JP2007017814A - Pattern forming material, pattern forming apparatus, and permanent pattern forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pattern forming material excellent in exposure sensitivity, giving a good resist surface shape and capable of forming a higher-definition pattern, in order to form a permanent pattern such as a solder resist. <P>SOLUTION: The pattern forming material has at least a photosensitive layer obtained by using a photosensitive composition comprising at least a binder, a polymerizable compound, a photopolymerization initiator, a heat crosslinking agent and a dye having an acid nucleus as a sensitizer. When the photosensitive layer is exposed and developed, the minimum energy of light which is used in the exposure and does not vary the thickness of the photosensitive layer in its part to be exposed after the exposure and development is 0.1-100 mJ/cm<SP>2</SP>. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a pattern forming material suitable for forming a permanent pattern such as a protective film, an interlayer insulating film, and a solder resist, a pattern forming apparatus provided with the pattern forming material, and a permanent pattern forming method using the pattern forming material About.

  When a permanent pattern such as a wiring pattern is formed, a pattern forming material in which a photosensitive layer is formed by applying and drying a photosensitive resin composition on a support is used. As the method for producing the permanent pattern, for example, a laminate is formed by laminating the pattern forming material on a substrate such as a copper clad laminate on which the permanent pattern is formed, and the photosensitive layer in the laminate is formed. After the exposure, the photosensitive layer is developed to form a pattern, and then an etching process or the like is performed to form the permanent pattern.

On the other hand, in order to increase the transparency of the support, a pattern forming material for photoresist using a highly transparent substance having a haze value of 5.0% or less such as polyethylene terephthalate (PET) as a support is known. Yes.
For this type of pattern forming material, for example, the binder can be copolymerized with (meth) acrylic acid and (meth) acrylic acid alkyl ester, mainly for the purpose of improving sensitivity, resolution, adhesion, etc. A pattern forming material containing a copolymer obtained by copolymerizing a vinyl monomer (see Patent Document 1), a photosensitive layer with a predetermined amount of (a) a carboxyl group-containing polymer and (b) an ethylenically unsaturated compound , (C) a lophine dimer, (d) a photopolymerization initiator, (e) a pattern forming material containing a leuco dye (see Patent Document 2), (a) a carboxyl group-containing binder, (b) at least one in the molecule A photopolymerizable compound having two polymerizable ethylenically unsaturated groups, (c) a pattern-forming material containing a photopolymerization initiator (see Patent Document 3), and a photosensitive layer against ultraviolet rays having a wavelength of 365 nm. That transmittance, the pattern forming material (see Patent Document 4) have been proposed as 5 to 75%. In addition, as a support, the thickness is 10 μm or more and 25 μm or less, and the polycondensation metal catalyst residue is less than 150 ppm for the purpose of providing transparency, light transmittance, slipperiness, winding property, resolution, and recyclability. There is also proposed a support in which the antimony metal is 15 mmol% or less with respect to the total acid component (see Patent Document 5).
However, these pattern forming materials and the like are resists used for printed wiring, and are removed after the process is completed.

On the other hand, in a permanent pattern forming material such as a solder resist, proposals have been made in which a sensitizer such as a coumarin compound is added to the permanent pattern forming material for the purpose of improving exposure sensitivity (Patent Documents 6 to 6). 7).
However, in these cases, there is no disclosure about the haze value of the support or the transmittance for ultraviolet rays, and the function of the sensitizer is sufficiently exhibited by the light irradiated through the support. It was not possible to judge whether it was done or not.
Therefore, it is possible to improve the sensitivity of the photosensitive layer for the purpose of forming a permanent pattern such as a solder resist, and when the photosensitive layer is formed on the support, a highly transparent substance is used as the support. And a pattern forming material capable of sufficiently exerting the function of the high-sensitivity photosensitive layer by light irradiated through the support, and capable of forming a high-definition pattern, and the pattern forming material A pattern forming apparatus provided and a permanent pattern forming method using the pattern forming material have not been provided yet, and further improvements and developments are desired.
Japanese Patent No. 3425597 Japanese Patent No. 3100040 International Publication No. 00/79344 Pamphlet Japanese Patent Laid-Open No. 2001-13681 JP 2002-60598 A Japanese Patent No. 3295012 JP 2002-256063 A

  This invention is made | formed in view of this present condition, and makes it a subject to achieve the following objectives. That is, in the present invention, for the purpose of forming a permanent pattern such as a solder resist, by adding a dye having an acidic nucleus as a sensitizer to the photosensitive layer, the exposure sensitivity is excellent, the resist surface shape is good, and An object of the present invention is to provide a pattern forming material capable of forming a higher definition pattern, a pattern forming apparatus including the pattern forming material, and a permanent pattern forming method using the pattern forming material.

Means for solving the problems are as follows. That is,
<1> At least a photosensitive layer obtained using a photosensitive composition containing at least a binder, a polymerizable compound, a photopolymerization initiator, a thermal crosslinking agent, and a dye having an acidic nucleus as a sensitizer. And when the photosensitive layer is exposed and developed, the minimum energy of light used for the exposure that does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development is 0.1 to 100 mJ / cm ² is a pattern forming material.
<2> The pattern forming material according to <1>, wherein the dye having an acidic nucleus is a merocyanine dye.
<3> The pattern forming material according to any one of <1> to <2>, wherein the dye having an acidic nucleus is a rhodacyanine dye.
<4> The pattern forming material according to any one of <1> to <3>, wherein the dye having an acidic nucleus has a maximum absorption wavelength of 500 nm or less.
<5> The pattern formation according to any one of <1> to <4>, which has at least a support and a photosensitive layer on the support, and the haze value of the support is 5.0% or less. Material.
<6> The pattern forming material according to <5>, wherein the support has a total light transmittance of 86% or more.
<7> The pattern forming material according to any one of <5> to <6>, wherein the haze value of the support and the light wavelength when determining the total light transmittance of the support are 405 nm.
<8> The pattern forming material according to any one of <1> to <7>, wherein the binder exhibits either swellability or solubility in an alkaline aqueous solution.
<9> The pattern forming material according to any one of <1> to <8>, wherein the binder is an epoxy acrylate compound.
<10> The pattern forming material according to any one of <1> to <9>, wherein the binder is made of a vinyl copolymer having a (meth) acryloyl group and an acidic group in a side chain.
<11> The binder according to any one of <1> to <10>, wherein the binder includes 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. It is a pattern formation material of description.
<12> The epoxy acrylate compound is a saturated polybasic carboxylic acid, an unsaturated polybasic carboxylic acid, and any of a partial esterification reaction product and a total esterification reaction product of an epoxy resin compound and an unsaturated carboxylic acid, and The pattern forming material according to <9> to <11>, which is an unsaturated group-containing polycarboxylic acid resin obtained by reacting with any of these anhydrides.
<13> The epoxy resin compound is a novolak type epoxy compound, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a hydrogenated bisphenol A type epoxy compound, a brominated bisphenol A type epoxy compound, an amino group-containing epoxy compound, phenol, and Epoxy resin obtained by glycidyl etherification of one kind selected from cresol and p-hydroxybenzaldehyde condensate, bis (glycidyloxyphenyl) fluorene type epoxy resin, bis (glycidyloxyphenyl) adamantane type epoxy resin, alicyclic epoxy compound And the pattern forming material according to <12>, which is a mixture with at least one epoxy compound selected from glycidyl ether type epoxy compounds.
<14> The pattern forming material according to <12>, wherein the epoxy resin compound is a novolac epoxy compound.
<15> The pattern forming material according to any one of <13> to <14>, wherein the novolac epoxy compound is any one of a cresol novolac epoxy compound and a phenol novolac epoxy compound.
<16> From the above <1> to <8>, wherein the <16> 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 pattern forming material according to any one of the above.
<17> The binder is (a) maleic anhydride, (b) an aromatic vinyl monomer, (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. > And <16>.
<18> From the above <1>, 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. 18>. The pattern forming material according to any one of 18>.
<19> The pattern forming material according to <18>, wherein the thermal crosslinking agent is an alkylated methylol melamine. In the pattern forming material according to <19>, when a permanent pattern is formed using the pattern forming material by adding alkylated methylol melamine as the thermal crosslinking agent, the film strength of the cured film is improved. Figured.
<20> The pattern forming material according to <18>, wherein the thermal crosslinking agent is an epoxy compound including at least an epoxy group having an alkyl group at the β-position. In the pattern forming material according to <20>, by using an epoxy compound containing at least an epoxy group having an alkyl group at the β-position as the crosslinking agent, the storage stability of the previous pattern forming material is improved, and When a permanent pattern is formed using the pattern forming material, the strength of the cured film can be improved.
<21> The photopolymerization initiator is a halogenated hydrocarbon derivative, phosphine oxide, hexaarylbiimidazole, oxime derivative, organic peroxide, thio compound, ketone compound, acylphosphine oxide compound, aromatic onium salt, and ketoxime ether. The pattern forming material according to any one of <1> to <20>, including at least one selected from the group consisting of:
<22> After the photosensitive layer modulates the light from the light irradiation means by the light modulation means having n drawing parts for receiving and emitting the light from the light irradiation means, the emission surface in the drawing part The pattern forming material according to any one of <1> to <21>, wherein the pattern forming material is exposed to light that has passed through a microlens array in which microlenses having aspherical surfaces capable of correcting an aberration due to distortion of the lens are arranged.
In the pattern forming material according to <22>, the light irradiation unit irradiates light toward the light modulation unit. The n picture elements in the light irradiation means receive and emit light from the light irradiation means, thereby modulating the light received from the light irradiation means. The light modulated by the light modulation means passes through the aspherical surface in the microlens array, so that the aberration due to the distortion of the exit surface in the pixel portion is corrected, and the image formed on the photosensitive layer is distorted. It is suppressed. As a result, the photosensitive layer is exposed with high definition. Thereafter, when the photosensitive layer is developed, a high-definition permanent pattern is formed.
<23> The pattern forming material according to any one of <5> to <16>, wherein the support includes a synthetic resin and is transparent.
<24> The pattern forming material according to any one of <5> to <23>, wherein the support has a long shape.
<25> The pattern forming material according to any one of <1> to <24>, which is long and wound in a roll shape.
<26> The pattern forming material according to any one of <1> to <25>, wherein a protective film is provided on the photosensitive layer.
<27> The pattern forming material according to any one of <1> to <26>, wherein the photosensitive layer has a thickness of 3 to 100 μm.

