JP2007086374A - Pattern forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a permanent pattern forming method by which fine permanent patterns such as a protective film, an insulating film and a solder resist pattern can be formed with a high degree of accuracy, by making each drawing unit uniform in light quantity while curbing costs, in exposure using a digital exposure apparatus equipped with an exposure head in which drawing units are two-dimensionally distributed. <P>SOLUTION: The permanent pattern forming method includes at least exposing a photosensitive layer by illuminating a light beam emitted from a light illuminating means onto a light modulating means through a condensing optical system having a light distribution correcting means, and illuminating the light beam modulated by the light modulating means onto the photosensitive layer, wherein, in the exposure, a distribution is provided to light quantity in the illumination region of the light beam illuminated from the light illuminating means onto the light modulating means, and the light quantity distribution of the light beam modulated by the light modulating means is corrected so that it is made uniform on a surface of the photosensitive layer to be exposed. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention forms an image of light modulated by a light modulation means such as a spatial light modulation element on a photosensitive layer, exposes the photosensitive layer, and performs high performance in the field of printed wiring boards including package substrates, or in the semiconductor field. The present invention relates to a permanent pattern forming method for efficiently forming fine permanent patterns (a protective film, an interlayer insulating film, and a solder resist pattern).

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

  The DMD is a mirror device in which a large number of micromirrors whose reflection surfaces change in response to control signals are two-dimensionally arranged on a semiconductor substrate such as silicon. In an exposure method using a conventional digital exposure type exposure apparatus using the DMD, for example, a light source that emits laser light, a lens system that collimates the laser light emitted from the light source, and a substantially focal point of the lens system. An exposure head having a lens system that forms an image on the scanning surface of the DMD disposed at a position and the laser beam reflected by the DMD is controlled by a control signal generated according to pattern information or the like. Each of the micromirrors is controlled on and off to modulate the laser light, and the modulated laser light (light beam) is set on the stage of the exposure apparatus and moved along the scanning direction and a liquid crystal display A pattern is scanned and exposed to a photosensitive material such as an element.

In the exposure method using the digital exposure apparatus having the exposure head in which the drawing units are two-dimensionally distributed as described above, the light amount of the drawing units is uniform in order to form a fine pattern with high accuracy. This is very important.
However, in reality, the light emitted from the exposure head has a problem that the light intensity in the peripheral portion is lower than the central portion of the optical axis due to the factors of each lens system in the exposure head. This is particularly remarkable in a system in which light of each drawing unit is irradiated with light condensed through a microlens array.

  To solve this problem, drive control is performed so that the light intensity distribution (light quantity) of the light emitted from the exposure head is measured, and the drive timing of each pixel part of the spatial light modulator is changed according to the light intensity distribution. Thus, the present applicant has already proposed a shading technique for correcting the light amount of each drawing unit to be uniform (see, for example, Patent Documents 1 and 2).

  However, in the techniques of Patent Documents 1 and 2 described above, the load applied to the drive controller of the spatial light modulator increases and the processing speed is affected, and such an exposure apparatus has an electrical circuit configuration. In some cases, the processing software becomes complicated and the cost increases. Since the cost of the electrical control system occupies a large proportion of the cost of the entire apparatus, a new technology that can reduce the load on the control system is desired in order to reduce the cost.

  Therefore, in exposure using a digital exposure apparatus including an exposure head in which drawing units are two-dimensionally distributed, the light amount of each drawing unit distributed two-dimensionally is made uniform while suppressing costs, A permanent pattern forming method capable of forming a fine permanent pattern such as an insulating film and a solder resist pattern with high accuracy has not yet been provided, and further improvement and development are desired.

JP 2005-22248 A Japanese Patent Application No. 2005-22249

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, according to the present invention, in exposure using a digital exposure apparatus including an exposure head in which drawing units are two-dimensionally distributed, the light amount of each drawing unit distributed two-dimensionally is made uniform while suppressing costs. Another object of the present invention is to provide a permanent pattern forming method capable of forming a fine permanent pattern such as a protective film, an insulating film, and a solder resist pattern with high accuracy.

Means for solving the problems are as follows. That is,
<1> For the photosensitive layer formed on the surface of the substrate with a photosensitive composition containing at least a binder, a polymerizable compound, a photopolymerization initiation system compound, and a thermal crosslinking agent,
There are n (where n is a natural number of 1 or more) two-dimensionally arranged pixel parts, and light modulation means for changing the light modulation state for each pixel part according to pattern information Irradiating the light beam emitted from the irradiating means through a condensing optical system having a light distribution correcting means, irradiating and developing the light beam modulated by the light modulating means, and developing,
The exposure gives a distribution of the amount of light in the irradiation region of the light beam irradiated from the light irradiation unit to the light modulation unit, and the light amount distribution of the light beam modulated by the light modulation unit is the photosensitive layer. This is a permanent pattern forming method characterized in that the correction is performed so as to be uniform on the exposed surface. In the method for forming a permanent pattern described in <1>, the light condensing optical system having the light amount distribution correcting unit causes the light amount in the irradiation region of the light beam irradiated to the light modulating unit to have a distribution. Since the light amount distribution on the exposure surface of the light beam modulated by the light modulation unit is corrected to be uniform, the light amount of each drawing unit is corrected to be uniform in the image element unit, Accurate exposure is performed, and then the photosensitive layer is developed to form a high-definition permanent pattern.
<2> The permanent pattern forming method according to <1>, wherein the light modulation unit is configured to irradiate the light modulation unit with the light beam emitted from the light irradiation unit as a light beam having a distribution in the angle of the principal ray by a condensing optical system. In the permanent pattern forming method according to <2>, the light beam emitted from the light irradiating unit is irradiated to the light modulating unit as a light beam having a distribution in the angle of the principal ray by the condensing optical system. The light intensity in the irradiation area of the light beam applied to the light modulation means is distributed. As a result, the light amount distribution on the exposure surface is made uniform, exposure with extremely high accuracy is performed, and then the photosensitive layer is developed to form a very fine permanent pattern.
<3> The method for forming a permanent pattern according to <1>, wherein the light modulating unit is irradiated with the light beam emitted from the light irradiation unit as telecentric light by a condensing optical system. In the method for forming a permanent pattern according to <3>, since the light beam emitted from the light irradiation unit is irradiated to the light modulation unit as telecentric light by the condensing optical system, the light modulation unit The telecentricity of the light applied to the light and the uniformity of the light quantity distribution on the exposure surface of the light modulated by the light modulation means can be achieved, and extremely high-precision exposure is performed. For example, after that, the photosensitive layer is developed to form an extremely fine pattern.
<4> A first optical lens having an aspherical shape in which the lens power decreases as the condensing optical system moves away from the optical axis center, and an aspherical shape in which the lens power increases as the distance from the optical axis center increases. The method for forming a permanent pattern according to <3>, further including a light distribution correction unit including a second optical lens having In the method for forming a permanent pattern according to <4>, the condensing optical system has an aspherical shape (such as a convex lens that condenses a parallel incident beam) such that the lens power decreases as the distance from the optical axis center increases. And a second optical lens having an aspherical shape (such as a concave lens that diverges a parallel incident beam) such that the lens power increases as the distance from the optical axis center increases. Because of having means, a situation is realized in which the light that has passed near the center is stronger than the light that has passed through the peripheral portion of the first optical lens, and the degree to which the light is away from the optical axis is increased. A telecentric optical system is realized by reversing the change in lens power between the first optical lens and the second optical lens. As a result, the light amount distribution of the light beam emitted from the telecentric optical system has a higher distribution density in the periphery with respect to the center of the optical axis, the light amount distribution on the exposure surface is made uniform, and extremely high-precision exposure is possible. After that, the photosensitive layer is developed to form a very fine permanent pattern.

  <5> Any one of the items <1> to <4>, wherein the condensing optical system increases the amount of light in the peripheral part rather than the central part in the irradiation region of the light beam irradiated from the light irradiation unit to the light modulation unit The method for forming a permanent pattern according to the above. In the permanent pattern forming method according to <5>, the light collecting optical system has a light amount in a peripheral portion rather than a central portion in an irradiation region of a light beam irradiated from the light irradiation unit to the light modulation unit. Therefore, in the irradiation region of the light beam applied to the light modulation means, the light amount of the peripheral portion that is lower than the central portion is increased by the condensing optical system, and the light use efficiency in exposure is improved.

<6> The method for forming a permanent pattern according to any one of <1> to <5>, wherein the light modulator is a spatial light modulator.
<7> The method for forming a permanent pattern according to <6>, wherein the spatial light modulator is a digital micromirror device (DMD).

<8> The permanent pattern forming method according to any one of <1> to <7> 6, wherein the formation of the photosensitive layer is performed by applying the photosensitive composition to the surface of the substrate and drying.
<9> The formation of the photosensitive layer is carried out by subjecting a photosensitive film having a support and a photosensitive layer formed by laminating the photosensitive composition on the support to a substrate under at least one of heating and pressurization. The permanent pattern forming method according to any one of <1> to <7>, wherein the method is performed by laminating on a surface.
<10> The above <1> to <9>, wherein the binder contains at least one of an epoxy acrylate compound and at least one of a vinyl copolymer having a (meth) acryloyl group and an acidic group in a side chain. The permanent pattern forming method according to any one of the above.
<11> From the above <1> to <9>, wherein the binder is a copolymer obtained by reacting 0.1 to 1.2 equivalents of a primary amine compound with respect to the anhydride group of the maleic anhydride copolymer. The permanent pattern forming method according to any one of the above.
<12> The binder is (a) maleic anhydride, (b) an aromatic vinyl monomer, and (c) a vinyl monomer, and the glass transition temperature (Tg) of the homopolymer of the vinyl monomer <1> to <9 obtained by reacting 0.1 to 1.0 equivalent of a primary amine compound with an anhydride group of a copolymer comprising a vinyl monomer having a temperature of less than 80 ° C. The permanent pattern forming method according to any one of the above.
<13> From the above <1>, wherein the thermal crosslinking agent is at least one selected from an epoxy compound, an oxetane compound, a polyisocyanate compound, a compound obtained by reacting a polyisocyanate compound with a blocking agent, and a melamine derivative. 12>. The permanent pattern forming method according to any one of 12).
<14> The method for forming a permanent pattern according to <13>, wherein the melamine derivative is an alkylated methylol melamine.
<15> The method for forming a permanent pattern according to any one of <1> to <14>, wherein the polymerizable compound includes a monomer having at least one of a urethane group and an aryl group.
<16> The permanent pattern formation method according to any one of <1> to <15>, wherein the polymerizable compound includes a monomer having at least one of an ethylene oxide group and a propylene oxide group.
<17> The method for forming a permanent pattern according to any one of <1> to <16>, wherein the photosensitive composition contains a sensitizer.
<18> The above <17, wherein the sensitizer is at least one selected from a condensed ring compound and an amine compound substituted with at least two aromatic hydrocarbon rings or aromatic heterocyclic rings. > Is a method for forming a permanent pattern.
<19> The method for forming a permanent pattern according to any one of <9> to <18>, wherein the support includes a synthetic resin and is transparent.
<20> The method for forming a permanent pattern according to any one of <9> to <19>, wherein the support has an elongated shape.
<21> The method for forming a permanent pattern according to any one of <9> to <20>, wherein the photosensitive film is long and wound in a roll.
<22> The method for forming a permanent pattern according to any one of <9> to <21>, wherein the photosensitive film has a protective film on the photosensitive layer.
<23> The method for forming a permanent pattern according to any one of <1> to <22>, wherein the photosensitive layer has a thickness of 3 to 100 μm.
<24> The permanent pattern forming method according to any one of <1> to <23>, wherein the base material is a printed wiring board on which wiring is formed.

