasers LD1 to LD7 have a common oscillation wavelength, such as 405 nm, and a common maximum output, such as 100 mW for a multimode laser and 30 mW for a single mode laser. The GaN semiconductor lasers LD1 to LD7 may have oscillation wavelengths other than 405 nm as long as they are in the wavelength range of 350 nm to 450 nm.

The haptic laser source is housed in a box-shaped package 40 with an upper opening together with other optical elements as shown in FIGS. 30 and 31. The package 40 has a package lid 41 for closing the opening. After the degassing treatment, a sealing gas is introduced, and the opening of the package 40 is closed with the package lid 41 to create a sealed space or sealed space formed by the package 40 and the package lid 41, thereby generating the combined laser. The circle is placed in a sealed state.

The base plate 42 is fixed to the bottom of the package 40; On the upper surface of the base plate 42, the heating block 10, the condenser lens holder 45 for supporting the condenser lens 20, and the fiber holder 46 for supporting the incident end of the multimode optical fiber 30 are provided. It is installed. The exit end of the multimode optical fiber 30 is pulled out of the package from an opening formed in the wall surface of the package 40.

The collimator holder 44 is attached to the side wall of the heating block 10, whereby the collimator lenses 11 to 17 are supported. An opening is formed in the sidewall of the package 40, and a wiring 47 for supplying a driving current to the GaN semiconductor lasers LD1 to LD7 is drawn out of the package through the opening.

In FIG. 31, only the GaN semiconductor laser LD7 is shown with a reference number among a plurality of GaN semiconductor lasers, and only the collimator lens 17 is shown with a reference number among a plurality of GaN semiconductor lasers.

 Fig. 32 shows the front shape of the adhesive portion of the collimator lenses 11 to 17. Figs. Each of the collimator lenses 11 to 17 is formed in a shape in which a circular lens having an aspherical surface is cut into long pieces in a plane parallel to the area including the optical axis. This elongate collimator lens can be manufactured by a molding process. The collimator lenses 11 to 17 are arranged in close contact with each other in the arrangement direction of the light emitting points such that their longitudinal directions are perpendicular to the arrangement of the light emitting points of the GaN semiconductor lasers LD1 to LD7.

On the other hand, in the GaN semiconductor lasers LD1 to LD7, each of the laser beams B1 is provided with an active layer having a light emission width of 2 µm and having spreading angles of 10 and 30 degrees in the parallel and vertical directions with respect to the active layer. The following laser which emits ˜B7) can be used. GaN semiconductor lasers LD1 to LD7 are arranged so that the light emitting points are arranged in one column in parallel with the active layer.

Therefore, in the laser beams B1 to B7 emitted from the respective light emitting points, the direction in which the spread angle is large in the long collimator lenses 11 to 17 coincides with the longitudinal direction of each collimator lens, and the spread angle is small. The direction is incident in a state coinciding with the width direction of the collimator lens. That is, with respect to each collimator lens 11 to 17, the width is 1.1 mm and the length is 4.6 mm. For the laser beams B1 to B7 incident on the collimator lens, the beam diameter is 0.9 mm in the horizontal direction, and the vertical direction. It is 2.6mm. In each collimator lens 11-17, focal length f1 = 3mm, NA = 0.6, and the arranged lens pitch = 1.25mm.

The condensing lens 20 includes an optical axis and a portion of the circular lens, which is an aspherical surface, is cut into long pieces with respect to the parallel plane, and the long pieces are long in the arrangement direction of the collimator lenses 11 to 17, that is, in the horizontal direction. It is arranged in a short form in the vertical direction. In this condensing lens 20, the focal length f2 is 23 mm and NA is 0.2. This condensing lens 20 can be manufactured for molding resin or optical glass, for example.

In addition, since the high-intensity fiber array laser source is used by being arranged at the exit end of the optical fiber in the haptic laser source of the illuminating means for illuminating the DMD, a pattern forming apparatus having a high output and a deep depth of focus can be obtained. In addition, as the output of each fiber array laser source is increased, not only the number of fiber array laser sources required for obtaining the required output is reduced, but also the cost of the pattern forming apparatus is reduced.

In addition, since the cladding diameter at the exit end of the optical fiber is smaller than the cladding diameter at the incidence end, the diameter of the light emitting portion is smaller, resulting in higher luminance of the fiber array laser source. Therefore, a pattern forming apparatus having a deep depth of focus can be realized. For example, even in the case of ultra-high resolution exposure having a beam diameter of 1 µm or less and a resolution of 0.1 µm or less, sufficient depth of focus can be obtained, so that high-speed and precise exposure can be achieved. Therefore, the pattern forming apparatus is suitable for exposing a thin film transistor (TFT) that requires high resolution.

The luminaire is not limited to a fiber array laser source having a plurality of haptic laser sources; For example, a fiber array laser source having one fiber laser source can be used, and the fiber laser source is composed of one arrayed optical fiber that emits a laser beam from one semiconductor laser having a light emitting point.

Further, as a laser source having a plurality of light emitting points, for example, a laser including a plurality of (eg, seven) chip-shaped semiconductor lasers LD1 to LD7 disposed on the heating block 10 as shown in FIG. 33. Arrays can be used. Also, as shown in FIG. 34A, a multiple cavity laser 110 including a plurality of light emitting points 110a arranged in a predetermined direction is known. In the multi-cavity laser 110, the position of the light emitting point can be arranged with a higher positional accuracy than when the chip-shaped semiconductor laser is arranged, so that the laser beam emitted from each light emitting point can be easily combined. Preferably, when the number of light emitting points 110a increases, warpage is likely to occur in the multi-cavity laser 110 at the time of laser manufacture. Therefore, the number of light emitting points 110a is preferably 5 or less.

As the luminaire, the multi-cavity laser 110 or a multi-cavity array in which a plurality of multi-cavity lasers 110 are arranged in the same direction as the light emitting point 110a of each tip is arranged. It can be used as a laser source.

The combining laser source is not limited to the form of combining the plurality of laser beams emitted from the plurality of chip-shaped semiconductor lasers. For example, as shown in FIG. 21, a combined wave laser source including a chip-shaped multiple cavity laser 110 having a plurality of light emitting points 110a can be used. This multiplexing laser source includes a multi-cavity laser 110, one multimode optical fiber 130 and a condenser lens 120. The multiple cavity laser 110 may be composed of, for example, a GaN laser diode having an oscillation wavelength of 405 nm.

In the above configuration, each laser beam B emitted from each of the plurality of light emitting points 110a of the multi-cavity laser 110 is condensed by the condensing lens 120 and the core of the multimode optical fiber 130 is provided. It enters 130a. The laser beam incident on the core 130a propagates into the optical fiber, is combined with one laser beam, and then emitted from the optical fiber.

A plurality of light emitting points 110a of the multi-cavity laser 110 are arranged in a width substantially the same as the core diameter of the multimode optical fiber 130, and convex having a focal length substantially the same as the core diameter of the multimode optical fiber 130. By using a lens, and by using a rod lens that aims only the emission beam from the multi-cavity laser 110 into the plane perpendicular to the active layer thereof, the laser beam (B) for the multimode optical fiber 130 The coupling efficiency can be improved.

In addition, as shown in FIG. 35, by using the multi-cavity laser 110 having a plurality of (e.g., three) light emitting points, the plurality of (e.g., nine) multi-cavity lasers on the heating block 111. A combined laser source having the laser array 140 formed by arranging the 110 at the same interval may be used. The plurality of multi-cavity lasers 110 are arranged and fixed in the same direction as the light emitting points 110a of the respective tips.

The haptic laser source is a laser array 140, a plurality of lens array 114 disposed in correspondence with the multi-cavity laser 110, one rod disposed between the laser array 140 and the plurality of lens array 114 A lens 113, one multimode optical fiber 130, and a condenser lens 120 are provided. The lens array 114 includes a plurality of microlenses corresponding to the light emitting points of the multiple cavity lasers 110, respectively.

In the above-described configuration, the laser beam B emitted from the plurality of light emitting points 110a of the plurality of multi-cavity lasers 110 is focused in a predetermined direction by the rod lens 113, and then the lens array 114 Parallelized by each microlens of. The parallelized laser beam L is collected by the condenser lens 120 and is incident on the core 130a of the multimode optical fiber 130. The laser beam incident on the core 130a propagates in the optical fiber, and after being combined as one beam, exits from the optical fiber.

Another combination laser source is illustrated below. In the combined laser source, as shown in Figs. 36A and 36B, a heating block 182 having an L-shaped cross section in the optical axis direction is mounted on the rectangular heating block 180, and between two heating blocks. The storage space is formed. On the upper surface of the L-shaped heating block 182, a plurality of (e.g., two) multi-cavity lasers 110, in which a plurality of (e.g., five) light emitting points are arrayed, are formed at each tip-shaped light emitting point. It is arranged and fixed at equal intervals in the same direction as the arrangement direction.

A recess is formed in the rectangular heating block 180; A plurality of (eg, two) multiple cavity lasers 110 are disposed on an upper surface of the heating block 180, and a plurality of light emitting points (eg, five) are arrayed in each of the multiple cavity lasers 110. The light emitting point is located on the same vertical plane as the surface on which the light emitting point of the laser tip disposed on the heating block 182 is located.

On the laser beam exit side of the multi-cavity laser 110, a collimated lens array 184 in which collimated lenses are arranged is arranged corresponding to the light emitting point 110a of each tip. In the collimated lens array 184, the longitudinal direction of each collimated lens coincides with the direction or the axis direction in which the laser beam exhibits a larger spreading angle, and the width direction of each collimated lens has a smaller laser beam. It coincides with the direction of the spreading angle or the axis direction. Integrating the collimated lens by arraying can increase the space efficiency of the laser beam, increase the output of the combined laser source, and reduce the number of parts, thereby reducing the manufacturing cost.

On the laser beam exit side of the collimated lens array 184, one multimode optical fiber 130 and a condenser lens 120 for condensing and combining the laser beam at the incident end of the multimode optical fiber 130 are arranged.

In the above configuration, each laser beam B emitted from each light emitting point 110a of the plurality of multiple cavity lasers 110 disposed on the laser blocks 180 and 182 is parallel by a collimated lens array. After the light is collected and collected by the light collecting lens 120, the light is incident on the core 130a of the multimode optical fiber 130. The laser beam incident on the core 130a propagates into the optical fiber, is combined into one beam, and then emitted from the optical fiber.

The haptic laser source can be a high power source, in particular, by a multi-stage arrangement of multi-cavity lasers and an array of collimated lenses. Since the fiber laser source and the bundle fiber laser source can be formed by this combination laser source, it is suitable as a fiber laser source constituting the laser source of the pattern forming apparatus of the present invention.

On the other hand, the laser module can be configured by accommodating each of the haptic laser sources in a case and drawing the exit end of the multimode optical fiber 130.

In the above description, a high-brightness fiber array laser source is illustrated in which the exit end of the multimode optical fiber of the combined laser source is coupled to another optical fiber having the same core diameter as the multimode optical fiber and smaller clad directivity of the multimode optical fiber. ; For example, a multimode optical fiber having a clad diameter of 125 mu m, 80 mu m, 60 mu m, or the like may be used without bonding another optical fiber to the exit end.

The pattern forming method according to the present invention is further described.

As shown in FIG. 29, in each exposure head 166 of the scanner 162, the laser beam B1 emitted from the GaN semiconductor lasers LD1 to LD7 constituting the pulsation laser source of the fiber array laser source 66. , B2, B3, B4, B5, B6 and B7 are each parallelized by corresponding collimator lenses 11-17. The parallelized laser beams B1 to B7 are collected by the condensing lens 20 and converge at the incident cross section of the core 30a of the multimode optical fiber 30.

In this example, a condensing optical system is constituted by the collimator lenses 11 to 17 and the condensing lens 20, and the condensing optical system is constituted by the condensing optical system and the multimode optical fiber 30. That is, the laser beams B1 to B7 collected by the condenser lens 20 are incident on the core 30a of the multimode optical fiber 30, propagated into the optical fiber, and then merged into one laser beam B. It is emitted from the optical fiber 31 coupled to the exit end of the multimode optical fiber 30.

In each laser module, when the coupling efficiency of the laser beams B1 to B7 and the multimode optical fiber 30 is 0.85, and the respective outputs of the GaN semiconductor lasers LD1 to LD7 are 30 mW, they are arranged in an array. Each optical fiber 31 can obtain a combined laser beam B with an output of 180 mW (= 30 mW x 0.85 x 7). Therefore, the output from the laser exit portion 68 of the array of six optical fibers 31 is about 1 W (= 180 mW × 6).

The laser exit portions 68 of the fiber array laser source are arranged such that the high luminance light emitting points are aligned along the main-scanning direction. Since the conventional fiber laser source which combines the laser beam from one semiconductor laser to one optical fiber is low power, the desired power cannot be achieved unless a plurality of lasers are arranged; Since the haptic laser source can generate high power, a small number of array phantom laser sources (e.g., one) can produce the desired output.

For example, in a conventional fiber laser source combining one semiconductor laser and one optical fiber, a semiconductor laser having an output of about 30 mW is usually used, and a multimode optical fiber having a core diameter of 50 µm, a clad diameter of 125 µm, and an opening number of 0.2 Therefore, to obtain an output of about 1 W (Watt), 48 multimode optical fibers are required (8 x 6); since the area of the light emitting area is 0.62 mm 2 (0.675 mm x 0.925 mm), the laser The luminance at the exit portion 68 is 1.6 × 10 ⁶ (W / m ² ), and the luminance per optical fiber is 3.2 × 10 ⁶ (W / m ² ).