<28> The pattern forming material according to any one of <1> to <27> is provided,
A pattern forming apparatus comprising at least light irradiating means capable of irradiating light, and light modulating means for modulating light from the light irradiating means and exposing the photosensitive layer in the pattern forming material. is there.
<29> The light modulation means further includes pattern signal generation means for generating a control signal based on the pattern information to be formed, and the control signal generated by the pattern signal generation means is emitted from the light irradiation means. It is a pattern formation apparatus as described in said <28> modulated according to.
In the pattern forming apparatus according to <29>, since the light modulation unit includes the pattern signal generation unit, light emitted from the light irradiation unit corresponds to a control signal generated by the pattern signal generation unit. Modulated.
<30> The light modulation means has n pixel parts, and forms any less than n pixel parts continuously arranged from the n pixel parts. The pattern forming apparatus according to any one of <28> to <29>, which can be controlled according to pattern information.
In the pattern forming apparatus according to <30>, an arbitrary less than n pixel portions arranged continuously from n pixel portions in the light modulation unit are controlled according to pattern information. Thereby, the light from the light irradiation means is modulated at high speed.
<31> The pattern forming apparatus according to any one of <28> to <30>, wherein the light modulation unit is a spatial light modulation element.
<32> The pattern forming apparatus according to <31>, wherein the spatial light modulation element is a digital micromirror device (DMD).
<33> The pattern forming apparatus according to any one of <30> to <32>, wherein the picture element portion is a micromirror.
<34> The pattern forming apparatus according to any one of <28> to <33>, wherein the light irradiation unit is capable of combining and irradiating two or more lights.
In the pattern forming apparatus according to <34>, since the light irradiation unit can synthesize and irradiate two or more lights, exposure is performed with exposure light having a deep focal depth. As a result, the pattern forming material is exposed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.
<35> The light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that condenses the laser beams irradiated from the plurality of lasers and couples the laser beams to the multimode optical fiber. The pattern forming apparatus according to any one of <28> to <34>.
In the pattern forming apparatus according to <35>, the light irradiation unit can condense the laser beams emitted from the plurality of lasers by the collective optical system and couple the laser beams to the multimode optical fiber. Thus, exposure is performed with exposure light having a deep focal depth. As a result, the pattern forming material is exposed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.

<36> A permanent pattern forming method comprising at least exposing the photosensitive layer in the pattern forming material according to any one of <1> to <27>.
<37> The pattern forming method according to <36>, wherein the pattern forming material photosensitive composition according to any one of <1> to <27> is applied on a substrate and dried. It is.
<38> The permanent material according to <36>, wherein the pattern forming material according to any one of <1> to <27> is laminated and exposed on at least one of heating and pressurization on a substrate. This is a pattern forming method.
<39> The permanent pattern forming method according to any one of <37> to <38>, wherein the base material is a printed circuit board on which wiring is formed.
<40> The permanent pattern forming method according to any one of <36> to <39>, wherein the exposure is performed imagewise based on pattern information to be formed.
<41> The permanent pattern according to any one of <36> to <40>, wherein the exposure is performed using light that is generated based on pattern information to be formed and modulated according to the control signal. It is a forming method.
<42> From <36> to <41, wherein the exposure is performed using light irradiation means for irradiating light and light modulation means for modulating light emitted from the light irradiation means based on pattern information to be formed. The permanent pattern forming method according to any one of the above.
<43> The light modulation unit further includes a pattern signal generation unit that generates a control signal based on pattern information to be formed, and the pattern signal generation unit generates light emitted from the light irradiation unit. The method for forming a permanent pattern according to <42>, wherein modulation is performed according to a signal.
<44> The light modulation means has n pixel parts, and forms any less than n pixel elements arranged continuously from the n pixel parts. The permanent pattern forming method according to any one of <42> to <43>, which is controllable according to pattern information.
In the method for forming a permanent pattern according to <44>, any less than n pixel portions arranged continuously from n pixel portions in the light modulation means are controlled according to pattern information. By doing so, the light from the light irradiation means is modulated at high speed.
<45> The permanent pattern forming method according to any one of <42> to <44>, wherein the light modulation unit is a spatial light modulation element.
<46> The method for forming a permanent pattern according to <45>, wherein the spatial light modulation element is a digital micromirror device (DMD).
<47> The permanent pattern forming method according to any one of <44> to <46>, wherein the picture element portion is a micromirror.
<48> Exposure is performed through a microlens array in which microlenses having aspherical surfaces capable of correcting aberrations due to distortion of the exit surface of the picture element portion in the light modulation means after the light is modulated by the light modulation means. The method for forming a permanent pattern according to any one of <44> to <47>.
<49> The method for forming a permanent pattern according to <48>, wherein the aspherical surface is a toric surface.
In the method for forming a permanent pattern according to <49>, since the aspherical surface is a toric surface, aberration due to distortion of the radiation surface in the pixel portion is efficiently corrected, and an image is formed on the photosensitive layer. Image distortion is efficiently suppressed. As a result, the photosensitive layer is exposed with high definition. Thereafter, the photosensitive layer is developed to form a high-definition permanent pattern.
<50> The method for forming a permanent pattern according to any one of <36> to <49>, wherein the exposure is performed through an aperture array.
In the method for forming a permanent pattern according to <50>, the extinction ratio is improved by performing exposure through the aperture array. As a result, the exposure is performed with extremely high definition. Thereafter, the photosensitive layer is developed to form a very fine permanent pattern.
<51> The method for forming a permanent pattern according to any one of <36> to <50>, wherein the exposure is performed while relatively moving the exposure light and the photosensitive layer.
In the method for forming a permanent pattern according to <51>, exposure is performed at a high speed by performing exposure while relatively moving the modulated light and the photosensitive layer.
<52> The method for forming a permanent pattern according to any one of <36> to <51>, wherein the exposure is performed on a partial region of the photosensitive layer.
<53> The method for forming a permanent pattern according to any one of <42> to <52>, wherein the light irradiation unit can synthesize and irradiate two or more lights.
In the method for forming a permanent pattern according to <53>, since the light irradiation unit can synthesize and irradiate two or more lights, exposure is performed with exposure light having a deep focal depth. As a result, the exposure of the photosensitive layer is performed with extremely high definition. Thereafter, the photosensitive layer is developed to form a very fine permanent pattern.
<54> The above-mentioned <42, wherein the light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that collects laser beams irradiated from the plurality of lasers and couples the laser beams to the multimode optical fiber. > To <53>.
In the permanent pattern forming method according to <54>, the laser light emitted from each of the plurality of lasers is condensed by the collective optical system by the light irradiating means, and can be coupled to the multimode optical fiber. Thus, exposure is performed with exposure light having a deep focal depth. As a result, the exposure of the photosensitive layer is performed with extremely high definition. Thereafter, the photosensitive layer is developed to form a very fine permanent pattern.
<55> The permanent pattern forming method according to any one of <36> to <54>, wherein the exposure is performed using a laser beam having a wavelength of 350 to 415 nm.
<56> The permanent pattern forming method according to any one of <36> to <55>, wherein the photosensitive layer is developed after the exposure.
<57> The method for forming a permanent pattern according to any one of <36> to <56>, wherein after the development, the photosensitive layer is subjected to a curing treatment.
In the method for forming a permanent pattern described in <57>, after the development, the curing treatment is performed on the photosensitive layer. As a result, the film strength of the cured region of the photosensitive layer is increased.
<58> The method for forming a permanent pattern according to <57>, 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.
In the permanent pattern forming method according to <58>, curing of the resin in the pattern forming material is promoted in the entire surface exposure process. Moreover, the film | membrane intensity | strength of a cured film is raised in the whole surface heat processing performed on the said temperature conditions.
<59> The permanent pattern formation method according to any one of <36> to <58>, wherein at least one of a protective film, an interlayer insulating film, and a solder resist pattern is formed.
In the permanent pattern forming method according to <59>, since at least one of a protective film, an interlayer insulating film, and a solder resist pattern is formed, the wiring from the outside depends on the insulating property, heat resistance, etc. of the film. Protected from impact and bending.
<60> A permanent pattern formed by the method for forming a permanent pattern according to any one of <36> to <59>.
Since the permanent pattern according to <60> is formed by the permanent pattern forming method, it has excellent chemical resistance, surface hardness, heat resistance, and the like, and has high definition and multilayer wiring of semiconductors and components. This is useful for high-density mounting on boards and build-up wiring boards.
<61> The permanent pattern according to <60>, which is at least one of a protective film, an interlayer insulating film, and a solder resist pattern.
Since the permanent pattern according to <61> is at least one of a protective film, an interlayer insulating film, and a solder resist pattern, due to the insulating property, heat resistance, etc. of the film, the wiring may be subjected to external impact or bending. Protected from.