<25> The permanent pattern forming method according to any one of <1> to <24>, wherein the light irradiation unit can synthesize and irradiate two or more lights. In the method for forming a permanent pattern described in <25>, the light irradiation means can synthesize and irradiate two or more lights, so that exposure is performed with exposure light having a deep focal depth. As a result, the photosensitive layer is exposed with extremely high definition, and then the photosensitive layer is developed to form a very high definition pattern.
<26> The light irradiation means collimates the plurality of lasers, the multimode optical fiber, and the laser beams irradiated from the plurality of lasers, and converges them on the incident end face of the multimode optical fiber. It is a permanent pattern formation method in any one of said <1> to <25> which has a light source condensing optical system. In the method for forming a permanent pattern according to <26>, the laser beam emitted from each of the plurality of lasers is condensed by the light source condensing optical system by the light irradiation unit, and is incident on the multimode optical fiber. By converging on the end face, a light beam with high brightness and deep focal depth can be obtained. As a result, the photosensitive layer is exposed with extremely high definition, and then the photosensitive layer is developed to form a very high definition pattern.
<27> The method for forming a permanent pattern according to <26>, wherein the laser beam has a wavelength of 395 to 415 nm.

<28> The permanent pattern forming method according to any one of <1> to <27>, wherein the photosensitive layer is subjected to a curing treatment after development.
<29> The permanent pattern forming method according to <28>, wherein the curing treatment is at least one of a whole surface exposure treatment and a whole surface heat treatment performed at 120 to 200 ° C.
<30> The method for forming a permanent pattern according to any one of <1> to <29>, wherein at least one of a protective film, an interlayer insulating film, and a solder resist pattern is formed.

  According to the present invention, conventional problems can be solved, and each drawing that is two-dimensionally distributed while suppressing costs in exposure using a digital exposure apparatus that includes an exposure head in which drawing units are two-dimensionally distributed. By making the light quantity of the unit uniform, a permanent pattern forming method capable of forming a fine permanent pattern such as a protective film, an insulating film, and a solder resist pattern with high accuracy can be provided.

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

The exposure step includes n (where n is a natural number of 1 or more) two-dimensionally arranged pixel parts, and light that changes the light modulation state for each of the pixel parts according to pattern information. At least including irradiating the modulation means with a light beam emitted from the light irradiation means via a condensing optical system having a light distribution correction means, and irradiating with the light beam modulated by the light modulation means; ,
The exposure gives a distribution of the amount of light in the irradiation region of the light beam irradiated from the light irradiation unit to the light modulation unit, and the light amount distribution of the light beam modulated by the light modulation unit is the photosensitive layer. The correction is performed so as to be uniform on the exposed surface.

  There is no particular limitation on the method of giving the distribution of the amount of light within the irradiation region of the light beam irradiated from the light irradiating unit to the light modulating unit, and can be appropriately selected according to the purpose. A first embodiment in which a light beam emitted from the light irradiating means is radiated to the light modulating means as a light beam having a distribution in the principal ray angle by the condensing optical system, and emitted from the light irradiating means. There is a second embodiment in which the light modulation means is irradiated with the light beam as telecentric light by the condensing optical system.

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

[First embodiment]
<Schematic configuration of exposure apparatus>
FIG. 1 shows a schematic configuration of an exposure head 100 provided in the exposure apparatus according to the first embodiment.
As shown in FIG. 1, the exposure head 100 may represent an incident light beam as a pixel part (hereinafter referred to as “pixel”) according to pattern information (hereinafter also referred to as “image data”). ) As a light modulation means for modulating each time, a digital micromirror device (DMD) 50 of a spatial light modulation element is provided. The DMD 50 is connected to a controller (not shown) including a data processing unit and a mirror drive control unit.
The data processing unit of the controller generates a control signal for driving and controlling each micromirror of the DMD 50 that is a pixel part (pixel) based on the input pattern information (image data). The mirror drive control unit controls the angle of the reflection surface of each micromirror of the DMD 50 based on the control signal generated by the image data processing unit.
The control of the angle of the reflecting surface will be described later.

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

The condensing optical system 114 includes a pair of combination lenses 116 that condenses the laser light emitted from the fiber array light source 112, a rod integrator 118 that corrects the light amount distribution of the condensed laser light, and It is composed of a condensing lens 120 that condenses the laser light with the corrected light quantity distribution on the DMD.
Since the rod integrator 118 guides the light while totally reflecting the light inside the integrator, the rod integrator 118 can correct the laser light so that the light quantity distribution is uniform.

On the other hand, a projection optical system is provided on the light reflection side of the DMD 50.
The projection optical system projects a light source image from the DMD 50 side to project a light source image onto a photosensitive material (laminated body in which the photosensitive layer is laminated on a base material) 134 on the exposure surface on the light reflection side of the DMD 50. Optical members for exposure of the lens system 126, the microlens array 128, and the objective lens system 130 are arranged in order toward the photosensitive material 134.

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

As shown in FIG. 1, the microlens array 128 includes a plurality of microlenses 132 that correspond one-to-one to each micromirror 62 (see FIG. 2) of the DMD 50 that reflects the laser light emitted from the fiber array light source 112. The microlenses 132 are two-dimensionally arranged and integrally molded into a rectangular flat plate shape, and each microlens 132 is disposed on the optical axis of each laser beam transmitted through the lens system 126, respectively. .
The microlens array 128 can be formed, for example, by molding resin or optical glass.

-Light modulation means-
As shown in FIG. 2, the DMD 50 as an example of the light modulation means is configured such that a micromirror (micromirror) 62 is supported on a SRAM cell (memory cell) 60 and supported by a support column. This is a mirror device configured by arranging a large number (for example, 600 × 800) of micromirrors constituting a portion (also referred to as “pixel” or “pixel”) in a grid pattern.
Each pixel is provided with a micromirror 62 supported by a support column at the top, and a material having a high reflectance such as aluminum is deposited on the surface of the micromirror 62. The reflectance of the micromirror 62 is 90% or more.
A silicon gate CMOS SRAM cell 60 manufactured in a normal semiconductor memory manufacturing line is disposed directly below the micromirror 62 via a support including a hinge and a yoke, and is entirely monolithic (integrated type). ).

  When a digital signal is written in the SRAM cell 60 of the DMD 50, the micromirror 62 supported by the support is inclined within a range of ± α degrees (for example, ± 10 degrees) with respect to the substrate side on which the DMD 50 is disposed with the diagonal line as the center. It is done. 3A shows a state where the micromirror 62 is tilted to + α degrees when the micromirror 62 is on, and FIG. 3B shows a state where the micromirror 62 is tilted to −α degrees when the micromirror 62 is off. Therefore, by controlling the tilt of the micromirror 62 in each pixel of the DMD 50 according to the image signal as shown in FIG. 2, the light incident on the DMD 50 is reflected in the tilt direction of each micromirror 62. .

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

-Light irradiation means-
As shown in FIG. 4A, the fiber array light source 112 as an example of the light irradiation means includes a plurality of (25 in the figure) laser modules 64, and each laser module 64 includes a multimode optical fiber 30. One end is connected.
An optical fiber 31 having the same core diameter as that of the multimode optical fiber 30 and a cladding diameter smaller than that of the multimode optical fiber 30 is coupled to the other end of the multimode optical fiber 30. As shown in FIG. The laser emission part 68 is configured by arranging a plurality of emission end parts (light emission points) along a predetermined direction (three lines in the figure).

The multimode optical fiber 30 and the optical fiber 31 may be any of a step index type optical fiber, a graded index type optical fiber, and a composite type optical fiber. For example, a step index type optical fiber manufactured by Mitsubishi Cable Industries, Ltd. can be used.
In the present embodiment, the multimode optical fiber 30 and the optical fiber 31 are step index type optical fibers, and the multimode optical fiber 30 has a cladding diameter = 125 μm, a core diameter = 50 μm, NA = 0.2, an incident end face. The transmittance of the coat is 99.5% or more, and the optical fiber 31 has a cladding diameter = 60 μm, a core diameter = 50 μm, and NA = 0.2.

However, the cladding diameter of the optical fiber 31 is not limited to 60 μm. The clad diameter of the optical fiber used in the conventional fiber light source is 125 μm, but the depth of focus becomes deeper as the clad diameter becomes smaller. Therefore, the clad diameter of the multimode optical fiber is preferably 80 μm or less, more preferably 60 μm or less. Preferably, it is 40 μm or less.
On the other hand, since the core diameter needs to be at least 3 to 4 μm, the cladding diameter of the optical fiber 31 is preferably 10 μm or more.

The laser module 64 is configured by a combined laser light source (fiber light source) shown in FIG. This combined laser light source includes a plurality of (for example, seven) chip-like lateral multimode or single mode GaN-based semiconductor lasers LD1, LD2, LD3, LD4, LD5, LD6, arrayed and fixed on the heat block 10. And LD7, collimator lenses 11, 12, 13, 14, 15, 16, and 17 provided corresponding to each of the GaN-based semiconductor lasers LD1 to LD7, one condenser lens 20, and one multi-lens. Mode optical fiber 30.
The number of semiconductor lasers is not limited to seven. For example, as many as 20 semiconductor laser beams can be incident on a multimode optical fiber having a cladding diameter = 60 μm, a core diameter = 50 μm, and NA = 0.2. In addition, the number of optical fibers can be further reduced.

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

  As shown in FIGS. 6 and 7, the above combined laser light source is housed in a box-shaped package 40 having an upper opening together with other optical elements. The package 40 includes a package lid 41 created so as to close the opening thereof. After the deaeration process, a sealing gas is introduced, and the package 40 and the package lid 41 are closed by closing the opening of the package 40 with the package lid 41. 41. The combined laser light source is hermetically sealed in a closed space (sealed space) formed by 41.

  A base plate 42 is fixed to the bottom surface of the package 40. On the upper surface of the base plate 42, the heat block 10, a condensing lens holder 45 that holds the light source condensing lens 20, and the multimode optical fiber 30. A fiber holder 46 that holds the incident end of the optical fiber is attached. The exit end of the multimode optical fiber 30 is drawn out of the package from an opening formed in the wall surface of the package 40.

  Further, a collimator lens holder 44 is attached to the side surface of the heat block 10, and the collimator lenses 11 to 17 are held. An opening is formed in the lateral wall surface of the package 40, and wiring 47 for supplying a driving current to the GaN-based semiconductor lasers LD1 to LD7 is drawn out of the package through the opening.

  In FIG. 6, in order to avoid complication of the figure, only the GaN semiconductor laser LD7 is numbered among the plurality of GaN semiconductor lasers, and only the collimator lens 17 is numbered among the plurality of collimator lenses. is doing.

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

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

Accordingly, in the laser beams B1 to B7 emitted from the respective light emitting points, the direction in which the divergence angle is large coincides with the length direction and the divergence angle is small with respect to the elongated collimator lenses 11 to 17 as described above. Incident light is incident in a state where the direction coincides with the width direction (direction perpendicular to the length direction). That is, the collimator lenses 11 to 17 have a width of 1.1 mm and a length of 4.6 mm, and the horizontal and vertical beam diameters of the laser beams B1 to B7 incident thereon are 0.9 mm and 2. 6 mm. Each of the collimator lenses 11 to 17 has a focal length f ₁ = 3 mm, NA = 0.6, and a lens arrangement pitch = 1.25 mm.