In contrast, when the laser irradiation means is capable of irradiating a combined laser, the six multimode optical fibers can generate an output of about 1W. Since the area of the light emitting area in the laser emission unit 68 is 0.0081 mm 2 (0.325 mm x 0.025 mm), the luminance of the laser emission unit 68 is 123 x 10 ⁶ (W / m ² ), which is the luminance of conventional means. It is equivalent to about 80 times. The luminance per optical fiber is 90 × 10 ⁶ (W / m ² ), which corresponds to about 28 times the luminance of conventional means.

The difference in depth of focus between the conventional exposure head and the exposure head of the present invention will be described with reference to FIGS. 37A and 37B. For example, the diameter of the exposure head in the sub-scanning direction of the light emitting area of the bundled fiber laser source is 0.675 mm, and the diameter of the exposure head in the sub-scanning direction of the light emitting area of the fiber array laser source is 0.025 mm. As shown in Fig. 37A, in the conventional exposure head, since the light emitting area of the irradiation means or the bundled fiber laser source 1 is large, the angle of the laser beam incident on the DMD 3 becomes large, and as a result, the scanning surface 5 The angle of the laser beam incident on the light increases. Therefore, the beam diameter tends to increase in the condensing direction, and the focusing direction is shifted.

On the other hand, as shown in Fig. 37B, since the exposure head of the pattern forming apparatus of the present invention has a small diameter of the light emitting region of the fiber array laser source 66 in the sub-scanning direction, the DMD 50 is allowed to pass through the lens system 67. The angle of the laser beam incident on the laser beam becomes small, and as a result, the angle of the laser beam incident on the scanning surface 56 becomes small. That is, the depth of focus is deepened. In this example, since the diameter of the light emitting area is about 30 times the diameter of the conventional one in the sub-scanning direction, a depth of focus corresponding to the diffraction limit can be obtained, which is suitable for exposure of a micro spot. The effect on the depth of focus becomes larger as the amount of light required for the exposure head increases. In this example, the size of one drawing portion projected on the exposure surface is 10 μm × 10 μm. DMD is a reflective spatial light modulator; In FIG. 37A and 37B, in order to demonstrate an optical relationship, it shows as a development view.

Pattern information according to the exposure pattern is input to a controller (not shown) connected to the DMD 50, and stored once in the frame memory in the controller. This pattern information is data in which the density of each drawing part constituting the pixel is expressed by two values, namely, the presence or absence of dot recording.

The stage 152 which adsorbs the pattern forming material 150 to the surface is moved at a constant speed from the upstream side to the downstream side of the gate 160 along the guide 158 by a driving device (not shown). If the tip of the pattern forming material 150 is detected by the sensor 164 provided in the gate 160 while the stage 152 passes under the gate 160, the pattern information stored in the frame memory is divided into multiple lines. A control signal is generated in each of the exposure heads 166 sequentially read one by one and based on the pattern information read by the data processor. Each micromirror of the DMD 50 then performs on-off control for each exposure head 166 based on the generated control signal.

When the laser beam is irradiated to the DMD 50 from the fiber array laser source 66, the laser beam reflected by the micromirror of the DMD 50 in the on-state is transferred to the pattern forming material 150 by the lens system 54, 58. The image is formed on the exposure surface 56 of. In this way, the laser beam radiate | emitted from the fiber array laser source 66 performs on-off control with respect to each drawing part, and the pattern forming material 150 writes about the same number as the drawing part used for DMD50. It is exposed by the negative or exposure area 168. In addition, the pattern forming material 150 is moved together with the stage 152 at a constant speed, so that the pattern forming material 150 is sub-scanned by the scanner 162 in the opposite direction to the stage movement, so that each exposure head ( A band-shaped exposure area 170 is formed with respect to 166.

[Laminated body]

The material to be exposed can be appropriately selected without particular limitation as long as it is a pattern forming material including a photosensitive layer. Preferably, it exposes to the laminated body containing the said pattern formation material on a board | substrate.

<Pattern Forming Material>

The pattern forming material may be appropriately selected depending on the purpose without particular limitation as long as it includes a photosensitive layer on the support.

The photosensitive layer can be appropriately selected from conventional pattern forming materials without particular limitation; Preferably, the photosensitive layer contains, for example, a binder, a polymerizable compound, a photopolymerization initiator, and other components as necessary.

The number of laminated layers of the photosensitive layer can be appropriately selected without particular limitation; One layer may be sufficient as lamination number, or two or more layers may be sufficient as it.

It is preferable that the said binder can swell in aqueous alkali solution; More preferably, the binder is soluble in aqueous alkali solution. The binder which swells or is soluble in aqueous alkali solution has an acidic group, for example.

The acidic group may be appropriately selected depending on the purpose without particular limitation; Examples thereof include carboxyl group, sulfonic acid group, phosphoric acid group and the like. Of these groups, carboxyl groups are preferred.

Examples of the binder having a carboxyl group include vinyl copolymers, polyurethane resins, polyamic acid resins, and modified epoxy resins having carboxyl groups. Among them, vinyl copolymers having a carboxyl group are preferred from the viewpoints of solubility in a coating solvent, solubility and synthesis aptitude in an alkaline developer, and ease of adjusting film properties.

The vinyl copolymer having a carboxyl group can be synthesized by copolymerizing at least (i) a vinyl polymer having a carboxyl group and (ii) a monomer copolymerizable with a vinyl monomer.

Examples of the vinyl polymer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, 2-hydroxyethyl (meth) acrylate, and the like. The addition product of the monomer which has a hydroxyl group of-, cyclic anhydrides, such as maleic anhydride, phthalic anhydride, and cyclohexane dicarboxylic acid anhydride, and (omega)-carboxy- polycaprolactone mono (meth) acrylate is mentioned. Among these, (meth) acrylic acid is particularly preferable from the viewpoint of copolymerizability, cost, solubility and the like.

As the precursor of the carboxyl group, a monomer having anhydrides such as maleic anhydride, itaconic anhydride and citraconic anhydride may be used.

The copolymerizable monomer may be appropriately selected according to the purpose, and examples thereof include (meth) acrylate esters, crotonate esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylic acid amides, Vinyl esters, vinyl alcohol esters, styrene, methacrylonitrile; Heterocyclic compounds having a substituted vinyl group such as vinylpyridine, vinylpyrrolidone and vinyl carbazole; N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinylcaprolactone, 2-acrylamide-2-methylpropane sulfonic acid, monophosphate (2-acryloyloxyethyl ester), monophosphate ( 1-methyl-2-acryloyloxyethyl ester) and the vinyl monomer which has functional groups, such as a urethane group, a urea group, a sulfonamide group, a phenol group, and an imide group, are mentioned.

Examples of (meth) acrylate esters are methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, iso Butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butyl cyclohexyl (meth) acrylate, 2-ethylhexyl (meth ) Acrylate, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (Meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy- 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, di Tylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monophenyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol Monoethyl ether (meth) acrylate, polyethylene glycol mono methyl ether (meth) acrylate, polyethylene glycol monoethyl ether (meth) acrylate, β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxy polyethylene glycol ( Meta) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctyl Ethyl (meth) acrylate, tribromophenyl (meth) acrylate and tribromophenyloxyethyl ( Meth) acrylates are listed.

Examples of such crotonates include butyl crotonate and hexyl crotonate.

Examples of such vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinylmethoxyacetate and vinyl benzoate.

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

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

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

As said (meth) acrylamide, it is (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide , Nn-butyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl ( Meta) acrylamide, N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloyl morpholine and diacetone acrylamide do.

The styrene may be styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene Chloro methyl styrene; Hydroxystyrene having a protecting group such as t-Boc deprotectable by an acid substance; Vinylmethylbenzoate and α-methylstyrene.

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

The synthesis method of the vinyl monomer which has the said functional group is, for example by addition reaction of an isocyanate group, a hydroxyl group, or an amino group; Specifically, the addition reaction of the monomer which has an isocyanate group, the compound which has one hydroxyl group, or the compound which has one primary or secondary amino group, and the monomer which has a hydroxyl group, or the monomer which has a primary or secondary amino group, and monoisocyanate Addition reaction can be mentioned.

As an example of the monomer which has the said isocyanate group, the compound represented by following General formula (1)-(3) is mentioned.

In General Formulas (1) to (3), R ¹ represents a hydrogen atom or a methyl group.

Examples of such mono isocyanates include cyclohexyl isocyanate, n-butyl isocyanate, tolyl isocyanate, benzyl isocyanate and phenyl isocyanate.

Examples of the monomer having hydroxy include compounds represented by the following General Formulas (4) to (12).

In General Formulas (4) to (12), R ₁ represents a hydrogen atom or a methyl group, and “n” represents an integer of 1 or more.

Examples of the compound having one hydroxyl group include methanol, ethanol, n-propanol, i-propanol, n-butanol, sec-butanol, t-butanol, n-hexanol, 2-ethylhexanol, n-decanol, alcohols such as n-dodecanol, n-octadecanol, cyclopentanol, cyclohexanol, benzyl alcohol and phenylethyl alcohol; Phenols such as phenol, cresol and naphthol; Examples of the compound having further substituents include fluoroethanol, trifluoroethanol, methoxyethanol, phenoxyethanol, chlorophenol, dichlorophenol, methoxyphenol and acetoxyphenol.

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

Examples of the compound having a primary or secondary amino group include methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, sec-butylamine, t-butylamine, hexylamine, 2-ethyl Alkylamines such as hexylamine, decylamine, dodecylamine, octadecylamine, dimethylamine, diethylamine, dibutylamine and dioctylamine; Cyclic alkylamines such as cyclopentylamine and cyclohexylamine; Aralkyl amines such as benzylamine and phenethylamine; Arylamines such as aniline, tolyl amine, xylylamine and naphthylamine; Combinations thereof such as N-methyl-N-benzylamine; And amines having substituents such as trifluoroethylamine, hexafluoroisopropylamine, methoxyaniline and methoxypropylamine.

Examples of copolymerizable monomers other than the above include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, styrene and chloro Styrene, bromostyrene and hydroxystyrene.

The copolymerizable monomers may be used alone or in combination.

The vinyl copolymer can be prepared by copolymerizing a suitable monomer according to a conventional method; For example, the solution polymerization method which superposes | polymerizes in a solvent by dissolving the said monomer in a suitable solvent and adding a radical polymerization initiator can be used; Or so-called emulsion polymerization which polymerizes a monomer in the state which disperse | distributed the said monomer in the aqueous solvent can be used.

The solvent used for the solution polymerization method can be appropriately selected depending on the solubility of the monomer, the resulting copolymer, and the like; Examples of the solvent include methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile and tetrahydro Furan, dimethylformamide, chloroform and toluene are listed. You may use these solvents individually or in combination.

The radical polymerization initiator may be appropriately selected without particular limitation; Examples include azo compounds such as 2,2'-azobis (isobutyronitrile) (AIBN) and 2,2'-azobis- (2,4'-dimethylvaleronitrile); Peroxides such as benzoyl peroxide; Persulfates, such as potassium persulfate and ammonium persulfate, are mentioned.

The content of the polymerizable compound having a carboxyl group in the vinyl copolymer can be appropriately selected without particular limitation; 5-50 mol% is preferable, 10-40 mol% is more preferable, 15-35 mol% is further more preferable.

When the content is less than 5 mol%, developability with respect to an alkaline solution may be insufficient, and when the content is more than 50 mol%, resistance to a developing solution for a hardened portion or a drawing portion is insufficient.

The molecular weight of the binder having a carboxyl group can be appropriately selected without particular limitation; As a mass average molecular weight, 2,000-300,000 are preferable and 4,000-150,000 are more preferable.

When the said mass average molecular weight is less than 2,000, membrane strength will become inadequate easily, a manufacturing process will become unstable, and when a mass average molecular weight exceeds 300,000, developability will fall.

The binder which has the said carboxyl group may be used individually or in combination. As a combination of 2 or more types of binder, the combination of 2 or more types of binders from which a copolymer component differs, 2 or more types of binders from which a mass mean molecular weight differs, and 2 or more types of binders from which a dispersion degree differs, etc. can be mentioned.

In the binder having the carboxyl group, part or all of the carboxyl group may be neutralized with a basic substance. The binder may be combined with a heterogeneous resin selected from polyester resins, polyamide resins, polyurethane resins, epoxy resins, polyvinyl alcohols, gelatin and the like.

In addition, the binder which has the said carboxyl group may be resin which is soluble in the aqueous alkali solution of Unexamined-Japanese-Patent No. 2873889.

The content of the binder in the photosensitive layer can be appropriately selected without particular limitation; 10-90 mass% is preferable, 20-80 mass% is more preferable, 40-80 mass% is more preferable.

When the content is less than 10% by mass, the adhesion to an alkaline developer or adhesion with a substrate for forming a printed wiring board, such as a copper clad laminate, tends to decrease, and when the content exceeds 90% by mass, stability at development or The strength of the cured film or tenting film may become insufficient. Content of a binder can be considered as total content of binder content and the addition polymer binder content used together as needed.

The acid value of the binder may be appropriately selected depending on the purpose; 70-250 mgKOH / g is preferable, 90-200 mgKOH / g is more preferable, 100-180 mgKOH / g is still more preferable.

If the acid value is less than 70 mgKOH / g, developability may be insufficient, resolution may be insufficient, or a permanent pattern such as a wiring pattern cannot be obtained accurately, and if the acid value exceeds 250 mgKOH / g, Since resistance to the developer and / or adhesion of the pattern may be degraded, permanent patterns such as wiring patterns cannot be precisely formed.