  According to the present invention, the conventional problems can be solved, and for the purpose of forming a permanent pattern such as a solder resist, the photosensitive layer is excellent in exposure sensitivity by containing a dye having an acidic nucleus as a sensitizer. There are provided a pattern forming material having a good resist surface shape and capable of forming a higher definition pattern, a pattern forming apparatus provided with the pattern forming material, and a permanent pattern forming method using the pattern forming material. Can do.

(Pattern forming material)
The pattern forming material of the present invention is obtained by using a photosensitive composition containing at least a binder, a polymerizable compound, a photopolymerization initiator, a thermal crosslinking agent, and a dye having an acidic nucleus as a sensitizer. In the case where the photosensitive layer is exposed and developed, the thickness of the exposed portion of the photosensitive layer is not changed after the exposure and development. 1 to 100 mJ / cm ² .
Further, the pattern forming material of the present invention may have at least a support and a photosensitive layer on the support.
The pattern forming material is used in a pattern forming method to be described later. The pattern forming method is performed by applying a photosensitive composition of the pattern forming material onto a substrate and drying, or by supporting the support. This is done by laminating the photosensitive layer formed on the substrate.
When the photosensitive layer is exposed and developed, the minimum energy of light that does not change the thickness of the exposed portion of the photosensitive layer before and after the exposure and development is 0.1 to 100 mJ / cm ^2. There is no particular limitation and can be appropriately selected according to the purpose. For example, 0.5 to 70 mJ / cm ² is preferable, 1 to 50 mJ / cm ² is more preferable, and 1.5 to 30 mJ / cm ² is preferable. Particularly preferred.
The minimum energy is less than 0.1 mJ / cm ^2, may fogging in process step occurs, it exceeds 100 mJ / cm ^2, increases the time necessary for exposure, processing speed is slow Sometimes.

Here, “the minimum energy of light used for the exposure that does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development” is so-called development sensitivity, for example, when the photosensitive layer is exposed. It can be determined from a graph (sensitivity curve) showing the relationship between the amount of light energy (exposure amount) used for the exposure and the thickness of the cured layer generated by the development process following the exposure.
The thickness of the cured layer increases as the amount of exposure increases, and then becomes substantially the same and substantially constant as the thickness of the photosensitive layer before the exposure. The development sensitivity is a value obtained by reading the minimum exposure when the thickness of the cured layer becomes substantially constant.
Here, when the difference between the thickness of the cured layer and the thickness of the photosensitive layer before the exposure is within ± 1 μm, it is considered that the thickness of the cured layer is not changed by exposure and development.
A method for measuring the thickness of the cured layer and the photosensitive layer before exposure is not particularly limited and may be appropriately selected depending on the intended purpose. However, a film thickness measuring device, a surface roughness measuring machine (for example, Surfcom) 1400D (manufactured by Tokyo Seimitsu Co., Ltd.)) and the like.

<Support>
The support is not particularly limited as long as it has a haze value of 5.0% or less, and can be appropriately selected depending on the purpose. It is more preferable that the surface is smooth.

-Haze value-
The haze value of the support is required to be 5.0% or less with respect to 405 nm light, preferably 3.0% or less, and more preferably 1.0% or less. . When the haze value exceeds 5.0%, the amount of light scattering in the photosensitive layer increases, and the resolution when obtaining a fine pitch may be lowered.

  Moreover, it is preferable that the total light transmittance with respect to 405 nm light of the said support body is 86% or more, and it is more preferable that it is 87% or more.

There is no restriction | limiting in particular as a measuring method of the said haze value and total light transmittance, Although it can select suitably according to the objective, For example, the method demonstrated below is mentioned.
First, (1) the total light transmittance is measured. The method for measuring the total light transmittance is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an integrating sphere and a spectrophotometer capable of irradiating 405 nm light (for example, Shimadzu Corporation) And UV-2400). (2) In the total light transmittance measurement method, the parallel light transmittance is measured in the same manner as the total light transmittance measurement method except that the integrating sphere is not used. Next, the diffuse light transmittance calculated from (3) the following calculation formula, the total light transmittance-the parallel light transmittance, is calculated, and (4) the following calculation formula, the diffuse light transmittance / the total light transmission. The haze value can be obtained from the rate × 100.
In addition, the thickness of the measurement sample at the time of calculating | requiring the said total light transmittance and the said haze value is 16 micrometers.

  The support may be coated with inert fine particles on at least one side. The inert fine particles are preferably applied on the surface opposite to the surface on which the photosensitive layer is formed.

  Examples of the inert fine particles include crosslinked polymer particles, inorganic particles (for example, calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, etc. ), Organic particles (for example, hexamethylene bisbehenamide, hexamethylene bisstearyl amide, N, N'-distearyl terephthalamide, silicone, calcium oxalate, etc.), precipitated particles formed during polyester polymerization, etc. Of these, silica, calcium carbonate, and hexamethylene bisbehenamide are preferable.

  The precipitated particles are, for example, particles precipitated in a reaction system by polymerizing a system using an alkali metal or alkaline earth metal compound as a transesterification catalyst by a conventional method, and during the transesterification reaction or polycondensation reaction It may be precipitated by adding terephthalic acid. In the transesterification or polycondensation reaction, phosphoric acid, trimethyl phosphate, triethyl phosphate, tributyl phosphate, acidic ethyl phosphate, phosphorous acid, trimethyl phosphite, triethyl phosphite, tributyl phosphite, etc. One or more of the phosphorus compounds may be present.

The average particle diameter of the inert fine particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, still more preferably 0.03 to 1.0 μm, and 0.04 to 0.5 μm. Is particularly preferred.
When the average particle diameter of the inert fine particles is less than 0.01 μm, the transportability of the pattern forming material may be deteriorated, and by containing a large amount of the inert fine particles in order to obtain transportability, The haze value of the support may increase. On the other hand, when the average particle diameter of the inert fine particles exceeds 2.0 μm, the resolution may be lowered due to scattering of exposure light.

  There is no restriction | limiting in particular as a coating method of the said inert fine particle, According to the objective, it can select suitably. For example, a method of applying a coating solution containing the inert fine particles by a known method after the production of the synthetic resin film as the support is mentioned. Alternatively, the synthetic resin containing the inert fine particles may be melted and discharged from a die to be formed on a synthetic resin film serving as the support. Furthermore, you may form by the method as described in Unexamined-Japanese-Patent No. 2000-221688.

  The thickness of the coating layer containing the inert fine particles in the support is preferably 0.02 to 3.0 μm, more preferably 0.03 to 2.0 μm, and particularly preferably 0.04 to 1.0 μm.

  The synthetic resin film used as the support is preferably transparent. For example, a polyester resin film is preferable, and a biaxially stretched polyester film is particularly preferable.

  Examples of the polyester resin include polyethylene terephthalate, polyethylene naphthalate, poly (meth) acrylic acid ester copolymer, poly (meth) acrylic acid alkyl ester, polyethylene-2,6-naphthalate, polytetramethylene terephthalate, and polytetramethylene. And methylene-2,6-naphthalate. These may be used alone or in combination of two or more.

  Examples of the resin other than the polyester resin include polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride, Examples include vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoroethylene, cellulose resin, and nylon resin. These may be used alone or in combination of two or more.

  The synthetic resin film may be composed of one layer or may be composed of two or more layers. In the case of two or more layers, the inert fine particles are preferably contained in the layer farthest from the photosensitive layer.

The synthetic resin film is preferably a biaxially stretched polyester film from the viewpoint of mechanical strength characteristics and optical characteristics.
There is no restriction | limiting in particular in the biaxial orientation method of the said biaxially stretched polyester film, According to the objective, it can select suitably. For example, the polyester resin is melt-extruded into a sheet and rapidly cooled to form an unstretched film. When the unstretched film is biaxially stretched, the stretching temperature is 85 to 145 ° C., and the stretching ratio in the longitudinal and transverse directions is 2. It can be prepared by heat-fixing the film after biaxial stretching as necessary at a temperature of from 0.6 to 4.0 times at 150 to 210 ° C.
The biaxial stretching may be a sequential biaxial stretching method in which an unstretched film is stretched in the longitudinal direction or the transverse direction to form a uniaxially stretched film, and then the uniaxially stretched film is stretched in the transverse direction or the longitudinal direction. A simultaneous biaxial stretching method in which the unstretched film is stretched simultaneously in the machine direction and the transverse direction may be used. The biaxially stretched film can be further stretched in at least one of the longitudinal direction and the transverse direction as necessary.

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

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

<Photosensitive layer>
The photosensitive layer is obtained using a photosensitive composition containing at least a binder, a polymerizable compound, a photopolymerization initiator, a thermal cross-linking agent, and a dye having an acidic nucleus as a sensitizer. Other components appropriately selected according to the conditions may be included.

-Binder-
As the binder, for example, it is preferably swellable to an alkaline aqueous solution, and more preferably soluble to an alkaline aqueous solution. Moreover, it is also preferable to contain a polymerizable group in the binder.
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 51-131706, JP-A 52-94388, JP-A 64-62375, JP-A 2 Examples thereof include epoxy acrylate compounds having acidic groups described in JP-A-97513, JP-A-3-289656, JP-A-61-2243869, JP-A-2002-296776, and the like. Other binders include a vinyl copolymer having a (meth) acryloyl group and an acidic group in the side chain, a vinyl copolymer having an epoxy acrylate compound and a (meth) acryloyl group and an acidic group in the side chain, and And a maleic anhydride copolymer of the above combination.