The light source condensing lens 20 is obtained by cutting a region including the optical axis of a circular lens having an aspherical surface into a long and narrow plane in parallel planes, which is long in the arrangement direction of the collimator lenses 11 to 17, that is, in a horizontal direction and short in a direction perpendicular thereto. It is formed into a shape. The light source condenser lens 20 has a focal length f ₂ = 23 mm and NA = 0.2. Similarly to the collimator lens, the light source condensing lens 20 is also formed, for example, by molding resin or optical glass.

  In the fiber array light source 112 configured as described above, the laser beams B1, B2, B3, B4, B5, B6, and the like emitted from each of the GaN-based semiconductor lasers LD1 to LD7 constituting the combined laser light source, and Each of B7 is collimated by the corresponding collimator lenses 11-17. The collimated laser beams B <b> 1 to B <b> 7 are collected by the light source condenser lens 20 and converge on the incident end face of the core 30 a of the multimode optical fiber 30.

The collimator lenses 11 to 17 and the light source condensing lens 20 constitute a light source condensing optical system, and the light condensing optical system and the multimode optical fiber 30 constitute a multiplexing optical system.
In other words, the laser beams B1 to B7 condensed as described above by the light source condenser lens 20 enter the core 30a of the multimode optical fiber 30 and propagate through the optical fiber to be combined with one laser beam B. The light is emitted from the optical fiber 31 coupled to the output end of the multimode optical fiber 30.

  In each laser module, when the coupling efficiency of the laser beams B1 to B7 to the multimode optical fiber 30 is 0.85 and each output of the GaN-based semiconductor lasers LD1 to LD7 is 30 mW (when a single mode laser is used). Can obtain a combined laser beam B with an output of 180 mW (= 30 mW × 0.85 × 7) for each of the optical fibers 31 arranged in an array. Therefore, the output from the laser emitting unit 68 in which 25 optical fibers 31 are arranged in an array is about 4.5 W (= 180 mW × 25).

  In the laser emitting portion 68 of the fiber array light source 112, high-luminance light emitting points are arranged in the main scanning direction as described above. A conventional fiber light source that couples laser light from a single semiconductor laser to a single optical fiber has a low output, so a desired output could not be obtained unless multiple rows are arranged. Since the combined laser light source used in the form has a high output, a desired output can be obtained even with a small number of columns, for example, one column.

For example, in a conventional fiber light source in which a semiconductor laser and an optical fiber are coupled on a one-to-one basis, a laser having an output of about 30 mW (milliwatt) is usually used as the semiconductor laser, and the core diameter is 50 μm and the cladding diameter is 125 μm. If a multimode optical fiber with a numerical aperture (NA) of 0.2 can be used and an output of about 4.5 W (watts) is to be obtained, 225 (15 × 15) multimode optical fibers must be bundled. Since the area of the light emitting region is 3.6 mm ² (1.9 mm × 1.9 mm), the luminance at the laser emitting portion 68 is 1.25 (W / mm ² ), and the luminance per optical fiber is 10 (W / mm ² ).

On the other hand, in the present embodiment, as described above, an output of about 4.5 W can be obtained with 25 multimode optical fibers, and the area of the light emitting region at the laser emitting portion 68 is 0.2 mm ² (0 .18 mm × 1.13 mm), the luminance at the laser emitting portion 68 is 22.5 (W / mm ² ), and the luminance can be increased by 18 times compared to the conventional case. Further, the luminance per optical fiber is 90 (W / mm ² ), and the luminance can be increased by about 9 times compared with the conventional one.

  As the semiconductor laser constituting the combined laser light source, a blue laser having an oscillation wavelength near 400 nm is suitable. When the blue laser is used, the focused beam of each microlens 132 of the microlens array 128 can be reduced.

-Condensing optical system with light distribution correction means-
In the exposure head 100 of the present embodiment, which is the first embodiment, the condensing optical system 114 is different from the light quantity distribution correction function provided in the rod integrator 118 on the exposure surface of the exposure beam modulated by the DMD 50. In order to uniformly correct the light amount distribution with higher accuracy, the function of giving a predetermined distribution to the light amount in the irradiation region of the laser light irradiated to the DMD 50, specifically, to the laser light incident from the fiber array light source 112 On the other hand, it has a function of emitting a laser beam having a predetermined distribution of chief ray angles to irradiate the DMD 50.

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

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

In FIG. 9B, the laser light emitted from the condensing optical system 114 of the present embodiment is irradiated onto the illumination area on the DMD 50 in a state where the chief ray angle is distributed according to the distance from the optical axis center. FIG. As shown in FIG. 9B, the chief ray angle distribution of the laser beam irradiated on the illumination region (laser beam irradiation region) on the DMD 50 is parallel to the optical axis without tilting the chief ray at the center of the optical axis of the laser beam. Yes, the chief ray gradually tilts toward the + side and the tilt angle gradually increases from the center of the optical axis to the periphery of the illumination area, and when the predetermined distance YA is reached, the tilt angle of the chief ray toward the + side increases. The maximum (maximum tilt angle A), the tilt angle of the chief ray toward the + side gradually decreases after a predetermined distance YA, and when reaching the peripheral edge of the illumination area, the tilt of the chief ray is the same as the center of the optical axis. The distribution has disappeared.
By providing such a distribution of the chief ray angles of the laser light, the light density in the peripheral portion of the illumination area on the DMD 50 is increased compared to the center of the optical axis, that is, compared to the center of the optical axis. Laser light whose peripheral portion has increased brightness is irradiated.

In the case where the chief ray angle of the laser beam has the above-described distribution, the size of the distribution amount determined by the maximum tilt angle A of the chief ray is equal to or greater than the light amount reduction amount at the peripheral portion, and the exposure. The telecentricity (parallelism between the principal ray and the optical axis) of the exposure beam required on the surface is preferably set to an amount that satisfies the telecentricity.
In the case of the exposure head 100 of the present embodiment, the light amount reduction at the periphery of the exposure beam on the exposure surface is mainly caused by the microlens array 128 (see FIG. 1) of the projection optical system disposed on the light reflection side of the DMD 50. Therefore, it is desirable to set the magnitude of the distribution amount to be equal to or greater than the amount of light reduction in the peripheral portion caused by the micro lens array 128, for example.
Further, the predetermined distance YA can be appropriately set according to the light amount reduction amount and the light amount reduction region (region for correcting the light amount) of the peripheral portion. In the example shown in FIG. 9B, the illumination is performed from the center of the optical axis. If the distance to the peripheral edge of the area (the outer peripheral edge of the DMD 50) is YS, YS>YA> YS / 2 is set.

<Operation of exposure apparatus>
The operation of the exposure apparatus will be described.
In this exposure apparatus, when image data is input to a controller (not shown), the controller generates a control signal for driving and controlling each micromirror 62 of the DMD 50 provided in the exposure head 100 based on the input image data. The angle of the reflection surface of each micromirror 62 of the DMD 50 is controlled based on the generated control signal.

  Illumination light (laser light) irradiated to the DMD 50 from the fiber array light source 112 via the condensing optical system 114 is reflected and modulated in a predetermined direction according to the angle of the reflection surface of each micromirror 62 and modulated. The light beam is magnified by the lens system 126 and incident on each of the microlenses 132 provided in the microlens array 128 to be condensed. The condensed light beam is imaged on the exposure surface of the photosensitive material 134 by the objective lens system 130, and thus the laser light emitted from the fiber array light source 112 is turned on / off (modulated) for each pixel. Then, the photosensitive material 134 is exposed in pixel units (exposure areas) of approximately the same number as the number of used pixels of the DMD 36.

Normally, the light amount (light intensity) distribution of this light beam is lower in the peripheral portion than in the central portion of the optical axis due to factors of the lens system, but the exposure head 100 of this embodiment includes a fiber array light source. In order to make the light amount distribution of the laser light emitted from 112 uniform and irradiate the DMD 50, a rod integrator 118 is provided in the condensing optical system 114 disposed on the optical path on the light incident side of the DMD 50.
However, with this rod integrator 118 as well, in the system in which each drawing unit is condensed by the microlens array 128 as in the present embodiment, the light intensity at the peripheral portion with respect to the central portion of the optical axis is significantly reduced, and the image can be obtained with higher accuracy. It is difficult to correct the light quantity distribution to the required accuracy when performing exposure. In order to increase the correction accuracy of the light quantity distribution, it is conceivable to lengthen the rod integrator 118. However, since the rod integrator 118 is a very expensive optical component, the apparatus cost increases, and the exposure head 100 is increased. Has the disadvantage of becoming larger.

  On the other hand, in the exposure head 100 of the present embodiment, as described above, the laser light incident on the condensing optical system 114 from the fiber array light source 112 is the chief ray as indicated by (1) in FIG. Since the laser beam is emitted from the condensing optical system 114 and is irradiated to the DMD 50 by being a laser beam having a distribution in the angle of the angle and having a light intensity at the peripheral portion increased compared to the center of the optical axis, the amount of light in the laser beam irradiation region of the DMD 50 As shown in (2) of FIG. 10, the distribution is such that the amount of light in the peripheral portion is increased compared to the center of the optical axis. Therefore, the microlens array 128 having a characteristic that the light beam modulated for each pixel by the DMD 50 decreases the light transmission amount from the center of the optical axis to the periphery as shown in (3) in FIG. When the light is transmitted and irradiated onto the exposure surface of the photosensitive material 134, the light amount distribution of the light beam on the exposure surface is corrected to be uniform, as indicated by (4) in FIG.

As described above, in the exposure apparatus of the first embodiment, the light amount of each drawing unit is corrected to be uniform in a plurality of two-dimensionally distributed pixel units, and high-accuracy image exposure can be performed. .
Even when a combination of driving control techniques for changing the driving timing of each micromirror 62 of the DMD 50 according to the light amount distribution is used, the light amount of each drawing unit is corrected in advance so that the light amount of each drawing unit is uniform. The load on the drive control unit is reduced, the influence on the processing speed is reduced, the electrical circuit configuration and the processing software can be simplified, and the cost can be suppressed.

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

[Second Embodiment]
In the second embodiment, in the exposure head 100 of the exposure apparatus according to the first embodiment described above, the condensing optical system 114 is provided with a telecentric optical system having an aspheric lens as the light distribution correcting means. Similar to the first embodiment, this is a technique for uniformizing the light amount distribution of the light beam on the exposure surface.

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

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

The plano-convex lens 152 disposed on the laser beam incident side (fiber array light source 112 side) has an aspherical surface in which the surface shape of the incident surface S2 increases as the radius of curvature increases from the optical axis (optical axis center) X. For example, the curvature is an aspheric surface that decreases as the distance from the optical axis X increases, and the exit surface S3 is planar.
Further, the plano-convex lens 154 disposed on the laser beam emission side (DMD 50 side) has an aspherical surface in which the incident surface S4 has a flat surface and the surface shape of the output surface S5 decreases as the radius of curvature increases from the optical axis X. In other words, it is an aspheric surface whose curvature increases as the distance from the optical axis X increases.

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

The aspheric data is represented by a coefficient in the following formula (1) representing the aspheric shape.