<Polymeric Compound>

The polymerizable compound may be appropriately selected without particular limitation; It is preferable that a polymeric compound is a monomer or oligomer which has a urethane group and / or an aryl group; It is preferable that this polymeric compound has 2 or more types of polymeric groups.

Examples of the polymerizable group include ethylene such as a (meth) acryloyl group, a (meth) acrylamide group, a styryl group, a vinyl group (eg, vinyl ester, vinyl ether), and an allyl group (eg, allyl ether, allyl ester). Sex unsaturated bonds; And polymerizable cyclic ether groups such as epoxy groups and oxetane groups. Among these, ethylenically unsaturated bonds are preferable.

Monomer having a urethane group

The monomer having the urethane group can be appropriately selected without particular limitation; Examples include Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 51-37193, Japanese Patent Publication No. 5-50737, Japanese Patent Publication No. 7-7208 and Japanese Patent Publication 2001-154346, Japanese Patent Publication Those listed in 2001-356476, etc. are listed; Specifically, addition products of polyisocyanates having two or more isocyanate groups in a molecule and vinyl monomers having a hydroxy group in a molecule are listed.

Examples of the polyisocyanate compound having two or more isocyanate groups in the molecule include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, toluene diisocyanate, phenylene diisocyanate, norbornene diisocyanate, di Diisocyanates such as phenyl diisocyanate, diphenylmethane diisocyanate and 3,3'dimethyl-4,4'-diphenyl diisocyanate; Polyaddition products of these diisocyanates and difunctional alcohols, each end of which is an isocyanate group; Trimers, such as the said diisocyanate or the biuret of an isocyanate; The addition product obtained from the polyfunctional alcohol of the addition product of the diisocyanate of the said diisocyanate with polyfunctional alcohols, such as a trimetholol propane, pentaerythritol, and glycerin, or ethylene oxide is mentioned.

Examples of the vinyl monomer having a hydroxy group in the molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) ) Acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, octaethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) Acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, octapropylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, dibutylene glycol mono (meth) Acrylate, tributylene glycol mono (meth) acrylate, tetrabutylene glycol mono (meth) acrylate The agent, octa-butylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate, trimethylolpropane (meth) acrylate, and pentaerythritol (meth) acrylate are exemplified. Also listed are vinyl monomers having (meth) acrylates at one end of diol molecules having other alkylene oxides, such as random or block copolymers of ethylene oxide and propylene oxide.

Examples of the monomer having a urethane group include isosi such as tri (meth) acryloyloxyethyl isocyanurate, di (meth) acrylated isocyanurate and tri (meth) acrylate of ethylene oxide-modified isocyanuric acid. The compound which has an anurate ring is mentioned. Among these, the compound represented by General formula (13) or General formula (14) is preferable; It is especially preferable to contain the compound represented by general formula (14) at least from a tentability property. These compounds may be used alone or in combination.

In the formulas (13) and (14), R ¹ to R ³ each represent a hydrogen atom or a methyl group; X ₁ to X ₃ represent an alkylene oxide and may be the same or different from each other.

Examples of the alkylene oxide groups include ethylene oxide groups, propylene oxide groups, butylene oxide groups, pentylene oxide groups, hexylene oxide groups, and random or block combination groups. Among these, ethylene oxide groups, propylene oxide groups, butylene oxide groups and combinations thereof are preferable; Ethylene oxide group and propylene oxide group are more preferable.

In General Formulas (13) and (14), m1 to m3 represent an integer of 1 to 60, preferably an integer of 2 to 30, and more preferably an integer of 4 to 15.

In the general formulas (13) and (14), Y ¹ and Y ² are an alkylene group, arylene group, alkenylene group, alkynylene group, carbonyl group (-CO-), oxygen atom, sulfur atom, imino group (-NH -) A divalent organic group having 2 to 30 carbon atoms, such as a substituted imino group, a sulfonyl group (-SO _2- ), and a combination thereof in which a hydrogen atom of the imino group is substituted with a monovalent hydrocarbon group; Among these, an alkylene group, an arylene group, and its combination group are preferable.

The alkylene group may be branched or cyclic; Examples of the alkylene group include methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, pentylene group, neopentylene group, hexylene group, trimethylhexylene group, cyclohexylene group, heptylene group and octyl The group represented by a ethylene group, 2-ethylhexylene group, a nonylene group, a decylene group, a dodecylene group, an octadecylene group, and the following general formula is mentioned.

The arylene group may be substituted with a hydrocarbon group; Examples of the arylene group include phenylene group, triylene group, diphenylene group, naphthylene group and the following groups.

As said combiner, a xylene group is mentioned.

The alkylene group, arylene group and the combination group may further have a substituent; Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; Aryl group; Ethoxy groups such as methoxy group, ethoxy group and 2-ethoxyethoxy group; Aryloxy groups such as phenoxy group; Acyl groups, such as an acetyl group and a propionyl group; Acyloxy groups such as acetoxy group and butylyloxy group; Alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group; And aryloxycarbonyl groups such as phenoxycarbonyl group.

In the said General formula (13) or (14), it is preferable that "n" represents the integer of 3-6, and "n" is 3, 4, or 6 from a viewpoint of the raw material supply property for synthesizing a polymerizable monomer. .

In the formulas (13) and (14), "n" represents an integer of 3 to 6; Z represents a n-valent (n = 3-6) linking group, and the following group is listed as an example of Z.

In the above general formula, X ₄ represents an alkylene oxide; m4 represents the integer of 1-20; "n" represents the integer of 3-6; A represents an organic group in which "n" is (n = 3 to 6).

Examples of A of the organic group include n-valent aliphatic groups, n-valent aromatics, and these groups and alkylene groups, arylene groups, alkenylene groups, alkynylene groups, carbonyl groups, oxygen atoms, sulfur atoms, imino groups, and hydrogen atoms of these imino groups A substituted imino group substituted with a monovalent hydrocarbon group, and a combination group of a sulfonyl group (-SO _2- ); n-valent aliphatic groups, n-valent aromatic groups, and combinations of these groups with alkylene groups, arylene groups or oxygen atoms are more preferable; More preferred are n-valent aliphatic groups and combinations of n-valent aliphatic groups with alkylene groups or oxygen atoms.

1-100 are preferable, as for the number of carbon atoms of A of the said organic group, 1-50 are more preferable, and its 3-30 pieces are more preferable.

The n-valent aliphatic group may have a branched or cyclic structure. 1-30 are preferable, as for the number of the carbon atoms of the said aliphatic group, 1-20 are more preferable, and 3-10 are more preferable.

6-100 are preferable, as for the number of carbon atoms of the said aromatic group, 6-50 are more preferable, and 6-30 are more preferable.

The n-valent aliphatic group and n-valent aromatic group may further have a substituent; Examples of the substituent include a hydroxy group; Halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; Aryl group; Alkoxy groups, such as a methoxy group, an ethoxy group, and 2-ethoxyethoxy group; Aryloxy groups such as phenoxy group; Acyl groups, such as an acetyl group and a propionyl group; Acyloxy groups such as acetoxy group and butylyloxy group; Alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group; And aryloxycarbonyl groups such as phenoxycarbonyl group.

The alkylene group may have a branched structure or a cyclic structure. 1-18 are preferable and, as for the number of carbon atoms of the said alkylene group, 1-10 are more preferable.

The arylene group may be further substituted with a hydrocarbon group. 6-18 are preferable and, as for the number of carbon atoms of the said arylene group, 6-10 are more preferable.

1-18 are preferable and, as for the number of carbon atoms of the hydrocarbon group of the said substituted imino group, 1-10 are more preferable.

Below, the preferable example of A of the said organic group is as follows.

As a compound represented by the said General formula (13) and (14), the compound specifically, represented by following General formula (15)-(37) is mentioned.

In the formulas (15) to (37), each of n, n1, n2, and m represents an integer of 1 to 60; L represents an integer of 1 to 20; R represents a hydrogen atom or a methyl group.

Monomer having an aryl group

As the monomer having an aryl group, any monomer having an aryl group can be appropriately selected without particular limitation; Examples of the monomer having an aryl group include esters or amides between at least one of a polyhydric alcohol compound, a polyvalent amine compound, and a polyvalent aminoalcohol compound having an aryl group and at least one of an unsaturated carboxylic acid.

Examples of the polyhydric alcohol compound, polyvalent amine compound and polyvalent aminoalcohol compound having the aryl group include polystyrene oxide, xylenediol, di- (β-hydroxyethoxy) benzene, 1,5-dihydroxy-1,2,3 , 4-tetrahydronaphthalene, 2,2-diphenyl-1,3-propanediol, hydroxybenzyl alcohol, hydroxyethyl resorcinol, 1-phenyl-1,2-ethanediol, 2,3,5, 6-tetramethyl-p-xylene-α, α'-diol, 1,1,4,4-tetraphenyl-1,4-butanediol, 1,1,4,4-tetraphenyl-2-butyne-1, 4-diol, 1,1'-bi-2-naphthol, dihydroxynaphthalene, 1,1'-methylene-di-2-naphthol, 1,2,4-benzenetriol, biphenol, 2,2 ' -Bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (hydroxyphenyl) methane, catechol, 4-chlororesorcinol, hydroquinone, hydroxybenzyl Alcohol, methylhydroquinone, methylene-2,4,6-trihydroxybenzoate, fluoroglucinol, pyrogallol, resorcinol, α- (1- Aminoethyl) -p-hydroxybenzyl alcohol and 3-amino-4-hydroxyphenylsulfone are listed.

Moreover, addition product of glycidyl compounds, such as xylene-bis- (meth) acrylamide, a novolak-type epoxy resin, or bisphenol A diglycidyl ether, and (alpha), (beta)-unsaturated carboxylic acid; Ester compounds obtained from vinyl monomers containing an acid such as phthalic acid and trimellitic acid and a hydroxyl group; Cationically polymerizable divinyl ethers as polymerizable monomers such as diallyl phthalate, triallyl trimellitate, diallylbenzene sulfonate and bisphenol A divinyl ether; Epoxy compounds such as novolac type epoxy resins and bisphenol A diglycidyl ether; Vinyl esters such as divinyl phthalate, divinyl terephthalate and divinylbenzene-1,3-disulfonate; And styrene compounds such as divinylbenzene, p-allylstyrene, and p-isopropenestyrene. Among these, the compound represented by the following general formula (38) is preferable.

In the formula (38), R ⁴ and R ⁵ each represent a hydrogen atom or an alkyl group.

In the said General formula (38), X <_5> and X <_6> respectively represent an alkylene oxide group, and an alkylene oxide group may be 1 type, or 2 or more types. Examples of the alkylene oxide groups include ethylene oxide groups, propylene oxide groups, butylene oxide groups, pentylene oxide groups, hexylene oxide groups, and random or block combination groups thereof. Among these, ethylene oxide groups, propylene oxide groups, butylene oxide groups and combinations thereof are preferable; Ethylene oxide group and propylene oxide group are more preferable.

In the said General formula (38), m5 and m6 represent the integer of 1-60, respectively, Preferably it is an integer of 2-30, More preferably, it is an integer of 4-15.

In the formula (38), T represents a divalent linking group such as methylene group, ethylene group, MeCMe, CF ₃ cCF ₃ , CO, and SO ₂ .

In the general formula (38), Ar ¹ and Ar ² each represent an aryl group which may have a substituent; Examples of Ar ¹ and Ar ² include phenylene and naphthylene; Examples of the substituents include alkyl groups, aryl groups, aralkyl groups, halogen groups, alkoxy groups and combinations thereof.

Specific examples of the monomer having an aryl group include 2,2-bis [4- (3- (meth) acryloxy-2-hydroxypropoxy) phenyl] propane, 2,2-bis [4-((meth) Acryloxyethoxy) phenyl] propane; 2,2-bis [4-((meth) acryloyloxypolyethoxy) phenyl] propane having 2 to 20 ethoxy groups substituted in one phenolic OH group, such as 2,2-bis [4- ((Meth) acryloyloxydiethoxy) phenyl] propane, 2,2-bis [4-((meth) acryloyloxytetraethoxy) phenyl] propane, 2,2-bis [4-((meta ) Acryloyloxypentaethoxy) phenyl] propane, 2,2-bis [4-((meth) acryloyloxydecaethoxy) phenyl] propane and 2,2-bis [4-((meth) acrylic Royloxypentadecaethoxy) phenyl] propane and the like; 2,2-bis [4-((meth) acryloxypropoxy) phenyl] propane, 2,2-bis [4-((meth) having 2 to 20 ethoxy groups substituted in one phenolic OH group Acryloyloxypolypropoxy) phenyl] propane, such as 2,2-bis [4-((meth) acryloyloxydipropoxy) phenyl] propane, 2,2-bis [4-((meth) acrylo Yloxytetrapropoxy) phenyl] propane, 2,2-bis [4-((meth) acryloyloxypentapropoxy) phenyl] propane, 2,2-bis [4-((meth) acryloyloxy Decapropoxy) phenyl] propane, 2,2-bis [4-((meth) acryloyloxypentadecapropoxy) phenyl] propane and the like; Compounds having not only a polyethylene oxide skeleton but also a polypropylene skeleton in one molecule as the ether moiety of these compounds described in WO01 / 98832, and BPE-200, BPE-500 and BPE-1000 (manufactured by Shin-nakamura Chemical Co.) Commercial item; And polymerizable compounds having a polypropylene skeleton as well as a polyethylene oxide skeleton. In these compounds, the site | part obtained from bisphenol A may be changed into the site | part obtained from bisphenol F, bisphenol S, etc.