<Epoxy acrylate compound>
The epoxy acrylate compound of the present invention 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, for example, by 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, Dibasic acid anhydrides such as hydrochlorendic acid and 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.

  Also, 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 be used as the epoxy acrylate of the present invention.

  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.

<Other binders>
An acrylic resin having at least one polymerizable group such as an acidic group and 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.
As the other 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) 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 monomer, if necessary. (4) Synthesizing a polymer, and (4) (meth) acryloyl and a functional group reactive to at least one of an acidic group in the (co) polymer or a functional group available for polymer reaction It is obtained by polymer reaction with a compound having a group.
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).

However, in the structural formulas (1) to (9), R ¹ represents a hydrogen atom or a methyl group, and n, n1, and n2 represent 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 the above structural formula (10) ~ (12), R 1 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 H or Me.

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 other 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.” and the like 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.

<Maleic anhydride copolymer>
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.

In the Structural Formula (14), R ³ and R ⁴ represents 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 ¹ , for example, (—COOR ¹⁰ ), (—CONR ¹¹ R ¹² ), an aryl group which may have a substituent, (—OCOR ¹³ ), (—OR ¹⁴ ), substituents such as (—COR ¹⁵ ). Here, said R < ¹⁰ > -R < ¹⁵ > represents either a hydrogen atom (-H), the alkyl group which may have a substituent, an aryl group, and an aralkyl group. The alkyl group, aryl group and aralkyl group may have a cyclic structure or a branched structure.
Examples of R ^{10 to} R ¹⁵ 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 ¹ 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 ² 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 ² 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) Til, 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 pattern forming material of the present invention can be increased. In this respect, 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 the said pattern formation material solid content 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-
The polymerizable compound is not particularly limited and may be appropriately selected depending on the intended purpose. However, the polymerizable compound has at least one addition-polymerizable group in the molecule and has a boiling point of 100 ° C. or higher at normal pressure. A compound is preferable, for example, at least 1 sort (s) selected from the monomer which has a (meth) acryl group is mentioned suitably.

  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, monofunctional acrylate and monofunctional methacrylate (for example, polyethylene glycol mono (meth) acrylate, polypropylene glycol) Mono (meth) acrylate, phenoxyethyl (meth) acrylate, etc.), polyfunctional alcohol, and (meth) acrylated after addition reaction of ethylene oxide or propylene oxide (eg, polyethylene glycol di (meth) acrylate, polypropylene) Glycol di (meth) acrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, trimethylol propane diacrylate, neopentyl glycol 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 (acryloyl) Oxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate, trimethylolpropane, glycerin, bisphenol, etc.), urethane acrylates (for example, Japanese Patent Publication No. 48-41708) , JP-B-50-6034, JP-A-51-37193, etc.), polyester acrylates (for example, JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, etc.), polyfunctional acrylates and methacrylates (for example, epoxy resins and (meth) acrylic acid) Epoxy acrylates and the like, which are reaction products of 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 pattern formation material 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.

-Photopolymerization initiator-
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, it is visible from the ultraviolet region. Those having photosensitivity to the light of the above are preferred, and may be an activator that generates an active radical by causing some action with a photoexcited hetero-fused compound or sensitizer, depending on the type of monomer. It may be an initiator that initiates cationic polymerization.
The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a range of about 300 to 800 nm (more preferably 330 to 500 nm).

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

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

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

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

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

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

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

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

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

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

  Examples of the oxime derivative suitably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, and 2-acetoxy. Iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2- ON, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.

  Further, as other photopolymerization initiators, acylphosphine oxides are used. For example, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4 , 4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO and the like.

  Further, as photopolymerization initiators other than the above, N-phenylglycine and other polyhalogen compounds (for example, carbon tetrabromide, phenyltribromomethylsulfone, phenyltrichloromethyl ketone, etc.), amines (for example, 4-dimethylamino) Ethyl benzoate, n-butyl 4-dimethylaminobenzoate, phenethyl 4-dimethylaminobenzoate, 2-phthalimidoethyl 4-dimethylaminobenzoate, 2-methacryloyloxyethyl 4-dimethylaminobenzoate, pentamethylenebis (4 -Dimethylaminobenzoate), phenethyl of 3-dimethylaminobenzoic acid, pentamethylene ester, 4-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylaminobenzyl alcohol, ethyl (4-di- Tilaminobenzoyl) acetate, 4-piperidinoacetophenone, 4-dimethylaminobenzoin, N, N-dimethyl-4-toluidine, N, N-diethyl-3-phenetidine, tribenzylamine, dibenzylphenylamine, N- Methyl-N-phenylbenzylamine, 4-bromo-N, N-dimethylaniline, tridodecylamine, crystal violet lactone, leuco crystal violet, etc.), metallocenes (for example, bis (η5-2,4-cyclopentadiene-1) -Yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1- ), Etc.), JP-A-53-133428, Shoko Examples thereof include compounds described in 57-1819, 57-6096, and US Pat. No. 3,615,455.

  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, fluorenone, 2-benzyl-dimethyl Amino-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, benzoin propyl ether, benzoin isopropyl ether, benzoin phenyl ether, Le dimethyl ketal), and the like.

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 pattern formation material of the said photoinitiator, 0.1-30 mass% is preferable, 0.5-20 mass% is more preferable, 0.5-15 mass% is especially preferable.

-Pigment with acid nucleus (sensitizer)-
As the dye having an acidic nucleus, the thickness of the exposed portion of the photosensitive layer for the purpose of adjusting the exposure sensitivity and the photosensitive wavelength in exposure to the photosensitive layer described later, or when the photosensitive layer is exposed and developed. Is added from the viewpoint of improving the minimum energy (sensitivity) of the light that does not change before and after the development. For example, the sensitivity of the photosensitive layer can be very easily adjusted to 0.1 to 100 mJ / cm ² by using the dye having an acidic nucleus together.

If it is the pigment | dye which has the said acidic nucleus, there will be no restriction | limiting in particular, According to the said light irradiation means (for example, visible light, ultraviolet light, visible light laser, etc.), it can select suitably.
When combined with a laser having a wavelength of 350 to 415 nm as the light irradiation means, the maximum absorption wavelength of the dye having an acidic nucleus is preferably 500 nm or less, more preferably 480 nm or less, and particularly preferably 450 nm or less. .
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 dye having an acidic nucleus include merocyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes, rhodacyanine dyes, and oxonol dyes. Among these, merocyanine dyes and rhodacyanine dyes are preferable, and merocyanine dyes are more preferable. preferable.

Examples of the acidic nucleus include, for example, “The Theory of the Photographic Process” edited by James, 4th edition, Macmillan Publishing Co., Ltd., 1977, Chapter 8, “The Theory of the Photographic Process”. Sensitizing dyes and desensitizing dyes ", U.S. Pat. Nos. 3,567,719, 3,575,869, 3,804,634, 3,837,862, 4,002. No. 4,480, No. 4,925,777, JP-A-3-167546, and the like.
When the acidic nucleus is acyclic, the end of the methine bond is malononitrile, alkanesulfonylacetonitrile, cyanomethylbenzofuranyl ketone, cyanomethylphenyl ketone, malonic acid ester, acylaminomethyl-substituted ketones, etc. A group such as an active methylene compound is preferred.
5- or 6-membered nitrogen containing carbon, nitrogen, and chalcogen (typically oxygen, sulfur, selenium, and tellurium) atoms when the atomic group necessary to form the acidic nucleus is cyclic A heterocyclic ring is preferably formed. Examples of the nitrogen-containing heterocyclic ring include 2-pyrazolin-5-one, pyrazolidine-3, 5-dione, imidazolin-5-one, hydantoin, 2-thiohydantoin, 4 -Thiohydantoin, 2-iminooxazolidine-4-one, 2-oxazolin-5-one, 2-thiooxazoline-2, 4-dione, isoxazolin-5-one, 2-thiazoline-4-one, thiazolidine-4 -One, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, isorhodanine, indan-1,3-dione, thiof 3-one, thiophen-3-one-1,1-dioxide, indoline-2-one, indoline-3-one, 2-oxoindazolinium, 3-oxoindazolinium, 5,7-dioxo- 6,7-dihydrothiazolo [3,2-a] pyrimidine, cyclohexane-1,3-dione, 3,4-dihydroisoquinolin-4-one, 1,3-dioxane-4,6-dione, barbituric acid 2-thiobarbituric acid, chroman-2,4-dione, indazolin-2-one, pyrido [1,2-a] pyrimidine-1,3-dione, pyrazolo [1,5-b] quinazolone, pyrazolo [ 1,5-a] benzimidazole, pyrazolopyridone, 1,2,3,4-tetrahydroquinoline-2,4-dione, 3-oxo-2,3-dihydrobenzo [d] thiophene Examples include -1,1-dioxide, 3-dicyanomethine-2,3-dihydrobenzo [d] thiophene-1,1-dioxide nucleus.

  Examples of the acidic nucleus include the acidic heterocycles shown below.

Here, R represents a hydrogen atom, an aliphatic group, or an aromatic group.

  Specific examples of the dye having an acidic nucleus include compounds represented by the following structural formulas (15) to (22).