In the formula (1), each coefficient is defined as follows.
Z: Length of a perpendicular line (mm) drawn from a point on the aspheric surface at a height h from the optical axis to the tangent plane (plane perpendicular to the optical axis) of the apex of the aspheric surface
h: Distance from optical axis (mm) (h ² = x ² + y ² )
R: radius of curvature (curvature: 1 / R)
A: Aspheric data

  With the above configuration, in the exposure apparatus of the second embodiment, as shown in FIG. 11A, the focal length of the laser beam LB2 emitted from the plano-convex lens 152 increases as the distance from the optical axis X increases. Therefore, when the laser beam LB2 reaches the incident surface S4 of the plano-convex lens 154, the light that has passed near the center tends to be farther from the optical axis X than the light that has passed through the periphery of the plano-convex lens 152. Become stronger. Thereby, the brightness of light is higher in the peripheral portion than in the vicinity of the center of the lens. Also, the plano-convex lens 154 has a focal length that decreases as it moves away from the optical axis X, as opposed to the plano-convex lens 152. When these two plano-convex lenses 152 and 154 are combined, a telecentric optical system can be assembled. it can.

  As a result, the light amount distribution of the laser light LB3 collimated and emitted from the telecentric optical system 150 having the plano-convex lenses 152 and 154 has a higher distribution density in the peripheral portion with respect to the optical axis center, and the laser light LB3. In the DMD 50 irradiated with, the amount of light in the peripheral portion is increased more than the central portion (optical axis center) of the laser light irradiation region.

FIG. 11B shows a ray diagram of a telecentric optical system 160 of a spherical lens system that is a base of the telecentric optical system 150 of the present embodiment that is an aspheric lens system.
In the telecentric optical system 160, the incident surface S2 ′ of the plano-convex lens 162 arranged on the incident side of the laser beam (LB1) is a spherical surface, and the emission of the plano-convex lens 164 arranged on the emitting side of the laser beam (LB3 ′). The surface S5 ′ is a spherical surface. Therefore, in the telecentric optical system 160, the light amount distribution of the laser beam LB3 ′ emitted from the emission surface S5 ′ is from the center of the optical axis to the periphery as shown in FIG. 11B. Multiply to obtain a nearly even distribution.

  Thus, in the aspherical lens system (telecentric optical system 150) of the second embodiment, as can be seen from the comparison with the light amount distribution when the above spherical lens system (telecentric optical system 160) is used, the emission In the light amount distribution of the laser beam, the distribution density in the peripheral portion is higher than the center of the optical axis, and the light amount in the peripheral portion is increased from the center of the optical axis.

Therefore, similarly to the first embodiment, even if the light beam modulated by the DMD 50 passes through the microlens array 128 and the light amount in the peripheral portion with respect to the optical axis central portion is reduced, the light amount distribution on the exposure surface. Is irradiated with a light beam corrected so as to be uniform, and even with an exposure apparatus including the telecentric optical system 150, high-accuracy image exposure can be performed.
Further, as described above, since the laser light emitted from the telecentric optical system 150 is emitted as telecentric light and applied to the DMD 50, the telecentricity of the laser light applied to the DMD 50 and the light beam modulated by the DMD 50 It is possible to achieve both the uniformity of the light amount distribution on the exposure surface.

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

  In the second embodiment, since the amount of light at the peripheral portion of the laser light is increased using the telecentric optical system 150, a decrease in light use efficiency in exposure can be suppressed. As a result, the output of the laser light emitted from the fiber array light source 112 can also be reduced, so that the life of the fiber array light source 112 can be extended and the contamination / deterioration of the optical system due to high-intensity light can be suppressed. You can also. Further, the maintenance frequency of the fiber array light source 112 and the optical system can be reduced, and the maintenance cost of the exposure apparatus can be reduced.

  As mentioned above, although the exposure process was demonstrated in detail by 1st and 2nd embodiment, this invention is not limited to them, Various other forms can be implemented within the scope of the present invention.

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

  The optical modulation means includes a fiber array light source including a plurality of combined laser light sources, and a single optical fiber that emits laser light incident from a single semiconductor laser having one light emitting point. A fiber array light source in which fiber light sources are arrayed, a light source in which a plurality of light emitting points are two-dimensionally arranged (for example, an LD array, an organic EL array, etc.), and the like are applicable.

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

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

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

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

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

  The epoxy acrylate compound is a compound having a skeleton derived from an epoxy compound and containing an ethylenically unsaturated double bond and a carboxyl group in the molecule. Such a compound can be obtained by, for example, a method of reacting a polyfunctional epoxy compound with a carboxyl group-containing monomer and further adding a polybasic acid anhydride.

  Examples of the polyfunctional epoxy compound include a bixylenol type or bisphenol type epoxy resin (“YX4000; manufactured by Japan Epoxy Resin Co., Ltd.”) or a mixture thereof, a heterocyclic epoxy resin having an isocyanurate skeleton (“TEPIC; NISSAN CHEMICAL INDUSTRY CO., LTD. "ALALDITE PT810; Ciba Specialty Chemicals" etc.), bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolac Type epoxy resin, cresol novolac type epoxy resin, halogenated phenol novolak type epoxy resin, glycidylamine type epoxy resin (eg, tetraglycidyldiaminodiphenylmethane), hydantoin Epoxy resin, alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A novolac type epoxy resin, tetraphenylolethane type epoxy resin, glycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group-containing epoxy resin ( “ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.”, “HP-4032, EXA-4750, EXA-4700; manufactured by Dainippon Ink and Chemicals”, etc.), epoxy resins having a dicyclopentadiene skeleton (“HP -7200, HP-7200H; manufactured by Dainippon Ink & Chemicals, Inc. "); polyphenol compounds obtained by condensation reaction of phenolic compounds such as phenol, o-cresol, naphthol and aromatic aldehydes having phenolic hydroxyl groups and epi Reaction product of lorhydrin; reaction product of polyphenol compound obtained by addition reaction of phenol compound and diolefin compound such as divinylbenzene or dicyclopentadiene and epichlorohydrin; ring-opening polymer of 4-vinylcyclohexene-1-oxide Epoxidized with peracetic acid, etc .; epoxy resin having a heterocyclic ring such as triglycidyl isocyanurate; glycidyl methacrylate copolymer epoxy resin (“CP-50S, CP-50M; manufactured by NOF Corporation”), cyclohexyl Copolymerized epoxy resin of maleimide and glycidyl methacrylate; epoxy resin obtained by glycidyl etherification of one kind selected from phenol and cresol and p-hydroxybenzaldehyde condensate; bis (glycidyloxyphenyl) fluorene Type epoxy resin; bis (glycidyloxyphenyl) adamantane type epoxy resin; and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the carboxyl group-containing monomer include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, α-cyanocinnamic acid. Acrylic acid dimer; In addition, addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic acid anhydride such as maleic anhydride, phthalic anhydride, cyclohexanedicarboxylic anhydride; The reaction product with a halogen-containing carboxylic acid compound, ω-carboxy-polycaprolactone mono (meth) acrylate, and the like can be mentioned. Furthermore, commercially available products include Aronix M-5300, M-5400, M-5500 and M-5600 manufactured by Toa Synthetic Chemical Industry Co., Ltd., NK Esters CB-1 and CBX- manufactured by Shin-Nakamura Chemical Co., Ltd. 1. Kyoeisha Yushi Chemical Co., Ltd. HOA-MP and HOA-MS, Osaka Organic Chemical Industry Co., Ltd. biscoat # 2100, etc. can be used. These may be used individually by 1 type and may use 2 or more types together.

Examples of the polybasic acid anhydride include succinic anhydride, methyl succinic anhydride, 2,3-dimethyl succinic anhydride, 2,2-dimethyl succinic anhydride, ethyl succinic anhydride, dodecenyl succinic anhydride, nonenyl succinic anhydride, Maleic anhydride, methylmaleic anhydride, 2,3-dimethylmaleic anhydride, 2-chloromaleic anhydride, 2,3-dichloromaleic anhydride, bromomaleic anhydride, itaconic anhydride, citraconic anhydride, cisaccot anhydride , Phthalic anhydride, tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydro Phthalic anhydride, Hydrochlorendic acid and dibasic acid anhydrides such as 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trimellitic anhydride, pyromellitic anhydride Polybasic acid anhydrides such as 3,3 ′, 4,4′-benzophenonetetracarboxylic acid can also be used. These may be used individually by 1 type and may use 2 or more types together.
Each of them is reacted in order to obtain an epoxy acrylate, and the ratio of reacting them is preferably 0.8 to 1.2 equivalents of carboxyl groups of the carboxyl group-containing monomer with respect to 1 equivalent of epoxy groups of the polyfunctional epoxy compound. Is 0.9-1.1 equivalent, 0.1-1.0 equivalent of polybasic acid anhydride, preferably 0.3-1.0 equivalent.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  Examples of the polymerizable group include an ethylenically unsaturated bond (for example, (meth) acryloyl group, (meth) acrylamide group, styryl group, vinyl group such as vinyl ester and vinyl ether, allyl group such as allyl ether and allyl ester). Etc.) and a polymerizable cyclic ether group (for example, epoxy group, oxetane group, etc.) and the like. Among these, an ethylenically unsaturated bond is preferable.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Preferred examples of A ₂ are as follows.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

<< Sensitizer >>
In order to adjust the exposure sensitivity and the photosensitive wavelength in exposure to the photosensitive layer, it is possible to add a sensitizer in addition to the photopolymerization initiator.
The sensitizer can be appropriately selected by a visible light, an ultraviolet laser, a visible light laser, or the like as a light irradiation means described later.
The sensitizer is excited by active energy rays and interacts with other substances (for example, radical generator, acid generator, etc.) (for example, energy transfer, electron transfer, etc.), thereby generating radicals, acids, etc. It is possible to generate a useful group of

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

  The sensitizer is not particularly limited and may be appropriately selected from known sensitizers. For example, known polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, , Fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, indocarbocyanine, thiacarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, Methylene blue, toluidine blue), acridines (eg acridine orange, chloroflavin, acriflavine, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane), anthraquinones (eg anthraquinone), squalium (Eg, squalium), acridones (eg, acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone (eg, 2-chloro-10-butylacridone) Etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- ( 2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis (5,7-di-n-propoxycoumarin), 3,3 ′ -Carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxy bear 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5 7-dipropoxycoumarin, JP-A-5-19475, JP-A-7-271028, JP-A-2002-363206, JP-A-2002-363207, JP-A-2002-363208, JP-A-2002-363209, etc. And the like, and thioxanthone compounds (thioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propyloxythioxanthone, Quantacure QTX, etc.) and the like. , Aromatic rings and compounds Compounds rings are condensed (fused ring compounds), as well as amine compounds substituted with either of at least two aromatic hydrocarbon rings and aromatic heterocyclic rings are preferred.

  Among the condensed ring compounds, hetero-fused ketone compounds (acridone compounds, thioxanthone compounds, coumarin compounds, etc.) and acridine compounds are more preferable. Among the hetero-fused ketone compounds, an acridone compound and a thioxanthone compound are particularly preferable.

  The amine compound substituted with any one of the at least two aromatic hydrocarbon rings and the aromatic heterocyclic ring is preferably a sensitizer having an absorption maximum with respect to light in a wavelength region of 330 to 450 nm, For example, a disubstituted aminobenzophenone compound, a disubstituted amino-benzene compound having a heterocyclic group as a substituent at a carbon atom at the para position relative to an amino group on the benzene ring, Disubstituted amino-benzene compounds having a substituent containing a sulfonylimino group at the carbon atom at the position, disubstituted amino-benzene compounds having a carbostyryl skeleton, and at least two aromatic rings on the nitrogen atom Examples thereof include compounds having a di-substituted amino-benzene as a partial structure, such as a compound having a bonded structure.