Examples of the polymerizable compound having a polypropylene skeleton as well as the polyethylene oxide skeleton include addition products of bisphenol and ethylene oxide or propylene oxide, and 2-isocyanate ethyl (meth) acrylate, α, α-dimethyl-vinylbenzyl isocyanate, and the like. The compound which has a hydroxyl group at the terminal, is obtained as a polyaddition product, and has an isocyanate group and a polymeric group is mentioned.

-Other polymerizable monomers-

In the pattern formation method which concerns on this invention, you may use a polymeric monomer other than the monomer which has the said urethane group or an aryl group, or the monomer which has an aryl group within the range which does not deteriorate the characteristic of the said pattern formation material.

As a polymerizable monomer other than the monomer which has the said urethane group or aromatic ring, ester of unsaturated carboxylic acid and aliphatic polyhydric alcohol, such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, and isocrotonic acid, and unsaturated carboxylic acid and polyhydric amine Amides of the compounds are listed.

Examples of the ester of the unsaturated carboxylic acid and aliphatic polyhydric alcohol include ethylene glycol di (meth) acrylate as (meth) acrylate, polyethylene glycol di (meth) acrylate having 2 to 18 ethylene groups, such as diethylene glycol di (Meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, dodecaethylene glycol di (meth) acrylate, and tetradeca Ethylene glycol di (meth) acrylate and the like; Propylene glycol di (meth) acrylate having 2 to 18 propylene groups such as dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, dodecapropylene Glycol di (meth) acrylates and the like; Neopentylglycol di (meth) acrylate, ethylene oxide modified neopentylglycol di (meth) acrylate, propylene oxide modified neopentylglycol di (meth) acrylate, trimetholpropane tri (meth) acrylate, trimetholol Propane di (meth) acrylate, trimetholpropane tri (meth) acryloyloxypropyl ether, trimetholethane tri (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,3 -Butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, 1,4-cyclohexane Diol di (meth) acrylate, 1,2,4-butanetriol tri (meth) acrylate, 1,5-pentanediol (meth) acrylate, pentaerythritol di (meth) acrylate, pentaeryth Lithol tri (meth) acrylate, penta Ritthritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol Penta (meth) acrylate, sorbitol hexa (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, tricyclodecane di (meth) acrylate, neopentyl glycol modified trimetholpropane di (meth) acrylic Rate and the like; Di (meth) acrylates of alkylene glycol chains having at least one of an ethylene glycol chain and a propylene glycol chain, such as the compounds described in WO01 / 98832; Tri (meth) acrylate of trimetholpropane added with at least one of ethylene oxide and propylene oxide; Polybutylene glycol di (meth) acrylate, glycerin di (meth) acrylate, glycerin tri (meth) acrylate and xylenol di (meth) acrylate.

Ethylene glycol di (meth) acrylate, polyethyleneglycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate in the said (meth) acrylate from the point of the availability. Di (meth) acrylate, trimetholpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaene of an alkylene glycol chain having at least one of an ethylene glycol chain and a propylene glycol chain Rithritol triacrylate, pentaerythritol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, glycerin Di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,2,4-butanetriol tri (meth) acrylate, 1,4-cyclohexanedi The di (meth) acrylate, 1,5-pentanediol (meth) acrylate, neopentyl glycol di (meth) acrylate, and ethylene oxide addition tri (meth) acrylate of trimethylolpropane are preferred.

Examples of the ester of the itaconic acid and the aliphatic polyhydric alcohol compound, i. Methylene glycol diitaconate, pentaerythritol diitaconate and sorbitol tetraitaconate are listed.

Examples of esters of the crotonic acid and the aliphatic polyhydric alcohol compounds, ie crotonates, include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate and sorbitol tetracrotonate.

Examples of esters of the isocrotonic acid with the aliphatic polyhydric alcohol compounds, i.e. isocrotonates, include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate and sorbitol tetraisocrotonate.

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

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

As said polymerizable monomer, butanediol-1,4- diglycidyl ether, cyclohexane dimethanol glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglyci Α, β-unsaturated car to compounds having glycidyl groups such as dil ether, hexanediol diglycidyl ether, trimetholpropane triglycidyl ether, pentaerythritol tetraglycidyl ether and glycerin triglycidyl ether Compounds obtained by adding an acid; Polyester acrylates and polyester (meth) acrylate oligomers described in Japanese Patent Laid-Open No. 48-64183, Japanese Patent Laid-Open No. 49-43191, and Japanese Patent Laid-Open No. 52-30490; Butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, hexanediol diglycidyl ether, trimetholol Polyfunctional acrylates or methacrylates such as epoxy acrylate obtained from a reaction between methacrylic acid epoxy compounds such as propane triglycidyl ether, pentaerythritol tetraglycidyl ether and glycerin triglycidyl ether; Photocurable monomers and oligomers described in Adhesion Society of Japan, Vol. 20, No. 7, pp. 300-308 (1984); Allyl esters such as diallyl phthalate, diallyl adipate and diallyl malonate; Diallylamides, such as diallyl acetamide; Butanediol-1,4-divinyl ether, cyclohexane dimethanol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, dipropylene glycol divinyl ether, hexanediol divinyl ether, trimetholpropane trivinyl Cationically polymerizable divinyl ethers such as ether, pentaerythritol tetravinyl ether and glycerin trivinyl ether; Butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, hexanediol diol Epoxy compounds such as glycidyl ether, trimetholpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, and glycerin triglycidyl ether; Oxetane, such as 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene and those described in WO 01/22165; Two or more different ethylenically unsaturated double bonds such as N-β-hydroxyethyl-β-methacrylamide ethyl acrylate, N, N-bis (β-methacryloxyethyl) acrylamide, and acryl methacrylate The compound which has is enumerated.

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

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

The polymerizable monomer may be combined with a polymerizable compound containing one polymerizable group in a molecule, that is, a monofunctional monomer.

Examples of the monofunctional monomers include compounds exemplified as raw materials for the binder, mono- (meth) acryloyloxyalkyl esters, mono-hydroxyalkyl esters and γ-chloro-β-hydroxypropyl-β'-methacryl Dibasic monofunctional monomers such as loyloxyethyl-o-phthalate and the compounds described in Japanese Patent Application Laid-Open Nos. 6-236031, Japanese Patent Publication Nos. 2744643 and 2548016, and WO00 / 52529.

5-90 mass% is preferable, as for content of the polymeric compound of the said photosensitive layer, 15-60 mass% is more preferable, 20-50 mass% is further more preferable.

If the content is less than 5% by mass, the strength of the tenting film may be lowered. If the content is more than 90% by mass, edge melting during storage may be insufficient, and a problem of bleeding may occur.

5-100 mass% is preferable, as for content of the polyfunctional monomer which has 2 or more of said polymerizable groups in a molecule, 20-100 mass% is more preferable, 40-100 mass% is more preferable.

<Photoinitiator>

The photopolymerization initiator may be appropriately selected from known ones without particular limitation as long as it has a characteristic of initiating polymerization; Initiators that exhibit photosensitivity to ultraviolet to visible light are preferred. The initiator may be an active substance which generates radicals by the action of a photoexcited photosensitizer or a substance which initiates cationic polymerization depending on the monomer species.

The photopolymerization initiator preferably contains at least one component having a molecular absorption coefficient of about 50 M ⁻¹ cm ⁻¹ in the range of about 300 to 800 nm, more preferably 330 to 500 nm.

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives such as those having a triazine skeleton or an oxadiazole skeleton, hexaaryl biimidazole, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, and acylphosphine oxides. And metallocenes. Of these compounds, halogenated hydrocarbons, oxime derivatives, ketone compounds, and hexaaryl-biimidazole compounds having a triazine skeleton are preferred from the viewpoint of adhesion between the photosensitive layer and the substrate for forming a printed circuit board.

Examples of the hexaaryl-biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-biimidazole, 2,2'-bis (o- Fluorophenyl) -4,4 ', 5,5'-tetraphenyl-biimidazole, 2,2'-bis (2-bromophenyl) -4,4', 5,5'-tetraphenyl-ratio Imidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-biimidazole, 2,2'-bis (2-chlorophenyl) -4, 4 ', 5,5'-tetra (3-methoxyphenyl) -biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (4-methoxy Phenyl) -biimidazole, 2,2'-bis (4-ethoxyphenyl) -4,4 ', 5,5'-tetraphenyl-biimidazole, 2,2'-bis (2,4-dichloro Phenyl) -4,4 ', 5,5'-tetraphenyl-biimidazole, 2,2'-bis (2-nitrophenyl) -4,4', 5,5'-tetraphenyl-biimidazole, 2,2'-bis (2-methylphenyl) -4,4 ', 5,5'-tetraphenyl-biimidazole, 2,2'-bis (2-trifluoromethylphenyl) -4,4', 5 , 5'-tetraphenyl-biimidazole, and the compounds described in WO00 / 52529.

The hexaaryl-biimidazoles are, for example, Bull. Chem. Soc., Japan, 33, 565 (1960), and J. Org. It may be readily prepared by the method described in Chem., 36 (16), 2262 (1971).

Examples of halogenated hydrocarbon compounds having a triazine backbone are described in Wakabayashi, Bull. Chem. Soc., Japan, 42, 2924 (1969); British Patent No. 1388492; Japanese Patent Laid-Open No. 53-133428; German Patent No. 3337024; F.C. Schaefer et al., J. Org. Chem., 29, 1527 (1964); Japanese Patent Application Laid-Open No. 62-58241, Japanese Patent Application Laid-open No. Hei 5-281728 and Japanese Patent Application Laid-open No. 5-34920; And compounds described in US Pat. No. 4,229,976.

Wakabayashi Me, Bull. Chem. Soc. Examples of compounds described in Japan, 42, 2924 (1969) include 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-chlorophenyl) -4,6 -Bis (trichloromethyl) -1,3,5-triazine, 2- (4-tolyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- Methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,4-dichlorophenyl) -4,6-bis (trichloromethyl) -1,3 , 5-triazine, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-tri Azine, 2-n-nonyl-4,6-bis (trichloromethyl) -1,3,5-triazine and 2- (α, α, β-trichloroethyl) -4,6-bis (trichloro Methyl) -1,3,5-triazine are listed.

Examples of the compounds described in British Patent No. 1384292 are 2-styryl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methylstyryl) -4,6 -Bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine and 2- (4-methoxystyryl) -4-amino-6-trichloromethyl-1,3,5-triazine is listed.

Examples of the compound described in Japanese Patent Application Laid-open No. 53-133428 include 2- (4-methoxynaphtho-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine , 2- (4-ethoxynaphtho-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [4- (2-ethoxyethyl) -naph To-1-yl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4,7-dimethoxynaphtho-1-yl) -4,6-bis ( Trichloromethyl) -1,3,5-triazine and 2- (acenaphtho-5-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine are listed.

Examples of the compound described in German Patent No. 3337024 include 2- (4-styrylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4- Methoxystyryl) phenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (1-naphthylvinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2-chlorostyrylphenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-thiophene-2-vinylenephenyl ) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-thiophene-3-vinylenephenyl) -4,6-bis (trichloromethyl) -1, 3,5-triazine, 2- (4-furan-2-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine and 2- (4-benzofuran-2 -Vinylene phenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine are listed.

F.C. Schaefer et al., J. Org. Examples of compounds described in Chem., 29, 1527 (1964) include 2-methyl-4,6-bis (tribromomethyl) -1,3,5-triazine, 2,4,6-tris (tribro Momethyl) -1,3,5-triazine, 2,4,6-tris (dibromomethyl) -1,3,5-triazine, 2-amino-4-methyl-6-tribromomethyl -1,3,5-triazine and 2-methoxy-4-methyl-6-trichloromethyl-1,3,5-triazine are listed.

Examples of the compound described in Japanese Patent Application Laid-Open No. 62-58241 include 2- (4-phenylethylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4 -Naphthyl-1-ethynylphenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-triethynyl) phenyl) -4,6-bis (Trichloromethyl) -1,3,5-triazine, 2- (4- (4-methoxyphenyl) ethynylphenyl) -4,6-bis (trichloromethyl) -1,3,5-tri In azine, 2- (4- (4-isopropylphenylethynyl) phenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine and 2- (4- (4-ethylphenyl Thynyl) phenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

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

Examples of the compound described in Japanese Patent Laid-Open No. 5-34920 include 2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethylamino) -3-bromophenyl ] -1,3,5-triazine, trihalomethyl-s-triazine compound described in US Pat. No. 4239850, and also 2,4,6-tris (trichloromethyl) -s-triazine and 2- (4-chlorophenyl) -4,6-bis (tribromomethyl) -s-triazine is listed.

Examples of the compound described in US Patent No. 4212976 include compounds having an oxadiazole skeleton, such as 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2-trichloromethyl-5- ( 4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5- Phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5-styryl-1 , 3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-methoxystyryl ) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl) -1,3,4-oxadiazole and 2-tribromomethyl-5- Styryl-1,3,4-oxadiazoles are listed.

Examples of the oxime derivatives include compounds represented by the following general formulas (39) to (72).

Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromo Benzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenone-tetracarboxylic acid and its tetramethyl ester, 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-dime Methoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chlorothione Oxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, fluorene, acridon, benzoin; Benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, and benzoin phenyl ether; Benzyl dimethylketal, acridon, chloroacridone, N-methylacridone, N-butylacridone and N-butyl-chloroacridone.