In the structural formula (15), L _{1 to} L ₄ represent a methine group. p ₁ represents 0 or 1. n ₁ represents 0, ₁ , 2, 3 or 4. Z ₁ and Z ₂ represent an atomic group necessary for forming a nitrogen-containing heterocycle. However, these rings may be condensed. The ring may be either an aromatic ring or a non-aromatic ring. An aromatic ring is preferred, and examples thereof include hydrocarbon aromatic rings such as benzene ring and naphthalene ring, and heteroaromatic rings such as pyrazine ring and thiophene ring.
R ₁ and R ₂ represent an alkyl group, an aryl group, or a heterocyclic group.
M ₁ represents a counter ion for charge balance, and m ₁ represents a number of 0 or more necessary for neutralizing the charge of the molecule.
However, R ₁ , R ₂ , Z ₁ , Z ₂ , L _{1 to} L ₄ have a cationic substituent when the structural formula (15) is a cationic dye, and the structural formula (15) is a betaine dye. In this case, it has one cationic substituent and one anionic substituent, and when the structural formula (15) is a nonionic dye, it does not have a cationic substituent and an anionic substituent.
The cationic dye may be any dye as long as the charge of the dye excluding the counter ion is cationic, but is preferably a dye having no anionic substituent. The anionic dye may be any dye as long as the charge of the dye excluding the counter ion is anionic, but is preferably a dye having one or more anionic substituents. The betaine dye is a dye that has a charge in the molecule but forms an inner salt, and the molecule does not have a charge as a whole. The nonionic dye is a dye having no charge in the molecule.
The anionic substituent is a substituent having a negative charge, for example, a proton dissociable acidic group dissociated by 90% or more between pH 5-8. Specifically, for example, sulfo group, carboxyl group, sulfato group, phosphoric acid group, boric acid group, alkylsulfonylcarbamoylalkyl group (for example, methanesulfonylcarbamoylmethyl group), acylcarbamoylalkyl group (for example, acetylcarbamoylmethyl group), acylsulfuric group. Examples include a famoylalkyl group (for example, acetylsulfamoylmethyl group) and an alkylsulfonylsulfamoylalkyl group (for example, methanesulfonylsulfamoylmethyl group). More preferred are a sulfo group and a carboxyl group. Particularly preferred is a sulfo group.
Examples of the cationic substituent include a substituted or unsubstituted ammonium group and a pyridinium group.
When the compound of the structural formula (15) is used alone, R ₁ is preferably a group having an aromatic ring.

In the structural formula _(16), L 5 ~L ₈ each represents a methine group. p ₂ represents 0 or 1. n ₂ represents 0, 1, ₂ , 3 or 4. Z ₃ and Z ₄ represent an atomic group necessary for forming a nitrogen-containing heterocycle. However, these rings may be condensed. The ring may be either an aromatic ring or a non-aromatic ring. An aromatic ring is preferred, and examples thereof include hydrocarbon aromatic rings such as benzene ring and naphthalene ring, and heteroaromatic rings such as pyrazine ring and thiophene ring.
R ₃ and R ₄ represent an alkyl group, an aryl group, or a heterocyclic group.
M ₂ represents a counter ion for charge balance, and m ₂ represents a number of 0 or more necessary for neutralizing the charge of the molecule.
However, at least one of R ₃ and R ₄ has an anionic substituent.

The structural formulas (15) and (16) will be described in more detail.
Examples of the nitrogen-containing heterocycle include a thiazoline nucleus, a thiazole nucleus, a benzothiazole nucleus, an oxazoline nucleus, an oxazole nucleus, a benzoxazole nucleus, a selenazoline nucleus, a selenazole nucleus, a benzoselenazole nucleus, and a 3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenine), imidazoline nucleus, imidazole nucleus, benzimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus, 3-isoquinoline Nuclei, imidazo [4,5-b] quinoxaline nuclei, oxadiazole nuclei, thiadiazole nuclei, tetrazole nuclei, pyrimidine nuclei, and the like. Preferred are benzothiazole nuclei, benzoxazole nuclei, and 3,3-dialkylindo. Renin nucleus (eg 3,3-dimethylindolenine) Benzimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus, and 3-isoquinoline nucleus, benzothiazole nucleus, benzoxazole nucleus, 3, 3 -Dialkylindolenin nucleus (for example, 3,3-dimethylindolenine) and benzimidazole nucleus are preferred, benzoxazole nucleus, benzothiazole nucleus and benzimidazole nucleus are more preferred, benzoxazole nucleus and benzothiazole nucleus are particularly preferred .

When the substituent on the nitrogen-containing heterocyclic ring is V, the substituent represented by V is not particularly limited. For example, a halogen atom (for example, chlorine, bromine, iodine, fluorine), a mercapto group, a cyano group, a carboxy group, and the like. Group, phosphate group, sulfo group, hydroxy group, carbamoyl group (for example, methylcarbamoyl, ethylcarbamoyl, morpholinocarbonyl), sulfamoyl group (for example, methylsulfamoyl, ethylsulfamoyl, piperidinosulfonyl), nitro group, alkoxy Groups (eg methoxy, ethoxy, 2-methoxyethoxy, 2-phenylethoxy), aryloxy groups (eg phenoxy, p-methylphenoxy, p-chlorophenoxy, naphthoxy), acyl groups (eg acetyl, benzoyl, trichloroacetyl), An acyloxy group (e.g. Tiloxy, benzoyloxy), acylamino groups (eg acetylamino), sulfonyl groups (eg methanesulfonyl, ethanesulfonyl, benzenesulfonyl), sulfinyl groups (eg methanesulfinyl, ethanesulfinyl, benzenesulfinyl), sulfonylamino groups (eg methanesulfonylamino) , Ethanesulfonylamino, benzenesulfonylamino), amino group, substituted amino group (eg, methylamino, dimethylamino, benzylamino, anilino, diphenylamino), ammonium group (eg, trimethylammonium, triethylammonium), hydrazino group (eg, trimethylhydra) Dino group), ureido group (eg ureido group, N, N-dimethylureido group), imide group (eg succinimide group), alkyl Thio group (for example, methylthio, ethylthio, propylthio), arylthio group (for example, phenylthio, p-methylphenylthio, p-chlorophenylthio, 2-pyridylthio, naphthylthio), alkoxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl, 2-benzyloxy) Carbonyl), aryloxycarbonyl groups (eg phenoxycarbonyl), unsubstituted alkyl groups (eg methyl, ethyl, propyl, butyl), substituted alkyl groups (eg hydroxymethyl, trifluoromethyl, benzyl, carboxyethyl, ethoxycarbonylmethyl, acetyl) Aminomethyl, and also here an unsaturated hydrocarbon group having 2 to 18 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 5 carbon atoms (eg vinyl group, ethynyl group 1-cyclyl). Lohexenyl group, benzylidine group, benzylidene group) are also included in the substituted alkyl group}, a substituted or unsubstituted aryl group (for example, phenyl, naphthyl, p-carboxyphenyl, p-nitrophenyl, 3,5-dichlorophenyl, p-cyanophenyl, m-fluorophenyl, p-tolyl), and substituted or unsubstituted heterocyclic groups (for example, pyridyl, 5-methylpyridyl, thienyl, furyl, morpholino, tetrahydrofurfuryl), etc. Among these, an alkyl group, an aryl group, an alkoxy group, a halogen atom, aromatic ring condensation, a sulfo group, a carboxy group, and a hydroxy group are preferable.
In addition, a structure in which a ring (an aromatic or non-aromatic hydrocarbon ring or a heterocyclic ring such as a benzene ring, a naphthalene ring, an anthracene ring, or a quinoline ring) is condensed can also be used.
On the substituent represented by V, the V may be further substituted.

As the substituent V on Z _{1 in the} structural formula (15) and Z _{3 in the} structural formula (16), an aromatic group or aromatic ring condensation is preferable.
Examples of the aromatic group include a hydrocarbon aromatic group and a heteroaromatic group. These are groups having a polycyclic condensed ring structure in which a hydrocarbon aromatic ring and a polycyclic condensed ring obtained by condensing heteroaromatic rings, or a combination of an aromatic hydrocarbon ring and an aromatic heterocyclic ring. It may be substituted with the substituent V or the like. The aromatic ring contained in the aromatic group includes benzene, naphthalene, anthracene, phenanthrene, fluorene, triphenylene, naphthacene, biphenyl, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine , Indole, benzofuran, benzothiophene, isobenzofuran, quinolidine, quinoline, phthalazine, naphthyridine, quinoxaline, quinoxazoline, quinoline, carbazole, phenanthridine, acridine, phenanthroline, thianthrene, chromene, xanthene, phenoxathiin, phenothiazine, phenazine, etc. Can be mentioned.

Z _{2 in the} structural formula (15) and Z _{4 in the} structural formula (16) represent an atomic group necessary for forming an acidic nucleus, for example, hydantoin, 2-thiohydantoin, 4-thiohydantoin, 2-oxazoline-5-one, 2-thiooxazoline-2,4-dione, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, barbituric acid, and 2-thiobarbituric acid Preferred are hydantoin, 2-thiohydantoin, 4-thiohydantoin, 2-oxazolin-5-one, rhodanine, barbituric acid, and 2-thiobarbituric acid, and 2-thiohydantoin, 4-thio More preferred are hydantoin, 2-oxazolin-5-one, rhodanine, and barbituric acid.