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

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

  In the general formula (I), the aliphatic group represents an alkyl group, an alkenyl group, or an alkynyl group that may have a substituent, and the aromatic group has a substituent. Represents an aryl group or a heterocyclic (heterocyclic) group, and the monovalent substituent may be a halogen atom, an amino group which may have a substituent, an alkoxycarbonyl group, a hydroxyl group, an ether group, or a thiol group. , A thioether group, a silyl group, a nitro group, a cyano group, and an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group, each of which may have a substituent.

Examples of the aromatic group include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples include phenyl Groups, naphthyl groups, anthryl groups, phenanthryl groups, indenyl groups, acenaphthenyl groups, and fluorenyl groups. Among them, phenyl groups and naphthyl groups are particularly preferable.
In addition, these aromatic groups may have a substituent, and examples of such a substituent include a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom. For example, what was shown as a substituent in the below-mentioned alkyl group, a substituted alkyl group, or a substituted alkyl group can be mentioned.

The heterocyclic (heterocyclic) group includes a pyrrole ring group, a furan ring group, a thiophene ring group, a benzopyrrole ring group, a benzofuran ring group, a benzothiophene ring group, a pyrazole ring group, an isoxazole ring group, and an isothiazole ring. Group, indazole ring group, benzisoxazole ring group, benzoisothiazole ring group, imidazole ring group, oxazole ring group, thiazole ring group, benzimidazole ring group, benzoxazole ring group, benzothiazole ring group, pyridine ring group, Quinoline ring group, isoquinoline ring group, pyridazine ring group, pyrimidine ring group, pyrazine ring group, phthalazine ring group, quinazoline ring group, quinoxaline ring group, acylidine ring group, phenanthridine ring group, carbazole ring group, purine ring group, Pyran ring group, piperidine ring group, piperazine ring group, morpholine ring group, India Ring group, indolizine ring group, chromene ring group, cinnoline ring group, acridine ring group, phenothiazine ring group, tetrazole ring group, triazine ring group, etc., among which furan ring group, thiophene ring group, imidazole ring group , Thiazole ring group, benzothiazole ring group, pyridine ring group, indole ring group, and acridine ring group are particularly preferable.
Moreover, these heterocyclic groups may have a substituent, and examples of such a substituent include a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom. For example, what was shown as a substituent in the below-mentioned alkyl group, a substituted alkyl group, or a substituted alkyl group can be mentioned.

  Examples of the monovalent substituent include a halogen atom, an amino group that may have a substituent, an alkoxycarbonyl group, a hydroxyl group, an ether group, a thiol group, a thioether group, a silyl group, a nitro group, and a cyano group. An alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group which may have a hydrogen atom is preferred.

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

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

Examples of the substituent of the alkyl group which may have a substituent include a substituent composed of a monovalent non-metal atom excluding a hydrogen atom. Preferred examples include halogen atoms (—F, —Br, -Cl, -I), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkyl Carbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcal Moyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkyl Ureido group, N′-arylureido group, N ′, N′-diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N -Alkylureido group, N'-alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N-arylureido group, N'-aryl-N -Alkylureido group, N'-aryl-N-arylureido group, N ', N'-diaryl-N-alkylureido group, N', N'-diary Ru-N-arylureido group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, Acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl- N-arylcarbamoyl group, al Killsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N— Alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group _(-PO 3 _{H 2)} and its conjugated base group (a phosphonato And referred), a dialkyl phosphono group _(-PO 3 _{(alkyl) 2)} "alkyl = alkyl group, hereinafter the" diarylphosphono group _(-PO 3 _{(aryl) 2)} "aryl = aryl group, hereinafter the same", An alkylarylphosphono group (—PO ₃ (alkyl) (aryl)), a monoalkylphosphono group (—PO ₃ (alkyl)) and a conjugate base group thereof (referred to as an alkylphosphonate group), a monoarylphosphono group ( -PO ₃ H (aryl)) and its conjugate base group (referred to as arylphosphonate group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (referred to as phosphonatoxy group), dialkylphosphonooxy group (— _{OPO 3 H (alkyl) 2)} , diaryl phosphono group _{(-OPO 3 (aryl) 2)} , alkylaryl Phosphonooxy group _(-OPO 3 (alkyl) (aryl)), monoalkyl phosphono group _(-OPO 3 H (alkyl)) and (referred to as alkylphosphonato group) a conjugate base group thereof, monoarylphosphono group (—OPO ₃ H (aryl)) and its conjugate base group (referred to as arylphosphonatoxy group), cyano group, nitro group, aryl group, alkenyl group, alkynyl group, heterocyclic group, silyl group and the like.

  Specific examples of the alkyl group in these substituents include the above-described alkyl groups, and specific examples of the aryl group in the substituent include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, and a mesityl group. , Cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group , Methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylpheny Group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group, phosphate Hona preparative phenyl group.

Examples of the alkenyl group in the substituent include a vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group, and the like. Examples of the alkynyl group in the substituent Examples thereof include an ethynyl group, a 1-propynyl group, a 1-butynyl group, and a trimethylsilylethynyl group.
Examples of the heterocyclic group in the substituent include a pyridyl group and a piperidinyl group.
Examples of the silyl group in the substituent include a trimethylsilyl group.
The substituent may contain an acyl group (R ⁰¹ CO—), and examples of the acyl group include those in which R ⁰¹ is a hydrogen atom, the above alkyl group, or an aryl group.

Examples of R ⁰¹ of the acyl group (R ⁰¹ CO—) include a hydrogen atom, and the alkyl group and aryl group. Among these substituents, halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N are more preferable. -Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group Group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfa group Moyl group, N-arylsulfur Amoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonato group, dialkylphosphono group, diarylphosphono group, monoalkylphosphono group, alkylphosphonato group, monoarylphosphono group, arylphospho Examples thereof include a nato group, a phosphonooxy group, a phosphonatooxy group, an aryl group, and an alkenyl group.

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

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

  Preferred examples of the substituted aryl group include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group, hydroxyphenyl. Group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, benzoyloxyphenyl Group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, Nyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl group, methyl Phosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allylphenyl group, 1-propenylmethylphenyl group, 2-butenylphenyl group, 2-methylallylphenyl group, 2- Examples thereof include a methylpropenylphenyl group, a 2-propynylphenyl group, a 2-butynylphenyl group, and a 3-butynylphenyl group.

Examples of the alkenyl group, the substituted alkenyl group, the alkynyl group, and the substituted alkynyl group (-C (R ⁰² ) = C (R ⁰³ ) (R ⁰⁴ ) and -C≡C (R ⁰⁵ )) include R ^{A group in which 02} , R ⁰³ , R ⁰⁴ and R ⁰⁵ are monovalent non-metallic atoms can be used.
R ⁰² , R ⁰³ , R ⁰⁴ , and R ⁰⁵ are preferably a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group, and specific examples thereof are shown in the above examples. Things can be mentioned. Among these, a hydrogen atom, a halogen atom, and a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms are more preferable.
Specifically, vinyl group, 1-propenyl group, 1-butenyl group, 1-pentenyl group, 1-hexenyl group, 1-octenyl group, 1-methyl-1-propenyl group, 2-methyl-1-propenyl group 2-methyl-1-butenyl group, 2-phenyl-1-ethenyl group, 2-chloro-1-ethenyl group, ethynyl group, 1-propynyl group, 1-butynyl group, phenylethynyl group and the like.
Examples of the heterocyclic group include the pyridyl group exemplified as the substituent of the substituted alkyl group.

As the substituted oxy group (R ⁰⁶ O—), a group in which R ⁰⁶ is a group composed of a monovalent nonmetallic atom excluding a hydrogen atom can be used. Preferred substituted oxy groups include alkoxy groups, aryloxy groups, acyloxy groups, carbamoyloxy groups, N-alkylcarbamoyloxy groups, N-arylcarbamoyloxy groups, N, N-dialkylcarbamoyloxy groups, N, N-diarylcarbamoyloxy groups. Groups, N-alkyl-N-arylcarbamoyloxy groups, alkylsulfoxy groups, arylsulfoxy groups, phosphonooxy groups, and phosphonatoxy groups. Examples of the alkyl group and aryl group in these include the alkyl groups, substituted alkyl groups, aryl groups, and substituted aryl groups described above. Examples of the acyl group (R ⁰⁷ CO—) in the acyloxy group include those in which R ⁰⁷ is an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group mentioned above. Among these substituents, an alkoxy group, an aryloxy group, an acyloxy group, and an arylsulfoxy group are more preferable. Specific examples of preferred substituted oxy groups include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, pentyloxy, hexyloxy, dodecyloxy, benzyloxy, allyloxy, phenethyloxy, Carboxyethyloxy group, methoxycarbonylethyloxy group, ethoxycarbonylethyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, morpholinoethoxy group, morpholinopropyloxy group, allyloxyethoxyethoxy group, Phenoxy group, tolyloxy group, xylyloxy group, mesityloxy group, mesityloxy group, cumenyloxy group, methoxyphenyloxy group, ethoxyphenyloxy group, chlorophenyl Alkoxy group, bromophenyl group, acetyloxy group, benzoyloxy group, naphthyloxy group, a phenylsulfonyloxy group, a phosphonooxy group, phosphonatoxy group, and the like.

As the substituted amino group (R ⁰⁸ NH—, (R ⁰⁹ ) (R ⁰¹⁰ ) N—) including an amide group, R ⁰⁸ , R ⁰⁹ , and R ⁰¹⁰ are a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom. Can be used. R ⁰⁹ and R ⁰¹⁰ may be bonded to form a ring. Preferred examples of the substituted amino group include an N-alkylamino group, an N, N-dialkylamino group, an N-arylamino group, an N, N-diarylamino group, an N-alkyl-N-arylamino group, an acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N′-arylureido group, N ′, N′-diarylureido group N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N′-alkyl-N′-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, '-Dialkyl-N'-arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N-arylureido group, N', N'-diaryl-N-alkylureido group, N ', N′-diaryl-N-arylureido group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxy A carbonylamino group, an N-alkyl-N-alkoxycarbonylamino group, an N-alkyl-N-aryloxycarbonylamino group, an N-aryl-N-alkoxycarbonylamino group, and an N-aryl-N-aryloxycarbonylamino group. Can be mentioned. Examples of the alkyl group and aryl group include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group, such as acylamino group, N-alkylacylamino group, and N-arylacylamino. R ⁰⁷ groups definitive acyl group (R ⁰⁷ CO-) are as described above. Of these, more preferred are an N-alkylamino group, an N, N-dialkylamino group, an N-arylamino group, and an acylamino group. Specific examples of preferred substituted amino groups include methylamino group, ethylamino group, diethylamino group, morpholino group, piperidino group, pyrrolidino group, phenylamino group, benzoylamino group, acetylamino group and the like.

As the substituted sulfonyl group (R ⁰¹¹ —SO ₂ —), those in which R ⁰¹¹ is a group composed of a monovalent nonmetallic atomic group can be used. More preferable examples include an alkylsulfonyl group and an arylsulfonyl group. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Specific examples of such a substituted sulfonyl group include a butylsulfonyl group, a phenylsulfonyl group, a chlorophenylsulfonyl group, and the like.

As described above, the sulfonate group (—SO ₃ ^— ) means a conjugated base anion group of the sulfo group (—SO ₃ H), and is usually preferably used together with a counter cation. Examples of such counter cations include those generally known, that is, various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.), and metal ions (Na ⁺ , K ⁺ , Ca). ²⁺ , Zn ^{2+ and the} like).