Examples of the metallocene include bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), and Japanese Patent Application Laid-Open No. 53-133428, Patent Publication No. 57-1819, and Patent Publication No. 57- 6096, and the compounds described in US Patent 3615455.

As a photoinitiator of that excepting the above, Acridine derivatives, such as 9-phenyl acridine and 1,7-bis (9,9'- acridinyl) heptane; Polyhalogenated compounds such as carbon tetrabromide, phenyltribromosulfone and phenyltrichloromethylketone; 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) coumarin, 3-benzoylfuroyl-7-diethylaminocoumarin , 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3'-carbonyl bis (5,7-di- n-propoxycoumarin), 3,3'-carbonyl bis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin and 7 -Kumarins such as benzotriazole-2-ylcoumarin and Japanese Patent Application Laid-Open Nos. 5-19475, Patent Publication No. 7-271028, Patent Publication 2002-363206, Patent Publication 2002-363207, Patent Publication 2002-363208 Coumarin compounds described in Japanese Patent Application Laid-Open No. 2002-363209; Ethyl 4-dimethylaminobenzoate, n-butyl 4-dimethylaminobenzoate, phenethyl 4-dimethylaminobenzoate, 2-phthalimide 4-dimethylaminobenzoate, 2-methacryloyloxyethyl 4-dimethyl Aminobenzoate, pentamethylene-bis (4-dimethylaminobenzoate), phenethyl 3-dimethylaminobenzoate, pentamethylene ester, 4-dimethylamino benzaldehyde, 2-chloro-4-dimethylamino benzaldehyde, 4-dimethylamino Benzyl alcohol, ethyl (4-dimethylaminobenzoyl) acetate, 4-piperidine acetophenone, 4-dimethylaminobenzoin, N, N-dimethyl-4-toluidine, N, N-diethyl-3-phenetidine Amines such as tribenzylamine, dibenzylphenylamine, N-methyl-N-phenylbenzylamine, 4-bromo-N, N-diethylaniline, and tridodecylamine; Amino fluoranes such as ODB and ODBII; Leucocrystal violet; Acylphosphine oxides such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethylbenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide and lucirin TPO Are listed.

In addition, bisinal polyketaldonyl compounds described in US Patent No. 2367660; Acyloin ether compounds described in US Patent 2448828; Aromatic acyloin compounds substituted with α-hydrocarbons described in US Patent No. 2722512; Polynuclear quinone compounds described in US Pat. Nos. 3046127 and 2951758; Organoboron compounds, radical generators, triarylsulfonium salts, such as salts with hexafluoroantimony or hexafluorophosphate, phosphonium salts, such as (phenylthiophenyl) diphenyl sulfone, described in Japanese Patent Application Laid-Open No. 2002-229194; Various substances, such as phonium (effective as a cation polymerization initiator), and the onium compound of WO01 / 71428, are mentioned.

You may use these photoinitiators individually or in combination. Combinations of two or more photopolymerization initiators include, for example, combinations of hexaaryl-biimidazole compounds and aminoketones described in US Pat. No. 3549367; A combination of the benzothiazole compound and trihalomethyl-s-triazine compound described in JP-A-51-48516; A combination of an aromatic ketone compound such as thioxanthone and a hydrogen donor substance such as a dialkylamino-containing compound or a phenol compound; Combination of a hexaaryl-biimidazole compound and titanocene; And combinations of coumarin, tinanocene and phenylglycine.

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

<Other ingredients>

As other components, a sensitizer, a thermal polymerization inhibitor, a plasticizer, a coloring agent, a coloring agent, etc. are mentioned; In addition, other auxiliary agents such as adhesion promoters, pigments, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, thermal crosslinking agents, surface tension modifiers, and chain transfer agents may be used together with the substrate surface. . By suitably including these components, desired characteristics of the pattern forming material such as stability over time, photographic properties, developability, and film characteristics can be adjusted.

-Sensitizer-

The sensitizer is not limited to known materials and can be appropriately selected. Examples of the sensitizer include polynuclear aromatics such as pyrene, perylene, and triphenylene; Xanthenes such as fluorescein, eosin, erythrosine, rhodamine B, and rose bengal; Cyanines such as indocarbocyanine, thiacarbocyanine and oxacarbocyanine; Menocyanines, such as merocyanine and carbomerocyanine; Thiazines such as thionine, methylene blue and toluidine blue; Acridines such as acridine orange, chloroflavin and acriflavin; Anthraquinones such as anthraquinone; Scariums such as scarium; Acridons such as acridon, chloroacridone, N-methylacridone, N-butylacridone and N-butyl-chloroacridone; 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) coumarin, 3-benzofuroyl-7-diethylaminocoumarin , 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3'-carbonyl bis (5,7-di- n-propoxycoumarin), 3,3'-carbonyl bis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin and the like Kumarins and Japanese Patent Application Laid-Open Nos. 5-19475, Patent Publication No. 7-271028, Patent Publication 2002-363206, Patent Publication 2002-363207, Patent Publication 2002-363208, and Patent Publication 2002-363209 Listed coumarin compounds are listed.

Examples of the combination of the photopolymerization initiator and the sensitizer include (1) an electron donor type initiator and a sensitizing dye as described in Japanese Patent Application Laid-Open No. 2001-305734, (2) an electron acceptor type initiator and a sensitizing dye, and (3) Initiation mechanisms including electron transfer, such as combinations of electron donor initiators, electron acceptor initiators, and sensitizing dyes (ternary mechanisms), are listed.

0.05-30 mass% is preferable with respect to the whole composition of the photosensitive resin, 0.1-20 mass% is more preferable, and, as for content of the said sensitizer, 0.2-10 mass% is more preferable.

When the content is less than 0.05% by mass, the sensitivity to the active energy ray is lowered, the exposure process takes a long time and the productivity tends to be lowered. When the content is more than 30% by mass, from the photosensitive layer during storage A sensitizer may precipitate.

Thermal polymerization inhibitor

The thermal polymerization inhibitor may be sufficiently blended with the photosensitive layer in order to prevent polymerization due to high temperature or time.

Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxy benzophenone, 4-methoxy-2-hydroxy benzophenone , Cuprous chloride, phenothiazine, chloranyl, naphthylamine, β-naphthol, 2,6-di-t-butyl-4-cresol, 2,2'-methylene-bis (4-methyl-6- t-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, reaction product of copper and organic chelating agent, methyl salicylate, nitroso compound, nitroso compound and Al chelate compound And the like.

0.001-5 mass% is preferable with respect to the said polymeric compound of the said photosensitive layer, as for content of the said thermal polymerization inhibitor, 0.005-2 mass% is more preferable, 0.01-1 mass% is still more preferable. If the content is less than 0.001% by mass, the storage stability may be insufficient. If the content exceeds 5% by mass, the sensitivity to the active energy ray may be lowered.

Plasticizer

The plasticizer may be blended to adjust the film properties of the photosensitive layer, ie flexibility.

Examples of the plasticizer include dimethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diheptyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butylbenzyl phthalate, diisodecyl phthalate, diphenyl phthalate, diallyl. Phthalic acid esters such as phthalate and octylcaprylphthalate; Glycol esters such as triethylene glycol diacetate, tetraethylene glycol diacetate, dimethylglycophthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate and triethylene glycol dicaprylate ester ; Phosphoric acid esters such as tricresyl phosphate and triphenyl phosphate; Amides such as 4-toluenesulfonamide, benzenesulfonamide, N-n-butylbenzenesulfonamide and N-n-acetoamide; Aliphatic dibasic acid esters such as diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sebacate, dioctyl sebacate and dibutyl maleate; Triethyl citrate, tributyl citrate, glycerin triacetyl ester, butyl laurate, 4,5-diepoxycyclohexane-1,2-dicarboxylic acid dioctyl; And glycols such as polyethylene glycol and polypropylene glycol.

0.1-50 mass% is preferable with respect to the total component of the said photosensitive layer, as for content of the said plasticizer, 0.5-40 mass% is more preferable, 1-30 mass% is further more preferable.

Coloring Agent

The coloring agent may be used to form a visible image or impart developability to the photosensitive layer after exposure.

Examples of the colorant include tris (4-dimethylaminophenyl) methane (leucocrystal violet), tris (4-diethylaminophenyl) methane, tris (4-dimethylamino-2-methylphenyl) methane, tris (4-diethyl Amino-2-methylphenyl) methane, bis (4-dibutylaminophenyl)-[4- (2-cyanoethyl) methylaminophenyl] methane, bis (4-dimethylaminophenyl) -2-quinolylmethane and tris Aminotriaryl methanes such as (4-dipropylaminophenyl) methane; Aminoxanthenes such as 3,6-bis (dimethylamino) -9-phenylxanthene and 3-amino-6-dimethylamino-2-methyl-9- (2-chlorophenyl) xanken; Aminothioxanthenes such as 3,6-bis (diethylamino) -9- (2-ethoxycarbonylphenyl) thioxanthene and 3,6-bis (dimethylamino) thioxanthene; Such as 3,6-bis (diethylamino) -9,10-dihydro-9-phenylacridine and 3,6-bis (benzylamino) -9,10-dihydro-9-methyl acridine Amino-9,10-dihydroacridines; Aminophenoxazines such as 3,7-bis (diethylamino) phenoxazine; Aminophenothiazines such as 3,7-bis (ethylamino) phenothiazine; Aminodihydrophenazines such as 3,7-bis (diethylamino) -5-hexyl-5,10-dihydrophenazine; Aminophenylmethanes such as bis (4-dimethylaminophenyl) anilinomethane; Aminohydrocinnamic acids such as 4-amino-4'-dimethylaminodiphenylamine and 4-amino-α, β-dicyanohydrocinnamate methyl ester; Hydrazines such as 1- (2-naphthyl) -2-phenylhydrazine; Amino-2,3-dihydroanthraquinones such as 1,4-bis (ethylamino) -2,3-dihydroanthraquinone; Phenethylanilines such as N, N-diethyl-4-phenethylaniline; Acyl derivatives of leuco pigments containing basic NH such as 10-acetyl-3,7-bis (dimethylamino) phenothiazine; oxidizable such as tris (4-diethylamino-2-tolyl) ethoxycarbonylmethane Leuco-type compounds which do not have hydrogen but can be oxidized to a coloring compound; Leucoindigo dye; In the form of color such as 4,4'-ethylenediamine, diphenylamine, N, N-dimethylaniline, 4,4'-methylenediaminetriphenylamine and N-vinylcarbazole described in US Pat. Nos. 3,042,515 and 3,042,517 Listed are organic amines that can be oxidized. Among these, triaryl methanes, such as a leuco crystal violet, are especially preferable.

In addition, the coloring agent may be combined with a halogen compound for coloring from the leuco compound.

Examples of the halogen compound include tetrabromocarbon, iodineform, ethylene bromide, methylene bromide, amyl bromide, isoamyl bromide, amyl iodide, isobutylene bromide, butyl iodide, diphenylmethyl bromide, hexachloromethane , 1,2-dibromoethane, 1,1,2,2-tetrabromoethane, 1,2-dibromo-1,1,2-trichloroethane, 1,2,3-tribromo Propane, 1-bromo-4-chlorobutane, 1,2,3,4-tetrabromobutane, tetrachlorocyclopropene, hexachlorocyclopentadiene, dibromocyclohexane and 1,1,1-trichloro Halogenated hydrocarbons such as rho-2,2-bis (4-chlorophenyl) ethane; 2,2,2-trichloroethanol, tribromoethanol, 1,3-dichloro-2-propanol, 1,1,1-trichloro-2-propanol, di (iodohexamethylene) aminoisopropanol, tribro Halogenated alcohol compounds such as parent-t-butyl alcohol and 2,2,3-trichlorobutane-1,4-diol; 1,1-dichloroacetone, 1,3-dichloroacetone, hexachloroacetone, hexabromoacetone, 1,1,3,3-tetrachloroacetone, 1,1,1-trichloroacetone, 3,4-di Halogenated carbonyl compounds such as bromo-2-butanone and 1,4-dichloro-2-butanone-dibromocyclohexanone; Halogenated ether compounds such as 2-bromoethyl methyl ether, 2-bromoethylethyl ether, di (2-bromoethyl) ether and 1,2-dichloroethyl ethyl ether; Bromoethyl acetate, ethyl trichloroacetate, trichloroethyl trichloroacetate, homo or copolymer of 2,3-dibromopropyl acrylate, trichloroethyl dibromopropionate and ethyl α, β-dichloroacrylic Halogenated ester compounds such as late; Chloroacetamide, bromoacetamide, dichloroacetamide, trichloroacetamide, tribromoacetamide, trichloroethyltrichloroacetamide, 2-bromoisopropionamide, 2,2,2-trichloropropionamide Halogenated amide compounds such as N-chlorosuccinimide and N-bromosuccinimide; Tribromomethylphenylsulfone, 4-nitrophenyltribromomethylsulfone, 4-chlorophenyltribromomethylsulfone, tris (2,3-dibromopropyl) phosphate and 2,4-bis (trichloromethyl)- And compounds having sulfur and / or phosphorus such as 6-phenyltriazole.

In the organic halogenated compound, it is preferable to contain two or more halogen atoms bonded to one carbon atom, and more preferably contain three halogen atoms bonded to one carbon atom. These organic halogenated compounds can be used individually or in combination. Among these halogenated compounds, tribromomethylphenyl sulfone and 2,4-bis (trichloromethyl) -6-phenyltriazole are preferable.