R ₁ and R _{2 in} the structural formula (15) and R ₃ and R _{4 in} the structural formula (16) are an alkyl group, an aryl group, and a heterocyclic group. Specifically, for example, carbon An unsubstituted alkyl group of atoms 1 to 18 (preferably 1 to 7, particularly preferably 1 to 4) (eg methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), carbon atom 1 To 18 (preferably 1 to 7, particularly preferably 1 to 4) substituted alkyl groups {for example, an alkyl group substituted with V as a substituent. Preferably, an aralkyl group (for example, benzyl, 2-phenylethyl), an unsaturated hydrocarbon group (for example, allyl group), a hydroxyalkyl group (for example, 2-hydroxyethyl, 3-hydroxypropyl), a carboxyalkyl group (for example, carboxymethyl) , 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl), an alkoxyalkyl group (for example, 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl), an aryloxyalkyl group (for example, 2-phenoxyethyl, 2- (1-naphthoxy) ethyl), alkoxycarbonylalkyl group (eg ethoxycarbonylmethyl, 2-benzyloxycarbonylethyl), aryloxycarbonylalkyl group (eg 3-phenoxycarbonylpropyl), acyloxyalkyl group For example, 2-acetyloxyethyl), acylalkyl groups (for example, 2-acetylethyl), carbamoylalkyl groups (for example, 2-morpholinocarbonylethyl), sulfamoylalkyl groups (for example, N, N-dimethylsulfamoylmethyl), sulfo An alkyl group (for example, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2- [3-sulfopropoxy] ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl), sulfo Alkenyl group, sulfatoalkyl group (for example, 2-sulfatoethyl group, 3-sulfatopropyl, 4-sulfatobutyl), heterocycle-substituted alkyl group (for example, 2- (pyrrolidin-2-one-1-yl) Ethyl, tetrahydrofurfuryl), alkylsulfoni A carbamoylalkyl group (eg methanesulfonylcarbamoylmethyl group), an acylcarbamoylalkyl group (eg acetylcarbamoylmethyl group), an acylsulfamoylalkyl group (eg acetylsulfamoylmethyl group), an alkylsulfonylsulfamoylalkyl group (eg methane) A sulfonylsulfamoylmethyl group)}, an unsubstituted aryl group having 6 to 20 carbon atoms (preferably 6 to 10, more preferably 6 to 8) (for example, phenyl group, 1-naphthyl group), 6 to 20 carbon atoms ( Preferably 6 to 10 and more preferably 6 to 8) substituted aryl groups (for example, aryl groups substituted with the above-mentioned V as examples of substituents, specifically, p-methoxyphenyl group, p-methyl) (A phenyl group, p-chlorophenyl group, etc. are mentioned.) An unsubstituted heterocyclic group having 1 to 20 carbon atoms (preferably 3 to 10, more preferably 4 to 8) (for example, 2-furyl group, 2-thienyl group, 2-pyridyl group, 3-pyrazolyl group, 3- Isoxazolyl group, 3-isothiazolyl group, 2-imidazolyl group, 2-oxazolyl group, 2-thiazolyl group, 2-pyridazyl group, 2-pyrimidyl group, 3-pyrazyl group, 2- (1,3,5-triazolyl group) , 3- (1,2,4-triazolyl) group, 5-tetrazolyl group), a substituted heterocyclic group having 1 to 20 carbon atoms (preferably 3 to 10, more preferably 4 to 8) (for example, the substituent V And the like, and specific examples thereof include 5-methyl-2-thienyl group, 4-methoxy-2-pyridyl group, and the like.

As R < ₁ > and R < ₂ > of the said Structural formula (15), the group which has an aromatic ring is preferable. Examples of the aromatic ring include a hydrocarbon aromatic ring and a heteroaromatic ring, which further include a hydrocarbon aromatic ring, a polycyclic condensed ring obtained by condensing heteroaromatic rings, an aromatic hydrocarbon ring, and It may be a polycyclic fused ring combined with an aromatic heterocycle, and may be substituted with the substituent V or the like.

Group having an aromatic ring can be represented by -Lb-A _1. Here, Lb represents a single bond or a linking group. A ₁ represents an aromatic group. The linking group for Lb is preferably composed of an atom or an atomic group containing at least one of a carbon atom, a nitrogen atom, a sulfur atom, and an oxygen atom.
Specifically, the linking group is an alkylene group (for example, methylene, ethylene, propylene, butylene, pentylene), an arylene group (for example, phenylene, naphthylene), an alkenylene group (for example, ethenylene, propenylene), an alkynylene group (for example, ethynylene). , Propynylene), amide group, ester group, sulfoamide group, sulfonic acid ester group, ureido group, sulfonyl group, sulfinyl group, thioether group, ether group, carbonyl group, -N (Va)-(Va is a hydrogen atom, or one A monovalent substituent such as V described later), a heterocyclic divalent group (for example, a 6-chloro-1,3,5-triazine-2,4-diyl group, One or more of pyrimidine-2,4-diyl group, quinoxaline-2,3-diyl group) Linking group having a carbon number of 0 or more and 100 or less composed Te and the like, it is preferred carbon atom number is 1 to 20.
The linking group may further have a substituent represented by V and may contain a ring (aromatic or non-aromatic hydrocarbon ring or heterocyclic ring).

  Examples of the linking group include alkylene groups having 1 to 10 carbon atoms (for example, methylene, ethylene, propylene, butylene), arylene groups having 6 to 10 carbon atoms (for example, phenylene and naphthylene), and alkenylene having 2 to 10 carbon atoms. One or more groups (eg, ethenylene, propenylene), alkynylene groups having 2 to 10 carbon atoms (eg, ethynylene, propynylene), ether groups, amide groups, ester groups, sulfoamide groups, sulfonate ester groups It is preferably a divalent linking group having 1 to 10 carbon atoms configured in combination. These may be substituted with V.

  In addition, La is a linking group that may perform energy transfer or electron transfer by through-bond interaction. The through-bond interaction includes a tunnel interaction and a super-exchange interaction, and among them, a through-bond interaction based on the super-exchange interaction is preferable. Through-bond and superexchange interactions are interactions defined by Shammai Speiser, Chem. Rev. 96, 1960-1963, 1996. . Examples of the linking group capable of energy transfer or electron transfer by such interaction are described in Shammai Speiser, Chem. Rev. 96, 1967-1969, 1996. Those are preferred.

As R ₁ and R _{2 in} the structural formula (15), specifically, as an alkyl group having a hydrocarbon aromatic ring, for example, an aralkyl group (for example, benzyl, 2-phenylethyl, naphthylmethyl, 2- (4-biphenyl) ethyl), aryloxyalkyl groups (eg, 2-phenoxyethyl, 2- (1-naphthoxy) ethyl, 2- (4-biphenyloxy) ethyl, 2- (o, m or p-halophenoxy)) Ethyl, 2- (o, m or p-methoxyphenoxy) ethyl), an aryloxycarbonylalkyl group (3-phenoxycarbonylpropyl, 2- (1-naphthoxycarbonyl) ethyl) and the like are preferable. Examples of the alkyl group having a heteroaromatic ring include 2- (2-pyridyl) ethyl, 2- (4-pyridyl) ethyl, 2- (2-furyl) ethyl, 2- (2-thienyl) ethyl, 2- (2-Pyridylmethoxy) ethyl is preferred. As the hydrocarbon aromatic group, 4-methoxyphenyl, phenyl, naphthyl, biphenyl and the like are preferable. As the heteroaromatic group, a 2-thienyl group, 4-chloro-2-thienyl, 2-pyridyl, 3-pyrazolyl and the like are preferable.
Moreover, the alkyl group which has the above-mentioned substituted or unsubstituted hydrocarbon aromatic ring or a heteroaromatic ring is more preferable, and the alkyl group which has the above-mentioned substituted or unsubstituted hydrocarbon aromatic ring is especially preferable.

As R < ₃ > and R < ₄ > of the said Structural formula (16), the group which has an aromatic ring is preferable, and it is preferable that at least 1 has an anionic substituent.
Examples of the aromatic ring include a hydrocarbon aromatic ring and a heteroaromatic ring. These include a hydrocarbon aromatic ring and a polycyclic condensed ring obtained by condensing heteroaromatic rings, or an aromatic hydrocarbon ring. And an aromatic heterocycle may be combined, and may be substituted with the substituent V or the like. As the aromatic ring, those shown as examples of the aromatic ring in the explanation of the aromatic group are preferable.

Group having an aromatic ring, can be represented by -Lc-A _2. Here, Lc represents a single bond or a linking group. A ₂ represents an aromatic group. Preferred examples of the linking group for Lc include the linking groups described above for La and the like. Preferred examples of the aromatic group for A ₂ include those mentioned above as examples of the aromatic group. Lc or A ₂ is preferably substituted with at least one anionic substituent.
As the alkyl group having a hydrocarbon aromatic ring, an aralkyl group substituted with any of a sulfo group, a phosphoric acid group, and a carboxyl group (for example, 2-sulfobenzyl, 4-sulfobenzyl, 4-sulfophenethyl, 3- Phenyl-3-sulfopropyl, 3-phenyl-2-sulfopropyl, 4,4-diphenyl-3-sulfobutyl, 2- (4′-sulfo-4-biphenyl) ethyl, 4-phosphobenzyl), sulfo group, phosphorus An aryloxycarbonylalkyl group (3-sulfophenoxycarbonylpropyl) substituted with either an acid group or a carboxyl group, an aryloxyalkyl group substituted with any of a sulfo group, a phosphate group, or a carboxyl group (for example, 2 -(4-sulfophenoxy) ethyl, 2- (2-phosphophenoxy) ethyl, 4,4-diph Enoxy-3-sulfobutyl) and the like are preferable.
Examples of the alkyl group having a heteroaromatic ring include 3- (2-pyridyl) -3-sulfopropyl, 3- (2-furyl) -3-sulfopropyl, 2- (2-thienyl) -2-sulfo. Propyl and the like are preferable. The hydrocarbon aromatic group includes an aryl group substituted with any of a sulfo group, a phosphate group, and a carboxyl group (for example, 4-sulfophenyl, 4-sulfonaphthyl), and the heteroaromatic group includes a sulfo group, phosphorus A heterocyclic group substituted with either an acid group or a carboxyl group (for example, a 4-sulfo-2-thienyl group, a 4-sulfo-2-pyridyl group) and the like are preferable.
In addition, an alkyl group having a hydrocarbon aromatic ring or a heteroaromatic ring substituted by any of the sulfo group, phosphate group, and carboxyl group is more preferable, and any of the sulfo group, phosphate group, and carboxyl group is preferred. Are particularly preferred alkyl groups having a substituted hydrocarbon aromatic ring, such as 2-sulfobenzyl, 4-sulfobenzyl, 4-sulfophenethyl, 3-phenyl-3-sulfopropyl, and 4-phenyl-4-sulfobutyl. Most preferred.