As the substituted carbonyl group (R ⁰¹³ —CO—), a group in which R ⁰¹³ is a monovalent nonmetallic atom can be used. Preferred examples of the substituted carbonyl group include formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N′-arylcarbamoyl group may be mentioned. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Among these, more preferred substituted carbonyl groups include formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-ary. A rucarbamoyl group can be mentioned, and even more preferred are a formyl group, an acyl group, an alkoxycarbonyl group and an aryloxycarbonyl group. Specific examples of preferred substituted carbonyl groups include formyl group, acetyl group, benzoyl group, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, allyloxycarbonyl group, dimethylaminophenylethenylcarbonyl group, methoxycarbonylmethoxycarbonyl group, N -Methylcarbamoyl group, N-phenylcarbamoyl group, N, N-diethylcarbamoyl group, morpholinocarbonyl group and the like.

As the substituted sulfinyl group (R ⁰¹⁴ —SO—), a group in which R ⁰¹⁴ is a monovalent nonmetallic atomic group can be used. Preferable examples include alkylsulfinyl group, arylsulfinyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl. Group, N-alkyl-N-arylsulfinamoyl group. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Of these, more preferred examples include an alkylsulfinyl group and an arylsulfinyl group. Specific examples of such a substituted sulfinyl group include a hexylsulfinyl group, a benzylsulfinyl group, and a tolylsulfinyl group.

  The substituted phosphono group means a group in which one or two hydroxyl groups on the phosphono group are substituted with other organic oxo groups, and preferred examples thereof include the above-mentioned dialkylphosphono group, diarylphosphono group, alkylarylphospho group. Group, monoalkylphosphono group and monoarylphosphono group. Of these, dialkylphosphono groups and diarylphosphono groups are more preferred. Specific examples thereof include a diethyl phosphono group, a dibutyl phosphono group, a diphenyl phosphono group, and the like.

As described above, the phosphonate group (—PO ₃ H ₂ ^— , —PO ₃ H ⁻ ) is a conjugate base anion derived from the acid first dissociation or acid second dissociation of the phosphono group (—PO ₃ H ₂ ). Means group. Usually, it is preferable to use it with a counter cation. Examples of such counter cations include those generally known, that is, various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.), and metal ions (Na ⁺ , K ⁺ , Ca). ²⁺ , Zn ^{2+ and the} like).

Of the substituents phosphonato group foregoing substituted phosphono group, but was replaced a hydroxyl group on one organic oxo group is the conjugate base anion group, as specific examples, the aforementioned monoalkyl phosphono group (-PO 3 _H ( alkyl)), and a conjugate base of a monoarylphosphono group (—PO ₃ H (aryl)).

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The said sensitizer may be used individually by 1 type, and may use 2 or more types together.
The blending amount of the sensitizer is preferably 0.01 to 4% by mass, more preferably 0.02 to 2% by mass, and particularly preferably 0.05 to 1% by mass in the total solid content of the photosensitive composition. .
When the content is less than 0.01% by mass, the sensitivity may decrease, and when the content exceeds 4% by mass, the shape of the pattern may be deteriorated.

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

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

From the viewpoint of storage stability at room temperature, the epoxy compound containing an epoxy group having an alkyl group at the β-position is substituted with β-alkyl in all epoxy groups in the total amount of the epoxy compound contained in the photosensitive composition. The proportion of glycidyl groups is preferably 30% or more, more preferably 40% or more, and particularly preferably 50% or more.
The β-alkyl-substituted glycidyl group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include β-methylglycidyl group, β-ethylglycidyl group, β-propylglycidyl group, β-butylglycidyl group. Among these, a β-methylglycidyl group is preferred from the viewpoint of improving the storage stability of the photosensitive resin composition and the ease of synthesis.

  As the epoxy compound containing an epoxy group having an alkyl group at the β-position, for example, an epoxy compound derived from a polyhydric phenol compound and a β-alkylepihalohydrin is preferable.

  The β-alkylepihalohydrin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, β-methylepichlorohydrin, β-methylepibromohydrin, β-methylepifluorohydrin, etc. Β-methyl epihalohydrin, β-ethyl epichlorohydrin, β-ethyl epibromohydrin, β-ethyl epihalohydrin, such as β-ethyl epihalohydrin, β-propyl epichlorohydrin, β-propyl epibromohydrin Β-propyl epihalohydrin such as phosphorus and β-propyl epifluorohydrin; β-butyl epihalohydrin such as β-butyl epichlorohydrin, β-butyl epibromohydrin, β-butyl epifluorohydrin; . Among these, β-methylepihalohydrin is preferable from the viewpoint of reactivity with the polyhydric phenol and fluidity.

  The polyhydric phenol compound is not particularly limited as long as it is a compound containing two or more aromatic hydroxyl groups in one molecule, and can be appropriately selected according to the purpose. For example, bisphenol A, bisphenol F Bisphenol compounds such as bisphenol S, biphenol compounds such as biphenol and tetramethylbiphenol, naphthol compounds such as dihydroxynaphthalene and binaphthol, phenol novolac resins such as phenol-formaldehyde polycondensates, cresol-formaldehyde polycondensates 1 1-10 monoalkyl-substituted phenol-formaldehyde polycondensate, xylenol-formaldehyde polycondensate and the like, and C1-C10 dialkyl-substituted phenol-formaldehyde polycondensate, bisphenol A-formalde De polycondensates such bisphenol compounds of - formaldehyde polycondensates, phenol and copolycondensates of monoalkyl-substituted phenol and formaldehyde having 1 to 10 carbon atoms, and phenolic compounds and polyaddition products of divinylbenzene. Among these, when selecting for the purpose of improving fluidity | liquidity and storage stability, the said bisphenol compound is preferable, for example.

Examples of the epoxy compound containing an epoxy group having an alkyl group at the β-position include di-β-alkyl glycidyl ether of bisphenol A, di-β-alkyl glycidyl ether of bisphenol F, and di-β-alkyl glycidyl of bisphenol S. Di-β-alkyl glycidyl ethers of bisphenol compounds such as ethers; di-β-alkyl glycidyl ethers of biphenols such as di-β-alkyl glycidyl ethers of biphenols and di-β-alkyl glycidyl ethers of tetramethylbiphenol; Β-alkyl glycidyl ethers of naphthol compounds such as di-β-alkyl glycidyl ethers of binaphthol, di-β-alkyl glycidyl ethers of binaphthol; poly- of phenol-formaldehyde polycondensates β-alkyl glycidyl ether; poly-β-alkyl glycidyl ether of monoalkyl-substituted phenol-formaldehyde polycondensate having 1 to 10 carbon atoms such as poly-β-alkyl glycidyl ether of cresol-formaldehyde polycondensate; xylenol-formaldehyde C1-C10 dialkyl-substituted phenol-formaldehyde polycondensate poly-β-alkyl glycidyl ether such as poly-β-alkyl glycidyl ether of condensate; poly-β-alkyl glycidyl ether of bisphenol A-formaldehyde polycondensate Bisphenol compound-formaldehyde polycondensate poly-β-alkyl glycidyl ether; phenol compound-divinylbenzene polyaddition product poly-β-alkyl glycidyl ether; The
Among these, a bisphenol compound represented by the following structural formula (i), a β-alkyl glycidyl ether derived from a polymer obtained from the bisphenol compound and epichlorohydrin, and the following structural formula (ii) Poly-β-alkyl glycidyl ethers of phenol compound-formaldehyde polycondensates are preferred.

In the Structural Formula (i), R "represents any of an alkyl group having 1 to 6 carbon hydrogen and _{carbon, n 11} represents an integer of 0 to 20.
In the Structural Formula (ii), R "represents any of an alkyl group having 1 to 6 carbon hydrogen and carbon, R'represents either hydrogen atoms, and CH _3, n is 0 to 20 Represents an integer.
These epoxy compounds containing an epoxy group having an alkyl group at the β-position may be used alone or in combination of two or more. It is also possible to use together an epoxy compound having at least two oxirane rings in one molecule and an epoxy compound containing an epoxy group having an alkyl group at the β-position.

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

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

  Solid content in the said photosensitive composition of the said epoxy compound, the said oxetane compound, and the compound which can accelerate | stimulate thermosetting with these and carboxylic acid is 0.01-15 mass% normally.

  Further, as the thermal crosslinking agent, a polyisocyanate compound described in JP-A-5-9407 can be used, and the polyisocyanate compound is aliphatic, cycloaliphatic or aromatic containing at least two isocyanate groups. It may be derived from a group-substituted aliphatic compound. Specifically, bifunctional isocyanate (for example, a mixture of 1,3-phenylene diisocyanate and 1,4-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate, 1,3- and 1,4-xylylene). Diisocyanate, bis (4-isocyanate-phenyl) methane, bis (4-isocyanatocyclohexyl) methane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, etc.), the bifunctional isocyanate, trimethylolpropane, pentalithol tol Polyfunctional alcohols such as glycerin; alkylene oxide adducts of the polyfunctional alcohols and adducts of the bifunctional isocyanates; hexamethylene diisocyanate, hexamethylene-1,6-di Isocyanate and cyclic trimers thereof derivatives; and the like.

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

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

  1-50 mass% is preferable and, as for solid content content of the said thermal crosslinking agent in the said photosensitive composition, 3-30 mass% is more preferable. When the solid content is less than 1% by mass, improvement in the film strength of the cured film is not recognized, and when it exceeds 50% by mass, developability and exposure sensitivity may be deteriorated.

<Other ingredients>
Examples of the other components include thermal polymerization inhibitors, plasticizers, colorants (color pigments or dyes), extender pigments, and the like, and further adhesion promoters to the substrate surface and other auxiliary agents ( For example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, etc.) may be used in combination. By appropriately containing these components, properties such as stability, photographic properties, film physical properties, etc. of the intended photosensitive composition or the photosensitive film described later can be adjusted.

<< Thermal polymerization inhibitor >>
The thermal polymerization inhibitor may be added to prevent thermal polymerization or temporal polymerization of the polymerizable compound.
Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine. , Chloranil, naphthylamine, β-naphthol, 2,6-di-tert-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid 4-toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.

  As content of the said thermal-polymerization inhibitor, 0.001-5 mass% is preferable with respect to the said polymeric compound, 0.005-2 mass% is more preferable, 0.01-1 mass% is especially preferable. When the content is less than 0.001% by mass, stability during storage may be lowered, and when it exceeds 5% by mass, sensitivity to active energy rays may be lowered.

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

  The solid content in the photosensitive composition solid content of the color pigment can be determined in consideration of the exposure sensitivity, resolution, etc. of the photosensitive layer at the time of permanent pattern formation, depending on the type of the color pigment. Generally, 0.05 to 10% by mass is preferable, and 0.1 to 5% by mass is more preferable.

<< External pigment >>
If necessary, the photosensitive composition may be inorganic for the purpose of improving the surface hardness of the permanent pattern or keeping the linear expansion coefficient low, or keeping the dielectric constant or dielectric loss tangent of the cured film low. Pigments and organic fine particles can be added.
The inorganic pigment is not particularly limited and may be appropriately selected from known ones. For example, kaolin, barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, vapor phase method silica, amorphous Examples thereof include silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica.
The average particle diameter of the inorganic pigment is preferably less than 10 μm, and more preferably 3 μm or less. When the average particle size is 10 μm or more, resolution may be deteriorated due to light scattering.
There is no restriction | limiting in particular as said organic fine particle, According to the objective, it can select suitably, For example, a melamine resin, a benzoguanamine resin, a crosslinked polystyrene resin etc. are mentioned. Further, silica having an average particle diameter of 1 to 5 μm and an oil absorption of about 100 to 200 m ² / g, spherical porous fine particles made of a crosslinked resin, and the like can be used.