0.01-20 mass% is preferable with respect to the all components of the said photosensitive layer, as for content of the said coloring agent, 0.05-10 mass% is more preferable, 0.1-5 mass% is further more preferable. 0.001-5 mass% is preferable with respect to the all components of the said photosensitive layer, and, as for content of the said halogenated compound, 0.005-1 mass% is more preferable.

-dyes-

The photosensitive layer may be blended with dyes to impart color to facilitate handling or to improve storage stability.

Examples of the dyes include brilliant green, eosin, ethyl violet, erythrosine B, methyl green, crystal violet, basic fuxin, phenolphthalein, 1,3-diphenyltriazine, alicin red S, thymolphthalein, methyl Violet 2b, Quinaldine Red, Rose Bengal, Methyl-Yellow, Timolsulfophthalein, Xylenol Blue, Methyl Orange, Orange IV, Diphenyl Thiocarbazone, 2,7-Dichlorofluorescein, Paramethyl Red , Congo Red, Benzofurpurin 4b, α-naphthyl Red, Nile Blue 2b, Nile Blue A, Penacetarin, Methyl Violet, Malachite Green, Parafuxin, Oil Blue # 603 (Orient Chemical Industry Co., Ltd. Products), Rhodamine B, Rhodamine 6G, and Victoria Pure Blue BOH. Among these dyes, cationic dyes such as oxalate of malachite green and sulfate of malachite green are preferable. The counterion of the cationic dye may be a residue of an organic or inorganic acid such as bromic acid, iodic acid, sulfuric acid, phosphoric acid, oxalic acid, methanesulfonic acid and toluene sulfonic acid.

0.001-10 mass% is preferable with respect to the total component of the said photosensitive layer, as for content of the said dye, 0.01-5 mass% is more preferable, 0.1-2 mass% is still more preferable.

Adhesion Promoter

In order to improve the adhesiveness between an interlayer or a pattern forming material and a board | substrate, what is called adhesion promoter can be used.

Examples of the adhesion promoter include those described in Japanese Patent Application Laid-Open Nos. H5-11439, JP-A-5-341532 and JP-A-6-43638; Specific examples of the adhesion promoter include benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1 -Phenyl-triazole-2-thione, 3-morpholinomethyl-5-phenyl-oxadiazole-2-thione, 5-amino-3-morpholinomethyl-thiadiazole-2-thione, 2-mercapto -5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group containing benzotriazole and silane coupling agent are listed.

0.001-20 mass% is preferable with respect to the whole component of the said photosensitive layer, as for content of the said adhesion promoter, 0.01-10 mass% is more preferable, 0.1 mass%-5 mass% are more preferable.

The photosensitive layer may contain organic sulfur compounds, peroxides, redox reactive compounds, azo or diazo compounds, photoreductive dyes or organic halogen compounds as described in "Light Sensitive Systems, Chapter 5, J. Curser".

Examples of the organic sulfur compound include di-n-butyldisulfide, dibenzyldisulfide, 2-mercaptobenzthiazole, 2-mercaptobenzoxazole, thiophenol, ethyltrichloromethanesulfonate and 2-mercaptobenz Imidazoles are listed.

Examples of such peroxides include di-t-butylperoxide, benzoyl peroxide, methylethylketone peroxide.

The redox compound is a combination of persulfate ions and peroxides such as ferrous, peroxide and ferric ions and a reducing agent.

Examples of the azo or diazo compound include diazoniums such as α, α'-azobis-isobutylonitrile, 2-azobis-2-methylbutylonitrile and 4-aminodiphenylamine.

Examples of such photoreducible dyes include rose bengal, erythrosine, eosin, acriflavin, riboflavin and thionine.

-Surfactants-

In order to improve the surface nonuniformity which arises at the time of manufacture of the said pattern formation material of this invention, a well-known surfactant can be used.

The surfactant may be appropriately selected from anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and fluorine-containing surfactants.

As for content of the said surfactant, 0.001-10 mass% is preferable with respect to solid content of the photosensitive resin composition. If the content is less than 0.001% by mass, the nonuniformity improving effect may be insufficient. If the content is more than 10% by mass, the adhesion may deteriorate.

In addition, the surfactant contains an aliphatic group containing 40 mass% or more of fluorine atoms, a carbon chain of 3 to 20 carbon atoms, and a hydrogen atom bonded to the third carbon atom of the terminal carbon atom substituted with a fluorine atom. The fluorine-containing polymer surfactant containing the copolymerizable component of acrylate or methacrylate which is mentioned is also illustrated preferably.

The thickness of the photosensitive layer can be appropriately selected without particular limitation; 1-100 micrometers is preferable, as for thickness, 2-50 micrometers is more preferable, and its 4-30 micrometers are more preferable.

[Production of Pattern Forming Material]

The pattern forming material of the present invention can be produced as follows. First, the solution of the photosensitive resin composition is manufactured by melt | dissolving, emulsifying, or disperse | distributing the said various components or material in water or a solvent.

The solvent of the photosensitive resin composition solution can be appropriately selected depending on the purpose without particular limitation; Examples of the solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and n-hexanol; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and diisobutyl ketone; Esters such as ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate and methoxypropyl acetate; Aromatic hydrocarbons such as toluene, xylene, benzene and ethylbenzene; Halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride and monochlorobenzene; Ethers such as tetrahydrofuran, diethylene ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and 1-methoxy-2-propanol; Dimethylformamide, dimethylacetamide, dimethyl sulfoxide and sulfolane are listed. These may be used alone or in combination. Moreover, you may add a well-known surfactant to a solvent.

The photosensitive resin composition solution may be applied onto a support and dried to form a photosensitive layer to prepare a pattern forming material.

The coating method of the photosensitive resin composition solution can be appropriately selected depending on the purpose without particular limitation; Examples of the coating method include spray method, roll coating method, rotary coating method, slit coating method, extrusion coating method, curtain coating method, die coating method, gravure coating method, wire bar coating method and knife coating method.

Drying conditions in the coating method are generally different depending on various components, the type of solvent and the amount of solvent; Normal temperature is 60-110 degreeC, and time is 30 second-15 minutes.

<< Support and Protective Film >>

The support can be appropriately selected depending on the purpose without particular limitations; The support shows peelability to the photosensitive layer, and the support shows high transparency and has high surface smoothness.

Preferably, the support is made of a transparent synthetic resin; Examples of the synthetic resins include polyethylene terephthalate, polyethylene naphthalate, triacetyl cellulose, diacetyl cellulose, polyalkyl methacrylate, polymethacrylate copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, Cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinylchloride-vinylacetate copolymer, polytetrafluoroethylene, polytrifluoroethylene, cellulose film and nylon film; Among these resins, polyethylene terephthalate is more preferable. These resins may be used alone or in combination.

The thickness of the support can be appropriately selected depending on the purpose; 2-150 micrometers is preferable, as for thickness, 5-100 micrometers is more preferable, and its 8-50 micrometers are more preferable.

The shape of the support can be appropriately selected according to the purpose; Preferably the shape is long. The length of the elongate support is selected from 10 to 20,000 m, for example.

In the pattern forming material, a protective film may be formed on the photosensitive layer. The material of the protective film may be those exemplified in the above support, or may be paper, polyethylene or polypropylene laminated paper. Among these materials, polyethylene films and polypropylene films are preferred.

The thickness of the protective film can be appropriately selected without particular limitation; 5-100 micrometers is preferable, as for the thickness, 8-50 micrometers is more preferable, and 10-30 micrometers is more preferable.

In the use of the protective film, it is preferable that the adhesive force A between the photosensitive layer and the support and the adhesive force B between the photosensitive layer and the protective film exhibit the following relationship: adhesive force A> adhesive force B.

Examples of the combination of the support and the protective film, namely (support / protective film), include (polyethylene terephthalate / polypropylene), (polyvinyl chloride / cellophane), (polyimide / polypropylene), and (polyethylene terephthalate / polyethylene tere). Phthalates). In addition, by surface treatment of the support and / or the protective film, the relationship of the adhesive force as described above can be obtained. Surface treatment of the support may be performed to increase adhesion to the photosensitive layer; Examples of the surface treatment include an undercoat layer, corona discharge treatment, flame treatment, UV ray treatment, RF irradiation treatment, glow discharge treatment, active plasma treatment and laser beam treatment.

0.3-1.4 are preferable and, as for the static friction coefficient of the said support body and the said protective film, 0.5-1.2 are more preferable.

If the static friction coefficient is less than 0.3, it is too slippery and a winding shift may occur in the roll form. If the static friction coefficient exceeds 1.4, it is difficult to wind the material in the roll form.

Preferably, the pattern forming material is wound in a cylindrical winding core and stored in the shape of a long roll. The length of the long pattern forming material is not particularly limited, and the length thereof is, for example, 10 to 20,000 m. In addition, in order to facilitate handling during use, the pattern material may be slit processed and may be formed in rolls every 100 to 1,000 m. Preferably, the pattern forming material is wound up so that the support is on the outermost side of the roll form. Further, the pattern forming material may be slitted in sheet form. At the time of storage, Preferably, the moisture-proof separator which has a desiccant especially is provided in the cross section of a pattern formation material, and a package is also made with a high moisture-proof material in order to prevent edge melting.

You may surface-treat in order to adjust the adhesiveness of this protective film and the said photosensitive layer to the said protective film. The surface treatment is performed by, for example, forming an undercoat layer of a polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene and polyvinyl alcohol on the surface of the protective film. The undercoat layer may be formed by applying a polymer solution to the surface of the protective film, and then drying for 1 to 30 minutes at 30 to 150 ° C, particularly at 50 to 120 ° C. In addition to the photosensitive layer, the support, and the protective film, other layers such as a peeling layer, an adhesive layer, a light absorbing layer, and a surface protective layer may be formed.

<Substrate>

The said board | substrate can be suitably selected from a commercially available material, and may be a nonuniform surface other than the surface with high smoothness. Preferably, the substrate is plate-shaped; Specifically, the substrate is selected from materials such as printed wiring boards such as copper-clad laminates, glass plates such as soda glass plates, synthetic resin films, paper and metal plates.

The substrate is used by forming a laminate in which the photosensitive layer of the pattern forming material is integrated on the substrate. In such a configuration, the pattern can be formed by a developing step, for example, by exposing the photosensitive layer of the pattern forming material of the laminate and curing the exposed area.

Pattern forming material of the present invention is a printed wiring board, color filter; Display members such as column materials, rib materials, spacers, and separation walls; It can be used for holograms, micromachines and proofs. In addition, the pattern forming material may be used in the pattern forming method according to the present invention.

[Other Processes]

The other steps can be suitably carried out using a conventional step of forming a pattern such as a developing step, an etching step and a plating step. These processes can be used alone or in combination.

In the said developing process, after exposing the photosensitive layer of a pattern formation material and hardening the exposed area | region of the said photosensitive layer, a non-hardened area | region is removed and a pattern is manufactured.

The method of removing the uncured region can be appropriately selected without particular limitation; For example, the uncured region can be removed by a developer.

The developer can be appropriately selected depending on the purpose; Examples of the developer include an alkaline aqueous solution, an aqueous developer and an organic solvent; Among these, a weakly alkaline aqueous solution is preferable. Base components of the weakly alkaline aqueous solution include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, sodium phosphate, potassium phosphate, sodium pyrophosphate, and fatigue Potassium phosphate and borax are listed.

About 8-12 are preferable and, as for pH of the said weak alkaline aqueous solution, about 9-11 are more preferable. Examples of such a solution include sodium carbonate and potassium carbonate aqueous solutions having a concentration of 0.1 to 5% by mass. The temperature of the developer can be appropriately selected depending on the developability of the developer; For example, the temperature of a developing solution is about 25-40 degreeC.

The developer includes a surfactant, an antifoaming agent; Organic bases such as ethylene diamine, ethanol amine, tetramethylene ammonium hydroxide, diethylene triamine, triethylene pentamine, morpholine and triethanol amine; It can be used in combination with an organic solvent which promotes development of alcohols, ketones, esters, ethers, amides and lactones. The developer may be an aqueous developer selected from an aqueous solution, an aqueous alkali solution, a combination of an aqueous solution and an organic solvent, or may be an organic developer.

The said etching can be performed by the method suitably selected by the conventional etching method.

The etching liquid used for the said etching method can be suitably selected according to the objective; When the metal layer is made of copper, examples of the liquefied solution include a cupric chloride solution, a ferric chloride solution, an alkali etching solution, a hydrogen peroxide etching solution, and the like; Among them, the ferric chloride solution is preferable in view of the etching factor.

The pattern forming material may be etched and removed to form a permanent pattern on the substrate. The permanent pattern can be appropriately selected according to the purpose; For example, the pattern is a wiring pattern.

The plating process may be performed by a method selected from a conventional plating process.

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, nickel plating such as watt bath (nickel sulfate-nickel chloride) plating and nickel sulfamate plating, and hard gold plating; Gold plating such as soft gold plating is listed.

After the plating treatment in the plating step, the pattern forming material is removed and the permanent pattern can be formed by performing selective etching on unnecessary parts.

Since the pattern forming method according to the present invention can form the permanent pattern accurately and effectively by suppressing the distortion of the image formed on the pattern forming material, the pattern forming method can be used in various patterns, particularly high precision, requiring high precision exposure. It can be used suitably for the wiring pattern.

[Manufacturing method of printed wiring board]

The pattern forming method according to the present invention can be suitably used for the production of printed wiring boards, in particular for the production of printed wiring boards having through holes or via holes. The manufacturing method of the printed wiring board based on the pattern formation method which concerns on this invention is demonstrated below.