L _{1 to} L ₄ in the structural formula (15) and L _{5 to} L ₈ in the structural formula (16) each independently represent a methine group, and preferably an unsubstituted methine group.
The methine group may have a substituent, and examples of the substituent include V. A substituted or unsubstituted alkyl group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, particularly preferably 1 to 5 carbon atoms (eg, methyl, ethyl, 2-carboxyethyl), substituted or unsubstituted carbon number An aryl group having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms (eg phenyl, o-carboxyphenyl), substituted or unsubstituted 3 to 20 carbon atoms, preferably 4 to carbon atoms 15, more preferably a heterocyclic group having 6 to 10 carbon atoms (for example, N, N-dimethylbarbituric acid group), a halogen atom (for example, chlorine, bromine, iodine, fluorine), 1 to 15 carbon atoms, preferably carbon An alkoxy group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (for example, methoxy, ethoxy), 0 to 15 carbon atoms, preferably 2 to 10 carbon atoms, Preferably an amino group having 4 to 10 carbon atoms (for example, methylamino, N, N-dimethylamino, N-methyl-N-phenylamino, N-methylpiperazino), 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, More preferably, it is an alkylthio group having 1 to 5 carbon atoms (for example, methylthio, ethylthio), an arylthio group having 6 to 20, preferably 6 to 12, and more preferably 6 to 10 carbon atoms (for example, phenylthio, p-methyl). Phenylthio) and the like. The may form the other methine groups and rings, or may be respectively form a ring together with _{Z 1 ~Z 4, R 1 ~R} 4.

M ₂ of said M _1, and the structural formula of structure (15) (16), when necessary to the ion charge of the dye neutral expression to indicate the presence of a cation or anion Is included. Typical cations include inorganic cations such as hydrogen ions (H ⁺ ), alkali metal ions (eg, sodium ions, potassium ions, lithium ions), alkaline earth metal ions (eg, calcium ions), ammonium ions (eg, Organic ions such as ammonium ion, tetraalkylammonium ion, pyridinium ion, ethylpyridinium ion). The anion may be either an inorganic anion or an organic anion, such as a halogen anion (for example, fluorine ion, chlorine ion, iodine ion), a substituted aryl sulfonate ion (for example, p-toluenesulfonate ion, p- Chlorobenzenesulfonate ion), aryl disulfonate ion (for example, 1,3-benzenesulfonate ion, 1,5-naphthalene disulfonate ion, 2,6-naphthalenedisulfonate ion), alkyl sulfate ion (for example, methyl sulfate ion) ), Sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, trifluoromethanesulfonate ion. Furthermore, you may use the ionic polymer or the other pigment | dye which has a charge opposite to a pigment | dye. CO ₂ ⁻ and SO ₃ ⁻ can also be expressed as CO ₂ H and SO ₃ H when they have hydrogen ions as counter ions.

In the formula, Z _{5 to} Z ₁₀ each represents an atomic group necessary for forming a 5-membered or 6-membered nitrogen-containing heterocyclic ring.
D and D ′ represent an atomic group necessary for forming an acyclic or cyclic acidic nucleus.
R _{5 to} R ₈ and R ₁₀ represent an alkyl group. R ₉ represents an alkyl group, an aryl group or a heterocyclic group. L _{9 to} L ₂₈ represent a methine group.
M _{3 to} M ₅ represent a charge neutralization counter ion, and m _{3 to} m ₅ are a number of 0 or more necessary for neutralizing the charge in the molecule.
n ₃ , n ₅ , n ₆ , n ₇ and n ₁₁ are 0 or 1, and n ₄ , n ₇ , n ₉ and n ₁₀ are each an integer of 0 or more.

The structural formulas (17) to (19) will be described in more detail.
R _{5 to} R ₈ and R ₁₀ are preferably unsubstituted alkyl groups having 18 or less carbon atoms (for example, methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, octadecyl), or substituted alkyl groups {substituted Examples of the group include a carboxy group, a sulfo group, a cyano group, a halogen atom (for example, fluorine, chlorine, bromine), a hydroxy group, an alkoxycarbonyl group having 8 or less carbon atoms (for example, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, benzyl). Oxycarbonyl), an alkoxy group having 8 or less carbon atoms (for example, methoxy, ethoxy, benzyloxy, phenethyloxy), a monocyclic aryloxy group having 10 or less carbon atoms (for example, phenoxy, p-tolyloxy), 3 or less carbon atoms Acyloxy groups (eg acetyloxy) Ci, propionyloxy), an acyl group having 8 or less carbon atoms (for example, acetyl, propionyl, benzoyl, mesyl), carbamoyl group (for example, carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl), sulfamoyl group (for example, Sulfamoyl, N, N-dimethylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl), carbon substituted with an aryl group having 10 or less carbon atoms (for example, phenyl, 4-chlorophenyl, 4-methylphenyl, α-naphthyl) And an alkyl group having a number of 18 or less. Preferably an unsubstituted alkyl group (for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group), carboxyalkyl group (for example, 2-carboxyethyl group, carboxymethyl group) ), A sulfoalkyl group (for example, 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3-sulfobutyl group), methanesulfonylcarbamoylmethyl group. M ₃ m ₃ , M ₄ m ₄ and M ₅ m ₅ are in the formula to indicate the presence or absence of a cation or anion, as necessary to neutralize the ionic charge of the dye. Is included. Whether a certain dye is a cation, an anion, or has a net ionic charge depends on its auxiliary color groups and substituents. Typical cations are inorganic or organic ammonium ions and alkali metal ions, while the anions may be specifically inorganic or organic anions, such as halogen anions (eg fluorine ions, Chlorine ions, bromine ions, iodine ions), substituted aryl sulfonate ions (eg, p-toluene sulfonate ion, p-chlorobenzene sulfonate ion), aryl disulfonate ions (eg, 1,3-benzene disulfonate ion, 1, 5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion), alkyl sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetic acid Ion, trifluoromethane Preferably sulfonic acid ion and the like, ammonium ion, an iodine ion, a p- toluenesulfonic acid ion.