  The amount of the extender is preferably 5 to 60% by mass. When the addition amount is less than 5% by mass, the linear expansion coefficient may not be sufficiently reduced. When the addition amount exceeds 60% by mass, when the cured film is formed on the photosensitive layer surface, The film quality becomes fragile, and when a wiring is formed using a permanent pattern, the function of the wiring as a protective film may be impaired.

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

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

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

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

In the method for forming a photosensitive layer according to the first aspect, a photosensitive layer is formed by applying and drying the photosensitive composition on the substrate.
The method for coating and drying is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the photosensitive composition is dissolved, emulsified or dispersed on the surface of the base material in water or a solvent. And a method of laminating by preparing a photosensitive composition solution, applying the solution directly, and drying the solution.

  There is no restriction | limiting in particular as a solvent of the said photosensitive composition solution, According to the objective, it can select suitably, For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, n-hexanol Alcohols such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone, etc .; ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and Esters such as methoxypropyl acetate; aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene; carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, monochlorobenzene Halogenated hydrocarbons of: ethers such as tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane, etc. . These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.

The coating method is not particularly limited and can be appropriately selected depending on the purpose. For example, using a spin coater, a slit spin coater, a roll coater, a die coater, a curtain coater, etc. The method of apply | coating is mentioned.
The drying conditions vary depending on each component, the type of solvent, the use ratio, and the like, but are usually about 60 to 110 ° C. for about 30 seconds to 15 minutes.

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

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

[Photosensitive film]
The photosensitive film has at least a support and a photosensitive layer, preferably a protective film, and, if necessary, other layers such as a cushion layer and an oxygen barrier layer (PC layer). Having a layer.
The form of the photosensitive film is not particularly limited and may be appropriately selected depending on the purpose. For example, the photosensitive layer and the protective film are provided in this order on the support, On the support, the PC layer, the photosensitive layer, and the protective film are arranged in this order. On the support, the cushion layer, the PC layer, the photosensitive layer, and the protective film are arranged in this order. The form which has is mentioned. The photosensitive layer may be a single layer or a plurality of layers.

<Support>
The support is not particularly limited and may be appropriately selected depending on the intended purpose. However, it is preferable that the photosensitive layer can be peeled off and the light transmittance is good, and the surface smoothness is further improved. Is more preferable.

The support is preferably made of a synthetic resin and transparent, for example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester, poly ( (Meth) acrylic acid ester copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoro Various plastic films such as ethylene, cellulose-based film, nylon film and the like can be mentioned, and among these, polyethylene terephthalate is particularly preferable. These may be used alone or in combination of two or more.
As the support, for example, the support described in JP-A-4-208940, JP-A-5-80503, JP-A-5-173320, JP-A-5-72724, or the like is used. You can also.

  There is no restriction | limiting in particular as thickness of the said support body, Although it can select suitably according to the objective, For example, 4-300 micrometers is preferable and 5-175 micrometers is more preferable.

  There is no restriction | limiting in particular as a shape of the said support body, Although it can select suitably according to the objective, A long shape is preferable. There is no restriction | limiting in particular as the length of the said elongate support body, For example, the thing of length 10m-20000m is mentioned.

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

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

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

<Protective film>
The protective film has a function of preventing and protecting the photosensitive layer from being stained and damaged.
There is no restriction | limiting in particular as a location provided in the said photosensitive film of the said protective film, Although it can select suitably according to the objective, Usually, it is provided on the said photosensitive layer.
Examples of the protective film include those used for the support, silicone paper, polyethylene, paper laminated with polypropylene, polyolefin or polytetrafluoroethylene sheet, etc. Among these, polyethylene film, Polypropylene film is preferred.
There is no restriction | limiting in particular as thickness of the said protective film, Although it can select suitably according to the objective, For example, 5-100 micrometers is preferable and 8-30 micrometers is more preferable.
When the protective film is used, it is preferable that the adhesive force A between the photosensitive layer and the support and the adhesive force B between the photosensitive layer and the protective film satisfy the relationship of adhesive force A> adhesive force B.
Examples of the combination of the support and the protective film (support / protective film) include polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate, and the like. . Moreover, the relationship of the above adhesive forces can be satisfy | filled by surface-treating at least any one of a support body and a protective film. The surface treatment of the support may be performed in order to increase the adhesive force with the photosensitive layer. For example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow treatment Examples thereof include a discharge irradiation process, an active plasma irradiation process, and a laser beam irradiation process.

Moreover, as a static friction coefficient of the said support body and the said protective film, 0.3-1.4 are preferable and 0.5-1.2 are more preferable.
When the coefficient of static friction is less than 0.3, slipping is excessive, so that winding deviation may occur when the roll is formed. Sometimes.

  The photosensitive film is preferably stored, for example, wound around a cylindrical core, wound in a long roll shape. There is no restriction | limiting in particular as the length of the said elongate photosensitive film, For example, it can select suitably from the range of 10m-20,000m. Further, slitting may be performed so that the user can easily use, and a long body in the range of 100 m to 1,000 m may be formed into a roll. In this case, it is preferable that the support is wound up so as to be the outermost side. Moreover, you may slit the said roll-shaped photosensitive film in a sheet form. When storing, from the viewpoint of protecting the end face and preventing edge fusion, it is preferable to install a separator (particularly moisture-proof and containing a desiccant) on the end face, and use a low moisture-permeable material for packaging. Is preferred.

The protective film may be surface-treated in order to adjust the adhesion between the protective film and the photosensitive layer. In the surface treatment, for example, an undercoat layer made of a polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, or polyvinyl alcohol is formed on the surface of the protective film. The undercoat layer can be formed by applying the polymer coating solution to the surface of the protective film and then drying at 30 to 150 ° C. (especially 50 to 120 ° C.) for 1 to 30 minutes.
In addition to the photosensitive layer, the support, and the protective film, a cushion layer, an oxygen blocking layer (PC layer), a release layer, an adhesive layer, a light absorption layer, a surface protective layer, and the like may be included. .
The cushion layer is a layer that has no tackiness at room temperature and melts and flows when laminated under vacuum and heating conditions.
The PC layer is usually a coating of about 0.5 to 5 μm formed mainly of polyvinyl alcohol.

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

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

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

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

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

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

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

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

[Curing process]
The curing treatment step is a step of performing a curing treatment on the photosensitive layer in the formed permanent pattern after the development step is performed.

  There is no restriction | limiting in particular as said hardening process, Although it can select suitably according to the objective, For example, a whole surface exposure process, a whole surface heat processing, etc. are mentioned suitably.

Examples of the entire surface exposure processing method include a method of exposing the entire surface of the laminate on which the permanent pattern is formed after the developing step. The entire surface exposure accelerates the curing of the resin in the photosensitive composition forming the photosensitive layer, and the surface of the permanent pattern is cured.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface exposure, Although it can select suitably according to the objective, For example, UV exposure machines, such as an ultrahigh pressure mercury lamp, are mentioned suitably.

Examples of the entire surface heat treatment method include a method of heating the entire surface of the laminate on which the permanent pattern is formed after the developing step. By heating the entire surface, the film strength of the surface of the permanent pattern is increased.
As heating temperature in the said whole surface heating, 120-250 degreeC is preferable and 120-200 degreeC is more preferable. When the heating temperature is less than 120 ° C., the film strength may not be improved by heat treatment. When the heating temperature exceeds 250 ° C., the resin in the photosensitive composition is decomposed, and the film quality is weak and brittle. Sometimes.
As heating time in the said whole surface heating, 10 to 120 minutes are preferable and 15 to 60 minutes are more preferable.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface heating, According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, IR heater etc. are mentioned.

When the substrate is a printed wiring board such as a multilayer wiring board, the permanent pattern of the present invention can be formed on the printed wiring board, and further soldered as follows.
That is, the development step forms a hardened layer that is the permanent pattern, and the metal layer is exposed on the surface of the printed wiring board. Gold plating is performed on the portion of the metal layer exposed on the surface of the printed wiring board, and then soldering is performed. Then, a semiconductor or a component is mounted on the soldered portion. At this time, the permanent pattern by the hardened layer functions as a protective film, an insulating film (interlayer insulating film), or a solder resist, and prevents external impact and conduction between adjacent electrodes.

In the permanent pattern forming method of the present invention, it is preferable to form at least one of a protective film, an interlayer insulating film, and a solder resist pattern.
The permanent pattern formed by the permanent pattern forming method can protect the wiring from external impact and bending, and particularly in the case of the interlayer insulating film, for example, a multilayer wiring board or a build-up wiring It is useful for high-density mounting of semiconductors and components on a substrate.

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

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

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

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

  Using the photosensitive film and laminate, exposure sensitivity and resolution of the photosensitive layer were measured by the following methods, and edge roughness was evaluated. The results are shown in Table 3.

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

-Measurement of exposure sensitivity-
The photosensitive layer in the laminate, from the polyethylene terephthalate film (support) side, using the following exposure device, light energy from 0.1 mJ / cm ² to 100 mJ / cm ² at ^{2 1/2} times the interval The exposure was performed by irradiating different amounts of light, and a part of the photosensitive layer was cured. After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) is peeled off from the laminate, and an aqueous sodium carbonate solution (30 ° C., 1% by mass) is applied to the entire surface of the photosensitive layer on the copper clad laminate. Spraying was performed twice as long as the shortest development time obtained by the above method to dissolve and remove uncured regions, and the thickness of the remaining cured regions was measured. Subsequently, the relationship between the light irradiation amount and the thickness of the cured layer was plotted to obtain a sensitivity curve. From the sensitivity curve thus obtained, the amount of light energy when the thickness of the cured region was the same as that before exposure was determined as the amount of light energy necessary for curing the photosensitive layer. Table 3 shows the amount of light energy (exposure sensitivity) required for curing the photosensitive layer thus obtained.

<< Exposure equipment >>
The combined laser light source shown in FIGS. 4A to 8 as the light irradiating means, and the DMD schematically shown in FIG. 2 as the light modulating means, and a micro-array having 1024 micromirrors arranged in the main scanning direction. An exposure apparatus having an exposure head having a DMD controlled to drive only 1024 × 256 rows out of 768 pairs of mirror rows arranged in the sub-scanning direction and the optical system shown in FIG. 1 is used. It was.

In the exposure head, the condensing optical system is a laser beam having a predetermined distribution of chief ray angles with respect to the laser beam incident from the fiber array light source, separately from the light amount distribution correction function provided in the rod integrator 118. Is emitted and irradiated to the DMD.
In addition, the magnitude of the light quantity distribution amount is set to be equal to or larger than the light quantity reduction amount in the peripheral portion caused by the microlens array, and the predetermined distance YA from the optical axis center shown in FIG. YS>YA> YS / 2, where YS is the distance to the part (the outer peripheral edge of the DMD).