In the method of manufacturing a printed wiring board having the through-hole and / or the via-hole, the pattern includes (i) forming a laminate by laminating a pattern forming material on a substrate of a printed wiring board having holes so that the photosensitive layer and the substrate face each other. (ii) irradiating the area forming wiring patterns and holes from the opposite side of the substrate to harden the photosensitive layer, (iii) removing the support of the pattern forming material from the laminate, and (iv ) By developing the photosensitive layer of the laminate to remove the cured portion of the laminate.

On the other hand, the support of (iii) can be removed between (i) and (ii) instead of between (ii) and (iv).

Then, using the formed pattern, the substrate of the printed wiring board is etched or plated by using a conventional subtractive method or an additive method such as a semi addition method or a pull addition method. A wiring board can be manufactured. Among these methods, the above removal method is preferable in order to form a printed wiring board by industrially advantageous tenting. After the treatment, the cured resin remaining on the substrate of the printed wiring board is peeled off, or in the case of the semi-addition method, the desired printed wiring board is obtained by etching the thin film portion after peeling. Also in the case of a multilayer printed wiring board, the same method as that of the printed wiring board can be used.

The manufacturing method of the printed wiring board which has a through hole using a pattern formation material is demonstrated below.

First, the board | substrate of the printed wiring board which covered the surface of the board | substrate with the metal plating layer is manufactured. The substrate of the printed wiring board may be a substrate manufactured by forming a copper plating layer on an insulating substrate such as a copper-clad laminate, glass or epoxy resin, or a substrate formed by laminating these substrates and forming a copper plating layer.

When the protective layer is present on the pattern forming material, the protective film is peeled off as a lamination step, and the photosensitive layer of the pattern forming material is pressed onto the surface of the substrate of the printed wiring board by using a pressure roller, thereby forming the printed wiring board. The laminated body containing a board | substrate and the said laminated body can be obtained.

The lamination temperature of the pattern forming material can be appropriately selected without particular limitation; The temperature may be room temperature, such as 15-30 degreeC, or high temperature, such as 30-180 degreeC, Preferably the substantially warm temperature, such as 60-140 degreeC, is preferable.

The roll pressure of the pressing roll can be appropriately selected without particular limitation; The pressure is preferably 0.1 to 1 MPa; The crimping speed can be appropriately selected without particular limitation, and the speed is preferably 1 to 3 m / sec.

The substrate of the printed wiring board may be preheated before pressing; The substrates may be laminated under reduced pressure.

The laminate laminates a pattern forming material on a substrate of a printed wiring board; Or you may apply | coat the photosensitive resin composition solution for pattern formation materials directly on the board | substrate of a printed wiring board, and dry the solution, and may laminate | stack and form the photosensitive layer on the board | substrate of the said printed wiring board.

Next, a laser beam is irradiated to the photosensitive layer from the opposite side to the board | substrate of the said laminated body to harden a photosensitive layer. In this case, if necessary, when the transparency of the support is low, the support is peeled off and then irradiated.

When a support exists on a board | substrate after laser irradiation, a support is peeled from a laminated body as a support peeling process.

In the developing step, a non-cured region of the photosensitive layer on the substrate of the printed wiring board is dissolved and removed using a suitable developer, and a pattern including a hardened layer for forming a wiring pattern and a hardened layer for protecting the metal layer of the through hole is formed. The metal layer is exposed on the substrate surface of the printed wiring board.

As needed, you may perform another process for accelerating the said hardening reaction by post-heating and post-exposure, for example. The above development may be a wet method or a dry method as described above.

Then, as an etching step, the metal layer exposed on the substrate surface of the printed wiring board is dissolved and removed with an etching solution. Since the opening of the through hole is covered with a cured resin or a tent film, the etching solution does not corrode the metal plating in the smear through hole in the through hole, so that the metal plating can maintain a specific behavior, so that a wiring pattern can be formed on the substrate of the printed wiring board. Can be.

The etchant can be appropriately selected depending on the purpose; Examples of the etching solution for forming the metal layer with copper include cupric chloride solution, ferric chloride solution, alkaline etching solution and hydrogen peroxide solution; Among these, a ferric chloride solution is preferable from the viewpoint of the etching factor.

Next, as a step of removing the cured material, the cured layer is removed from the substrate of the printed wiring board using, for example, a strong alkaline aqueous solution.

The basic component of the strongly alkaline aqueous solution can be appropriately selected without particular limitation, and examples of the basic component include sodium hydroxide and potassium hydroxide. PH of the said strong alkaline aqueous solution is about 12-14, for example, Preferably it is about 13-14. The strong alkaline aqueous solution may be an aqueous solution of sodium hydroxide or potassium hydroxide at a concentration of 1 to 10% by mass.

The printed wiring board may have a multilayer structure. In addition, you may apply the said pattern forming material to a plating process instead of the said etching process. The plating method includes copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high flow solder plating, nickel plating such as watt bath (nickel sulfate-nickel chloride) plating and nickel sulfamate plating, and hard gold plating and soft gold plating. Gold plating, etc. may be sufficient.

1 is a partially enlarged view showing an example of the configuration of a digital micromirror device (DMD).

2A is a diagram for explaining an example of the operation of the DMD.

2B is a diagram for explaining an example of the operation of the DMD.

3A is an exemplary plan view showing an exposure beam and a scan line when the DMD is not inclined.

3B is an exemplary plane view showing an exposure beam and a scan line when the DMD is inclined.

4A is an exemplary diagram illustrating a use area of a DMD.

4B is an exemplary view showing another usage area of the DMD.

5 is an exemplary plan view illustrating a method of exposing the photosensitive layer by one scan by a scanner.

6A is an exemplary plan view for explaining a method of exposing a photosensitive layer by scanning a plurality of times by a scanner.

6B is another exemplary plan view for explaining a method for exposing the photosensitive layer by plural extra scanning by a scanner.

7 is a schematic perspective view showing an example of a pattern forming apparatus.

8 is a schematic perspective view showing an example of a scanner configuration of a pattern forming apparatus.

9A is an exemplary plan view showing an exposure area formed on the photosensitive layer.

9B is an exemplary plan view showing an area exposed by each exposure head.

10 is a schematic perspective view showing an example of an exposure head including a laser modulator.

FIG. 11 is an exemplary cross-sectional view showing the configuration of the exposure head shown in FIG. 10 in the sub-scanning direction along the optical axis.

12 shows an example of a controller for controlling the DMD based on the pattern information.

13A is an exemplary cross-sectional view showing the configuration of another exposure head of another imaging optical system along the optical axis.

13B is an exemplary plan view showing an optical image projected on the exposure surface when no microlens is used.

13C is an exemplary plan view showing an optical image projected on the exposure surface when a microlens is used.

FIG. 14 is an exemplary view showing distortion of a reflecting surface of a micromirror constituting a DMD in a contour line. FIG.

15A is an exemplary graph illustrating a height displacement along the X direction of the micromirror.

15B is an exemplary graph illustrating a height displacement along the Y direction of the micromirror.

16A is an exemplary front view illustrating a microlens array used in a pattern forming apparatus.

16B is an exemplary side view illustrating a microlens array used in the pattern forming apparatus.

17A is an exemplary front view illustrating microlenses of a microlens array.

17B is an exemplary side view illustrating the microlenses of the microlens array.

18A is an exemplary view schematically showing a laser condensing state in the cross section of the microlens.

18B is an exemplary view schematically showing a laser condensing state at another cross section of the microlens.

19A is an exemplary diagram showing a simulation of a beam diameter near a condensing point of a microlens according to the present invention.

19B is an illustration showing another simulation similar to FIG. 19A at another position according to the present invention.

19C is an illustration showing another simulation similar to FIG. 19A at another position according to the present invention.

FIG. 19D is an exemplary view showing another simulation similar to FIG. 19A at another location in accordance with the present invention. FIG.

20A is an exemplary view showing a simulation of the beam diameter near the condensing point in the conventional pattern forming method.

20B is an exemplary view showing another simulation similar to FIG. 20A at another position.

20C is an exemplary view showing another simulation similar to FIG. 20A at another position.

20D is an exemplary view showing another simulation similar to FIG. 20A at another position.

21 is an exemplary plan view showing another configuration of the combined laser source.

22A is an exemplary front view illustrating microlenses of a microlens array.

22B is an exemplary side view illustrating the microlenses of the microlens array.

FIG. 23A is an exemplary view schematically showing a laser condensing state in the cross section of the microlens shown in FIG. 22B.

FIG. 23B is an exemplary view schematically showing a laser condensing state at another cross section of the microlens shown in FIG. 22B.

24A is an exemplary diagram for explaining the concept of correction by the light amount distribution correction optical system.

24B is another exemplary view for explaining the concept of correction by the light amount distribution correction optical system.

24C is another exemplary view for explaining the concept of correction by the light amount distribution correction optical system.

25 is an exemplary graph showing a light amount distribution of a Gaussian distribution without light amount correction.

Fig. 26 is an exemplary graph showing the light amount distribution corrected by the optical system of light amount distribution correction.

27A (A) is an exemplary perspective view showing the configuration of a fiber array laser source.

FIG. 27A (B) is a partially enlarged view of FIG. 27A (A).

27A (C) is an exemplary plan view showing an arrangement of light emitting points of a laser emitting unit.

27A (D) is an exemplary plan view showing another arrangement of laser light emitting points.

27B is an exemplary front view showing the arrangement of laser light emitting points in the fiber array laser source.

28 is an exemplary view showing a configuration of a multimode optical fiber.

29 is an exemplary plan view showing a configuration of a combined laser source.

30 is an exemplary plan view showing a configuration of a laser module.

FIG. 31 is an exemplary side view illustrating a configuration of the laser module illustrated in FIG. 30.

32 is a partial side view illustrating the configuration of the laser module illustrated in FIG. 30.

33 is an exemplary perspective view showing the configuration of a laser array.

34A is an exemplary perspective view showing the configuration of a multi-cavity laser.

34B is an exemplary perspective view showing a multi-cavity laser array in which the multi-cavity lasers shown in FIG. 34A are arranged in an array.

35 is an exemplary plan view showing another configuration of the combined laser source.

36A is an exemplary plan view showing still another configuration of a combined laser source.

36B is an exemplary cross-sectional view along the optical axis of FIG. 36A.

37A is an exemplary sectional view of the exposure apparatus showing the depth of focus in the pattern formation method of the prior art.

37B is an exemplary sectional view of the exposure element showing the depth of focus in the pattern forming method according to the present invention.

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated in detail with reference to an Example, this invention is not limited to these. Unless otherwise noted, all parts are parts by weight.

(Example 1)

Manufacturing of Pattern Forming Materials

The solution of the photosensitive resin composition containing the following component was apply | coated to the polyethylene terephthalate film of thickness 20micrometer as a support body, the apply | coated solution was dried, the photosensitive layer of thickness 15micrometer was formed, and the pattern forming material was manufactured.

[Component of Photosensitive Resin Composition Solution]

15 parts of copolymers of methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid

(Mass ratio: 50/20/7/23, mass average molecular weight: 90,000, acid value: 150)

7.0 parts of polymerizable monomers represented by the following general formula (73)

7.0 parts addition product of hexamethylene diisocyanate and tetraethylene oxide monomethacrylate (molar ratio: 1/2)

-N-methylacridone0.11part

2.17 parts of -2,2-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole

0.23 parts of 2-mercaptobenzimidazole

Malachite green oxalate 0.02parts

Royko Crystal Violet 0.26part

40 parts methyl methyl ketone

20 parts of -1-methoxy-2-propanol

Here, in general formula (73), m + n = 10. The compound represented by the general formula (73) includes those represented by the general formula (38).

A polyethylene film having a thickness of 20 μm was laminated as a protective film on the photosensitive layer of the pattern forming material. Next, a copper clad laminated board (no through hole, copper thickness: 12 µm) subjected to polishing, rinsing and drying was produced to obtain a substrate. By peeling the photosensitive layer on the copper clad laminate with a laminator (MODEL 8b-720-PH, manufactured by Taisei-Laminator Co.) so as to contact the photosensitive layer and the copper clad laminate while peeling off the protective layer of the pattern forming material. A laminate in which polyethylene terephthalate as a layer and a support was sequentially laminated was prepared.

The crimping conditions were the temperature of the press roll: 105 degreeC, the pressure of a press roll: 0.3 MPa, and the lamination | stacking speed: 1 m / min.

The resolution, exposure speed, and etching property were evaluated for the produced laminate. The results are shown in Table 3.

<Resolution>

(1) Measuring method of shortest developing time

After peeling the polyethylene terephthalate film as a support body from the said laminated body, the sodium carbonate aqueous solution of concentration 1 mass% was sprayed at 30 degreeC and 0.15 Mpa on the whole surface of the photosensitive layer on a copper clad laminated board. The time from the initial injection at which the photosensitive layer on the copper clad laminate was dissolved and removed was measured, and the time was defined as the shortest developing time. As a result, the shortest developing time was 10 seconds.

(2) measurement of sensitivity

The amount of light energy is changed at intervals of 2 ^1/2 times from 0.1 to 100 mJ / cm 2 to the photosensitive layer of the pattern forming material of the laminate, and the laser is emitted from the side surface of the polyethylene terephthalate film using a pattern forming apparatus described later. The beam was irradiated to cure part of the photosensitive layer.

After leaving at room temperature for 10 minutes, the polyethylene terephthalate film as a support was peeled from the laminate, and then an aqueous solution of sodium carbonate having a concentration of 1% by mass at 30 ° C and 0.15 MPa was applied to the entire surface of the photosensitive layer on the copper clad laminate at (1). After spraying for twice the time of the obtained shortest developing time, and removing the unhardened part, the thickness of the remaining hardened layer was measured. Then, the relationship between the amount of irradiation light and the thickness of the cured layer was plotted to obtain a sensitivity curve. From the obtained sensitivity curve, the amount of light energy when the thickness of the hardened region was 15 µm was measured, and the amount of light energy was used as the amount of light energy required to cure the photosensitive layer.

As a result, the amount of light energy required to cure the photosensitive layer was 3 mJ / cm 2.

<< pattern forming device >>

A harmonic laser source shown in Figs. 27A to 32 as the laser source; In the main-scan direction shown in FIG. 4, 1024 micromirrors are arranged in an array, 4,768 sets of arrays are arranged in the sub-scan direction, and only 1024 columns x 256 rows of these micromirrors can be driven. DMD 50 as a laser modulator; A microlens array 472 in which microlenses 474 having one surface are toric surfaces are arranged as shown in FIG. And optical systems 480 and 482 for forming a laser onto the pattern forming material through the microlens array.

The toric surface of the microlens is as follows. In order to correct the distortion of the emission surface of the microlens 474 as the drawing unit, the distortion of the emission surface was measured, and the result is shown in FIG. In Fig. 14, the contour lines represent reflective surfaces of the same height, and the pitch of the contour lines is 5 nm. In Fig. 14, the X and Y directions are diagonal lines of the two micromirrors 62, and the micromirrors 62 rotate along a rotation axis extending in the Y direction. 15A and 15B, the height displacement of the micromirror 62 is shown along the X and Y directions, respectively.

As shown in FIGS. 14 and 15A and 15B, distortion exists in the reflecting surface of the micromirror 62. In the central portion of the micromirror, the distortion in one diagonal direction, that is, the Y direction, is larger than the distortion in the other diagonal direction. Therefore, the shape of the laser beam B must be distorted at the condensing position through the microlens 55a of the microlens array 55.

16A and 16B, the front shape and the side shape of the entire microlens array 55 are shown in detail, and the sizes of the various parts are shown in units of mm. As described above with reference to FIG. 4, the micromirrors 62 of 1024 columns x 256 rows of the DMD 50 are driven; Correspondingly, the microlens array 55 is formed by arranging 1024 microlenses 55a in the width direction to form one row, and 256 rows in the longitudinal direction. In FIG. 16A, each position of the microlens array 55 is represented by "j" in the width direction and "k" in the longitudinal direction.

17A and 17B, the front shape and the side shape of the microlens 55a of the microlens array 55 are shown, respectively. 17A, the contour of the microlens 55a is also shown. The cross section of each microlens 55a is an aspherical surface for correcting aberration due to distortion of the reflecting surface of the micromirror 62. Specifically, the microlens 55a is a toric lens; The radius of curvature Rx in the optical X direction is -0.125 mm, and the radius of curvature Ry in the optical Y direction is -0.1 mm.

Therefore, the condensing state of the laser beam B in the cross section parallel to the X direction and the Y direction is as shown in Figs. 18A and 18B, respectively. That is, when comparing the X direction and the Y direction, the radius of curvature of the microlens 55a in the Y direction is small and the focal length is also short.

19A, 19B, 19C, and 19D show simulations of the beam diameter in the vicinity of the focal point of the microlens 55a of this shape. As a contrast, Figures 20A, 20B, 20C and 20D show simulations of microlenses with Rx = Ry = -0.1 mm. In this figure, the value of "# " indicates the evaluation position in the focal direction of the microlens 55a as a distance from the laser beam irradiation surface of the microlens 55a.

The surface shape of the microlens 55a in the simulation can be calculated by the following equation.

In the above formula, Cx means radius of curvature in the X direction (= 1 / Rx), Cy means radius of curvature in the Y direction (= 1 / Ry), and X is the distance from the optical axis O in the X direction. Y means the distance from the optical axis O in the Y direction.

From the comparison of FIGS. 19A to 19D and 20A to 20D, in the pattern forming method according to the present invention, a toric lens having a focal length of a cross section parallel to the Y direction is shorter than a focal length of a cross section parallel to the X direction. By using it as the lens 55a, it turns out that the distortion of the beam shape in the condensing position vicinity is reduced. As a result, the image may be exposed to the pattern forming material 150 more clearly and without distortion. Further, it can be seen from the embodiment of the present invention shown in Figs. 19A to 19D that the area having a small beam diameter is wider, that is, the depth of focus is longer.

In addition, the opening array 59 disposed near the condensing position of the microlens array 55 is configured so that each opening 59a receives only light passing through the corresponding microlens 55a. That is, the aperture array 59 can provide the respective openings as a countermeasure for preventing the incidence of light from the adjacent number 57a to increase the extinction ratio.

(3) measurement of resolution

The laminate was prepared under the same methods and conditions as in the evaluation method of (1) shortest developing time, and left for 10 minutes at 23 ° C. and 55% RH atmospheric conditions. Line pattern exposure is performed from the said polyethylene terephthalate film as a support body of the obtained laminated body on condition of line / space = 1/1, line width: 10-50 micrometers, and line increment: 5 micrometers / line. It was. The light amount of exposure was adjusted to the amount of light energy required to harden the photosensitive layer obtained by said (2) sensitivity measurement. After leaving for 10 minutes under atmospheric conditions, the polyethylene terephthalate film as a support was peeled off from the laminate, and then a 1% by mass aqueous sodium carbonate solution at 30 캜 and 0.15 MPa was applied to the entire surface of the photosensitive layer on the copper clad laminate in the above (1). The uncured portion was removed by spraying for twice the time of the obtained shortest developing time. The copper clad laminated board which has the obtained cured resin pattern is observed with an optical microscope; The narrowest line width without abnormality in lines such as clogging and deformation was measured, and the narrowest line width was taken as the resolution. In other words, the smaller the value, the better the resolution.

<Exposure Speed>

By using the pattern forming apparatus, the relative movement speeds of the exposure laser and the photosensitive layer were changed to measure the normal pattern formation speed. Exposure was performed from the polyethylene terephthalate film side on the photosensitive layer of the pattern forming material of the laminate. The faster the exposure speed, the more effectively the pattern can be formed.

<Etchability>

(3) Ferric chloride etchant (etching solution containing ferric chloride, 40 ° bame, solution temperature: 40 ° C.) on the surface of the bare copper clad laminate, using the laminate having the pattern formed in the resolution measurement described above. Was sprayed at 0.25 MPa for 36 seconds to etch away the bare copper layer without a hardened layer. Then, 2 mass% aqueous sodium hydroxide solution was sprayed to remove the pattern to prepare a printed wiring board having the wiring pattern as the permanent pattern. The obtained wiring pattern was optically examined with an optical microscope, and the narrowest line width of the wiring pattern was measured. The smaller the narrowest line width means that the wiring pattern is more precise and the etching is excellent.

(Example 2)

Method similar to Example 1 except having changed the addition product of hexamethylene diisocyanate and tetraethylene oxide monomethacrylate (molar ratio: 1/2) of the photosensitive resin composition solution to the compound represented by following General formula (74). A pattern forming material was prepared.

The resolution, exposure speed and etching property of the prepared pattern forming material were evaluated. The results are shown in Table 3.

The shortest developing time was 10 seconds, and the amount of light energy required to cure the photosensitive layer was 3 mJ / cm 2. The compound represented by the said General formula (74) is contained in what is represented by the said General formula (24).

(Example 3)

Except that the addition product of hexamethylene diisocyanate and tetraethylene oxide monomethacrylate (molar ratio: 1/2) of the photosensitive resin composition solution was changed to the compound represented by following General formula (75), it is the same as Example 1 A pattern forming material was prepared by the method.

The resolution, exposure speed and etching property of the prepared pattern forming material were evaluated. The results are shown in Table 3.

The shortest developing time was 10 seconds, and the amount of light energy required to cure the photosensitive layer was 3 mJ / cm 2. The compound represented by the said General formula (75) is contained in what is represented by the said General formula (22).

(Example 4)

Copolymer of methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid (mass ratio: 50/20/7/23, mass average molecular weight: 90,000, acid value: 150) to methyl methacrylate / A pattern forming material in the same manner as in Example 1 except for changing the copolymer of styrene / benzyl methacrylate / methacrylic acid (mass ratio: 8/30/37/25, mass average molecular weight: 60,000, acid value: 163). Was prepared.

The resolution, exposure speed and etching property of the prepared pattern forming material were evaluated. The results are shown in Table 3.

The shortest developing time was 10 seconds, and the amount of light energy required to cure the photosensitive layer was 3 mJ / cm 2.

(Comparative Example 1)

The resolution, exposure speed and etching property were evaluated in the same manner as in Example 1 except that the microlens array of the pattern forming apparatus of Example 1 was not used. The results are shown in Table 3.

The shortest developing time was 10 seconds, and the amount of light energy required to cure the photosensitive layer was 3 mJ / cm 2.

(Comparative Example 2)

Except not using the microlens array of the pattern forming apparatus of Example 1, the resolution, exposure speed, and etching property were evaluated in the same manner as in Example 1, and the entire micromirror of the DMD (1024 x 768) was controlled. Driven. The results are shown in Table 3.

The shortest developing time was 10 seconds, and the amount of light energy required to cure the photosensitive layer was 3 mJ / cm 2.

From the results in Table 3, the wiring patterns of Examples 1 to 4 are significantly more precisely than those of Comparative Examples 1 and 2, and the exposure speeds of Examples 1 to 4 are higher than those of Comparative Examples 1 and 2, which is efficient. It can be seen that the wiring pattern is formed.

In the pattern forming method according to the present invention, since the permanent pattern can be formed with high precision by suppressing the distortion of the image formed on the pattern forming material, the pattern forming method according to the present invention can be used in various types that require more accurate exposure. It can be used for pattern formation, especially for wiring pattern formation with high accuracy.

Claims (24)

Modulating the laser beam irradiated from the laser source; Correcting the modulated laser beam; And A pattern forming method comprising exposing a photosensitive layer with the modulated and corrected laser beam, The photosensitive layer is disposed on the support to form a pattern forming material, The modulation is performed by a laser modulator comprising a plurality of drawing sections capable of receiving a laser beam and emitting the modulated laser beam, respectively; Also The correction is performed by transmitting a modulated laser beam through a plurality of microlenses each having an aspherical surface capable of correcting aberration due to distortion of the exit surface of the drawing portion, wherein the plurality of microlenses are arranged in a microlens array. Pattern formation method characterized by. The method of claim 1, wherein the aspheric surface is a toric surface. The pattern forming method according to claim 1 or 2, wherein the laser modulator can control a part of the plurality of drawing units in accordance with pattern information. The pattern forming method according to any one of claims 1 to 3, wherein the laser modulator is a spatial light modulator. 5. The method of claim 4, wherein said spatial light modulator is a digital micromirror device (DMD). The pattern forming method according to any one of claims 1 to 5, wherein the exposure is performed by a laser beam transmitted through the aperture array. The pattern formation method according to any one of claims 1 to 6, wherein the exposure is performed while relatively moving the laser beam and the photosensitive layer. The pattern formation method according to any one of claims 1 to 7, wherein the post-exposure photosensitive layer is developed. The pattern forming method according to claim 8, wherein a permanent pattern is formed after the development. The method of claim 9, wherein the permanent pattern is a wiring pattern, and the permanent pattern is formed by at least one of an etching process and a plating process. The pattern forming method according to any one of claims 1 to 10, wherein the laser source can irradiate two or more kinds of lasers together. 12. The laser source according to any one of claims 1 to 11, wherein the laser source includes a plurality of lasers, a multimode optical fiber, and an aggregated optical system for focusing the laser beams from the plurality of lasers on the multimode optical fiber. Pattern formation method. The pattern forming method according to any one of claims 1 to 12, wherein the photosensitive layer comprises a binder, a polymerizable compound, and a photopolymerization initiator. The method of claim 13, wherein the binder contains an acid group. The pattern forming method according to claim 13 or 14, wherein the binder contains a vinyl copolymer. The pattern forming method according to any one of claims 13 to 15, wherein an acid value of the binder is 70 to 250 mgKOH / g. The pattern forming method according to any one of claims 13 to 16, wherein the polymerizable compound contains a monomer having at least one of a urethane group and an aryl group. 18. The photopolymerization initiator according to any one of claims 13 to 17, wherein the photopolymerization initiator consists of a halogenated hydrocarbon derivative, hexaaryl-biimidazole, oxime derivative, organic peroxide, thio compound, ketone compound, aromatic onium salt and metallocene. Pattern forming method characterized by containing a compound selected from the group. The said photosensitive layer contains 30-90 mass% of binders, 5-60 mass% of polymeric compounds, and 0.1-30 mass% of photoinitiators, The pattern in any one of Claims 1-18 characterized by the above-mentioned. Formation method. The pattern formation method of any one of Claims 1-19 whose thickness of the said photosensitive layer is 1-100 micrometers. The pattern forming method according to any one of claims 1 to 20, wherein the support comprises a synthetic resin and is transparent. The pattern forming method according to any one of claims 1 to 21, wherein the support has a long shape. The pattern forming method according to any one of claims 1 to 22, wherein the pattern forming material is a long shape formed by winding in a roll shape. The pattern forming method according to any one of claims 1 to 23, wherein the protective film is formed on the photosensitive layer of the pattern forming material.

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