<Measurement of resolution>
The laminate was prepared by the same method as above, and allowed to stand at room temperature (23 ° C., 55% RH) for 10 minutes. From the obtained polyethylene terephthalate film (support) of the laminate, using the pattern forming device, line / space = 1/1, and line widths of 5 to 20 μm are exposed in increments of 1 μm. Each line width was exposed in 5 μm increments until the line width was 20-50 μm. The exposure amount at this time is the amount of light energy necessary for effecting the photosensitive layer, obtained by measuring the exposure sensitivity.
After exposure, after standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) is peeled off from the laminate, and an aqueous sodium carbonate solution (as a developer) is applied to the entire surface of the photosensitive layer on the copper clad laminate. 30 ° C., 1% by mass) was sprayed at a spray pressure of 0.15 MPa twice the shortest development time determined by the above method to dissolve and remove uncured regions.
The surface of the copper-clad laminate with a cured resin pattern thus obtained was observed with an optical microscope, and the minimum line width without any abnormalities such as tsumari and twist was measured on the cured resin pattern line. did. The resolution is better as the numerical value is smaller. The results are shown in Table 3.

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

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

(Example 2)
In Example 1, a pattern was formed in the same manner as in Example 1 except that the exposure apparatus was changed to that described below, and the exposure sensitivity, resolution, and edge roughness were evaluated. The results are shown in Table 3.

<< Exposure equipment >>
The combined laser light source shown in FIGS. 4 to 8 as the light irradiating means, and the DMD schematically shown in FIG. 2 as the light modulating means, wherein the micromirrors have 1024 micromirrors arranged in the main scanning direction. An exposure apparatus provided with an exposure head having a DMD controlled to drive only 1024 × 256 rows out of 768 rows arranged in the sub-scanning direction and the optical system shown in FIG. 1 was used. . Between the rod integrator 118 and the condensing lens 120 of the exposure head shown in FIG. 1, a telecentric lens composed of a pair of plano-convex lenses 152 and 154 as shown in FIG. 11A as the light distribution correcting means. An optical system 150 is provided.

The plano-convex lens 152 disposed on the laser beam incident side (fiber array light source 112 side) has an aspherical surface in which the surface shape of the incident surface S2 increases as the radius of curvature increases from the optical axis (optical axis center) X. For example, the curvature is an aspheric surface that decreases as the distance from the optical axis X increases, and the exit surface S3 is planar.
Further, the plano-convex lens 154 disposed on the laser beam emission side (DMD 50 side) has an aspherical surface in which the incident surface S4 has a flat surface and the surface shape of the output surface S5 decreases as the radius of curvature increases from the optical axis X. In other words, it is an aspheric surface whose curvature increases as the distance from the optical axis X increases.

  By using this exposure apparatus, the light intensity distribution of the laser beam emitted in parallel from the telecentric optical system 150 has a higher distribution density in the periphery with respect to the center of the optical axis, and this laser beam was irradiated. In the DMD 50, the amount of light in the peripheral part is increased from the central part (optical axis center) of the laser light irradiation region. Thereafter, the laser beam passes through the microlens array 128 to cause a decrease in the amount of light at the peripheral portion with respect to the central portion of the optical axis, and the exposure surface is irradiated with the light beam corrected so that the light amount distribution is uniform.

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

Example 4
In Example 1, 0.2 part by mass of 1-chloro-4-propyloxythioxanthone in the photosensitive composition is replaced with 0.2 part by mass of the disubstituted amino-benzene compound represented by the following structural formula (41). A photosensitive composition was prepared in the same manner as in Example 1 except that. Using the obtained photosensitive composition, the photosensitive film and the laminate were produced in the same manner as in Example 1, and a permanent pattern was formed, and the exposure sensitivity of the photosensitive layer in the same manner as in Example 1, The resolution was measured, and the formed permanent pattern was evaluated for the presence or absence of jaggies and the edge roughness. The results are shown in Table 3.

(Comparative Example 1)
In Example 1, except that exposure was performed without setting and changing each parameter, a photosensitive film and a laminate were prepared in the same manner as in Example 1, a permanent pattern was formed, exposure sensitivity, Resolution and edge roughness were evaluated. The results are shown in Table 3.

(Comparative Example 2)
In the exposure apparatus of Example 2, a photosensitive film and a laminate were prepared in the same manner as in Example 2 except that an exposure head having a configuration in which the light distribution correction unit was not included in the condensing optical system was prepared. The exposure sensitivity, resolution, and edge roughness were evaluated. The results are shown in Table 3.

  From the results of Table 3, compared with the permanent patterns of Comparative Examples 1 and 2, the permanent patterns of Examples 1 to 4 using the exposure head equipped with the light distribution correcting means are high definition, and the edge roughness is small. It turned out to be highly accurate. Furthermore, it has been found that by using an exposure head provided with a light distribution correction means, high-definition exposure can be realized at low cost and efficient exposure can be achieved.

  The permanent pattern forming method of the present invention makes the light amount of each drawing unit distributed two-dimensionally uniform while controlling the cost in exposure using a digital exposure apparatus having an exposure head in which the drawing units are two-dimensionally distributed. Can provide a permanent pattern forming method capable of forming a fine permanent pattern with high accuracy, and is therefore preferably used for forming a high-definition permanent pattern such as a protective film, an insulating film, and a solder resist pattern. can do.

FIG. 1 is a schematic block diagram showing an optical system of an exposure head provided in an exposure apparatus used in the permanent pattern forming method of the present invention. FIG. 2 is an example of a partially enlarged view showing a configuration of a digital micromirror device (DMD). FIG. 3A is an explanatory diagram for explaining the operation of the DMD shown in FIG. FIG. 3B is an explanatory diagram for explaining the operation of the DMD shown in FIG. FIG. 4A is a perspective view showing a configuration of a fiber array light source. FIG. 4B is a plan view showing an array of light emitting points in the laser emitting portion of FIG. 4A. FIG. 5 is a plan view showing the configuration of the combined laser light source. FIG. 6 is a plan view showing the configuration of the laser module. FIG. 7 is a side view showing the configuration of the laser module shown in FIG. FIG. 8 is a partial side view showing the configuration of the laser module shown in FIG. FIG. 9A is a schematic diagram schematically showing the inclination of the principal ray of the laser light irradiated on the DMD. FIG. 9B is a graph showing a distribution of chief ray angles of laser light irradiated on the DMD. FIG. 10 shows the light amount distribution when the DMD is irradiated with the laser light having the chief ray angle distribution corresponding to the chief ray angle distribution (1) of the laser beam emitted onto the DMD shown in FIG. 9B. The graph (2), the graph (3) showing the light transmission characteristics between the DMD and the microlens array, and the amount of light in the exposure area by performing image exposure with the laser beam adjusted as shown in the graph (3). It is a graph figure (4) which shows the state where distribution was equalized and amended. FIG. 11A is a configuration diagram showing a telecentric optical system, and is a configuration diagram showing a telecentric optical system having an aspheric lens according to the second embodiment of the present invention. FIG. 11B is a configuration diagram showing a telecentric optical system, and is a configuration diagram showing a telecentric optical system having a spherical lens serving as a base of the telecentric optical system of FIG. 11A.

Explanation of symbols

50 DMD (Spatial Modulation Element)
62 Micromirror (Picture element)
100 Exposure head 112 Fiber array light source (light source)
114 Condensing optical system (light quantity distribution correcting means)
134 Laminate (photosensitive material)
150 Telecentric optical system 152 Plano-convex lens (first optical lens)
154 Plano-convex lens (second optical lens)
LB Laser light (light beam)
S2 entrance surface S3 exit surface S4 entrance surface S5 exit surface X optical axis

Claims (24)

For the photosensitive layer formed on the surface of the substrate with a photosensitive composition containing at least a binder, a polymerizable compound, a photopolymerization initiation system compound, and a thermal crosslinking agent,
There are n (where n is a natural number of 1 or more) two-dimensionally arranged pixel parts, and light modulation means for changing the light modulation state for each pixel part according to pattern information Irradiating the light beam emitted from the irradiating means through a condensing optical system having a light distribution correcting means, irradiating and developing the light beam modulated by the light modulating means, and developing,
The exposure gives a distribution of the amount of light in the irradiation region of the light beam irradiated from the light irradiation unit to the light modulation unit, and the light amount distribution of the light beam modulated by the light modulation unit is the photosensitive layer. A method for forming a permanent pattern, wherein the method is carried out by correcting so as to be uniform on the exposed surface.   The permanent pattern forming method according to claim 1, wherein the light modulation unit is configured to irradiate the light modulation unit with the light beam emitted from the light irradiation unit as a light beam having a distribution in the angle of the principal ray by the condensing optical system.   The permanent pattern forming method according to claim 1, wherein the light modulation unit irradiates the light modulation unit with the light beam emitted from the light irradiation unit as telecentric light by a condensing optical system.   The condensing optical system has a first optical lens having an aspheric shape in which the lens power decreases as the distance from the optical axis center increases, and a first optical lens having an aspheric shape in which the lens power increases as the distance from the optical axis center increases. The permanent pattern forming method according to claim 3, further comprising a light distribution correction unit including a second optical lens.   The permanent pattern formation according to any one of claims 1 to 4, wherein the condensing optical system increases the amount of light in the peripheral portion rather than the central portion in the irradiation region of the light beam irradiated from the light irradiation means to the light modulation means. Method.   6. The permanent pattern forming method according to claim 1, wherein the light modulation means is a spatial light modulation element.   The permanent pattern formation method according to any one of claims 1 to 6, wherein the photosensitive layer is formed by applying a photosensitive composition to a surface of a substrate and drying.   The photosensitive layer is formed by laminating a photosensitive film having a support and a photosensitive layer formed by laminating a photosensitive composition on the support on the surface of the substrate under at least one of heating and pressing. The permanent pattern formation method according to claim 1, wherein the permanent pattern formation method is performed.   The binder according to any one of claims 1 to 8, wherein the binder contains at least one of an epoxy acrylate compound and at least one of a vinyl copolymer having a (meth) acryloyl group and an acidic group in a side chain. Permanent pattern forming method.   The thermal crosslinking agent is at least one selected from an epoxy compound, an oxetane compound, a polyisocyanate compound, a compound obtained by reacting a polyisocyanate compound with a blocking agent, and a melamine derivative. The permanent pattern formation method as described.   The permanent pattern formation method in any one of Claim 1 to 10 in which a photosensitive composition contains a sensitizer.   The sensitizer is at least one selected from a condensed ring compound and an amine compound substituted with at least two aromatic hydrocarbon rings and aromatic heterocyclic rings. Permanent pattern forming method.   The permanent pattern forming method according to claim 8, wherein the support includes a synthetic resin and is transparent.   The permanent pattern forming method according to claim 8, wherein the support has a long shape.   The method for forming a permanent pattern according to claim 8, wherein the photosensitive film has a long shape and is wound into a roll.   The permanent pattern forming method according to claim 8, wherein the photosensitive film has a protective film on the photosensitive layer.   The permanent pattern forming method according to claim 1, wherein the photosensitive layer has a thickness of 3 to 100 μm.   The permanent pattern forming method according to claim 1, wherein the substrate is a printed wiring board on which wiring has been formed.   The method for forming a permanent pattern according to any one of claims 1 to 18, wherein the light irradiating means can synthesize and irradiate two or more lights.   The light irradiation means condenses the laser beams emitted from the plurality of lasers, the multimode optical fiber, and the lasers by collimating them, and converges them on the incident end face of the multimode optical fiber. The permanent pattern forming method according to claim 1, further comprising an optical system.   The permanent pattern formation method according to claim 20, wherein the wavelength of the laser beam is 395 to 415 nm.   The permanent pattern forming method according to claim 1, wherein after the development, the photosensitive layer is subjected to a curing process.   The permanent pattern forming method according to claim 22, wherein the curing process is at least one of a whole surface exposure process and a whole surface heat treatment performed at 120 to 200 ° C. The permanent pattern forming method according to claim 1, wherein at least one of a protective film and an interlayer insulating film is formed.