As the nucleus formed by Z _{5 to} Z ₈ and Z ₁₀ , a thiazole nucleus {thiazole nucleus (for example, thiazole, 4-methylthiazole, 4-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole), Benzothiazole nucleus (eg, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 5-nitrobenzothiazole, 4-methylbenzothiazole, 5-methylthiobenzothiazole, 5-methylbenzothiazole 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 6-methylthiazole Obenzothiazole, 5-ethoxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-carboxybenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5-chloro-6-methylbenzothiazole, 5,6-dimethyl Benzothiazole, 5,6-dimethylthiobenzothiazole, 5,6-dimethoxybenzothiazole, 5-hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole), naphthothiazole nucleus (for example, naphtho [2 , 1-d] thiazole, naphtho [1,2-d] thiazole, naphtho [2,3-d] thiazole, 5-methoxynaphtho [1,2-d] thiazole, 7-ethoxynaphtho [2,1-d ] Thiazole, 8-methoxynaphth [2,1-d] thiazole, 5-methoxynaphtho [2,3-d] thiazole)}, thiazoline nucleus (eg, thiazoline, 4-methylthiazoline, 4-nitrothiazoline), oxazole nucleus {oxazole nucleus (eg, Oxazole, 4-methyl oxazole, 4-nitro oxazole, 5-methyl oxazole, 4-phenyl oxazole, 4,5-diphenyl oxazole, 4-ethyl oxazole), benzoxazole nucleus (for example, benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-nitrobenzoxazole, 5-trifluoromethylbenzoxa 5-hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-nitrobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 5,6-dimethyl Benzoxazole, 4,6-dimethylbenzoxazole, 5-ethoxybenzoxazole), naphthoxazole nucleus (for example, naphtho [2,1-d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,3- d] oxazole, 5-nitronaphtho [2,1-d] oxazole)}, oxazoline nucleus (eg, 4,4-dimethyloxazoline), selenazole nucleus {selenazole nucleus (eg, 4-methylselenazole, 4-nitroselenazole) , 4-F Enylselenazole), benzoselenazole nucleus (eg, benzoselenazole, 5-chlorobenzoselenazole, 5-nitrobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, 6-nitrobenzoselenazole , 5-chloro-6-nitrobenzoselenazole, 5,6-dimethylbenzoselenazole), naphthoselenazole nucleus (for example, naphtho [2,1-d] selenazole, naphtho [1,2-d] selenazole)} Selenazoline nucleus (eg, selenazoline, 4-methylselenazoline), tellurazole nucleus {tellazole nucleus (eg, tellurazole, 4-methyltellazole, 4-phenyltellazole), benzotelrazole nucleus (eg, benzotelrazole, 5 -Chlorobenzotellazole, 5-me Benzotelrazole, 5,6-dimethylbenzotellazole, 6-methoxybenzotellazole), naphthotelrazole nucleus (for example, naphtho [2,1-d] tellazole, naphtho [1,2-d] tellazole)} Tellurazoline nuclei (eg, tellurazoline, 4-methyltellazoline), 3,3-dialkylindolenine nuclei (eg, 3,3-dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-5- Cyano indolenine, 3,3-dimethyl-6-nitro indolenine, 3,3-dimethyl-5-nitro indolenine, 3,3-dimethyl-5-methoxy indolenine, 3,3,5-trimethyl indolenine, 3,3-dimethyl-5-chloroindolenine), imidazole nucleus {imidazole nucleus (for example, 1-alkyloxy) Dazole, 1-alkyl-4-phenylimidazole, 1-arylimidazole), benzimidazole nucleus (eg, 1-alkylbenzimidazole, 1-alkyl-5-chlorobenzimidazole, 1-alkyl-5,6-dichlorobenzimidazole) 1-alkyl-5-methoxybenzimidazole, 1-alkyl-5-cyanobenzimidazole, 1-alkyl-5-fluorobenzimidazole, 1-alkyl-5-trifluoromethylbenzimidazole, 1-alkyl-6-chloro -5-cyanobenzoimidazole, 1-alkyl-6-chloro-5-trifluoromethylbenzimidazole, 1-allyl-5,6-dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole, 1-aryl Benzimidazo 1-aryl-5-chlorobenzimidazole, 1-aryl-5,6-dichlorobenzimidazole, 1-aryl-5-methoxybenzimidazole, 1-aryl-5-cyanobenzimidazole), naphthimidazole nucleus ( For example, alkylnaphtho [1,2-d] imidazole, 1-arylnaphtho [1,2-d] imidazole), and the aforementioned alkyl group has 1 to 8 carbon atoms, such as methyl, ethyl, propyl, An unsubstituted alkyl group such as isopropyl and butyl and a hydroxyalkyl group (for example, 2-hydroxyethyl, 3-hydroxypropyl) are preferable. Particularly preferred are a methyl group and an ethyl group. The aforementioned aryl groups represent phenyl, halogen (eg chloro) substituted phenyl, alkyl (eg methyl) substituted phenyl, alkoxy (eg methoxy) substituted phenyl. }, Pyridine nucleus (eg 2-pyridine, 4-pyridine, 5-methyl-2-pyridine, 3-methyl-4-pyridine), quinoline nucleus {quinoline nucleus (eg 2-quinoline, 3-methyl-2-pyridine) Quinoline, 5-ethyl-2-quinoline, 6-methyl-2-quinoline, 6-nitro-2-quinoline, 8-fluoro-2-quinoline, 6-methoxy-2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2-quinoline, 4-quinoline, 6-ethoxy-4-quinoline, 6-nitro-4-quinoline, 8-chloro-4-quinoline, 8-fluoro-4-quinoline, 8-methyl-4- Quinoline, 8-methoxy-4-quinoline, 6-methyl-4-quinoline, 6-methoxy-4-quinoline, 6-chloro-4-quinoline), isoquinoline nucleus (eg 6-nitro-1- Soquinoline, 3,4-dihydro-1-isoquinoline, 6-nitro-3-isoquinoline)}, imidazo [4,5-b] quinoxaline nucleus (eg, 1,3-diethylimidazo [4,5-b] quinoxaline, 6-chloro-1,3-diallylimidazo [4,5-b] quinoxaline), oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus, pyrimidine nucleus. However, in the general formula, when n ₄ is 1, neither Z ₅ nor Z ₆ is an oxazole nucleus or an imidazole nucleus. The nucleus formed by Z _{5 to} Z ₈ and Z ₁₀ is preferably a benzothiazole nucleus, a naphthothiazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzimidazole nucleus, a 2-quinoline nucleus, or a 4-quinoline nucleus.

The D and D ′ represent atomic groups necessary for forming an acidic nucleus, but can take the form of an acidic nucleus of any general merocyanine dye. Preferred substituents involved in the resonance of D are, for example, a carbonyl group, a cyano group, a sulfonyl group, and a sulfenyl group. Said D 'represents the remaining atomic group required in order to form an acidic nucleus. When D and D ′ are cyclic, they form a 5- or 6-membered heterocycle consisting of carbon, nitrogen, and chalcogen (typically oxygen, sulfur, selenium, and tellurium) atoms. Specifically, 2-pyrazolin-5-one, pyrazolidine-3,5-dione, imidazolin-5-one, hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidine-4-one, 2-oxazoline-5 ON, 2-thiooxazolidine-2,4-dione, isoxazoline-5-one, 2-thiazolin-4-one, thiazolidine-4-one, thiazolidine-2,4-dione, rhodamine, thiazolidine-2,4- Dithione, isorhodanine, indan-1,3-dione, thiophen-3-one, thiophen-3-one-1,1-dioxide, indoline-2-one, indoline-3-one, indazolin-3-one, 2- Oxoindazolinium, 3-oxoindazolinium, 5,7-dioxo-6,7-dihydrothiazolo [3 2-a] pyrimidine, cyclohexane-1,3-dione, 3,4-dihydroisoquinolin-4-one, 1,3-dioxane-4,4-dione, barbituric acid, 2-thiobarbituric acid, chroman- Examples include nuclei of 2,4-dione, indazolin-2-one, or pyrido [1,2-a] pyrimidine-1,3-dione. Among these, 3-alkyl rhodanine, 3-alkyl-2-thiooxazolidine-2,4-dione, and 3-alkyl-2-thiohydantoin are preferable.
The substituent bonded to the nitrogen atom contained in the nucleus and the R ₉ are a hydrogen atom, an alkyl group having 1 to 18 carbon atoms (preferably 1 to 7, particularly preferably 1 to 4) {for example, methyl, Ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl}, substituted alkyl groups (eg aralkyl groups (eg benzyl, 2-phenylethyl)), hydroxyalkyl groups (eg 2-hydroxyethyl, 3-hydroxy Pill), a carboxyalkyl group (for example, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, carboxymethyl), an alkoxyalkyl group (for example, 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl), A sulfoalkyl group (for example, 2-sulfoethyl, 3-sulfopro Pill, 3-sulfobutyl, 4-sulfobutyl, 2- [3-sulfopropoxy] ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl), a sulfatoalkyl group (for example, 3-sulfatopropyl, 4-sulfatobutyl), heterocyclic-substituted alkyl groups (for example, 2- (pyrrolidin-2-one-1-yl) ethyl, tetrahydrofurfuryl, 2-morpholinoethyl), 2-acetoxyethyl, carbomethoxymethyl, 2- Methanesulfonylaminoethyl), allyl group, aryl group (eg, phenyl, 2-naphthyl), substituted aryl group (eg, 4-carboxyphenyl, 4-sulfophenyl, 3-chlorophenyl, 3-methylphenyl), heterocyclic group ( For example, 2-pyridyl and 2-thiazolyl) are preferable. More preferably, an unsubstituted alkyl group (for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl), a carboxyalkyl group (for example, carboxymethyl, 2-carboxyethyl, sulfoalkyl group ( For example, 2-sulfoethyl).

The 5- or 6-membered nitrogen-containing heterocycle formed by Z _{9 is obtained} by removing an oxo group or a thiooxo group at an appropriate position from the cyclic heterocycle represented by D and D ′. It is. More preferably, the thiooxo group of the rhodanine nucleus is removed.

L _{9 to} L ₂₈ in the structural formulas (17) to (19) are methine groups or substituted methine groups {for example, substituted or unsubstituted alkyl groups (for example, methyl, ethyl, 2-carboxyethyl), substituted or unsubstituted Aryl group (for example, phenyl, o-carboxyphenyl), heterocyclic group (for example, barbituric acid), halogen atom (for example, chlorine atom, bromine atom), alkoxy group (for example, methoxy, ethoxy), amino group (for example, N , N-diphenylamino, N-methyl-N-phenylamino, N-methylpiperazino), alkylthio groups (for example, methylthio, ethylthio), etc.}, and form rings with other methine groups May be.
L ₉ , L ₁₃ , L ₁₄ , L _{15 in} the structural formula (17), L ₁₈ , L _{19 in} the structural formula (18), L ₂₅ and L ₂₆ in the structural formula (19) are none. A substituted methine group is preferred. Trimethine, pentamethine and heptamethine dyes are formed by L ₉ , L ₁₀ and L _{11 in the} structural formula (17). Although it is repeated when the unit n ₃ of L ₉ and L _{10 in} the structural formula (17) is 2 or 3, it does not have to be the same.

In the structural formula (20), L _{29 to} L ₃₁ each independently represents a methine group which may have a substituent, and when these represent a methine group having a substituent, the substituent is bonded. To form an unsaturated aliphatic ring or an unsaturated heterocyclic ring. Z ₁₁ represents an atomic group forming a 5-membered or 6-membered heterocyclic ring, and the heterocyclic ring may be condensed with an aromatic ring or a heterocyclic ring, and the 5-membered or 6-membered heterocyclic ring, and The aromatic ring or heterocyclic ring condensed to the heterocyclic ring may have a substituent. Y represents N (R ₁₁ ) R ₁₂ , OR ₁₃ , or S (O) _n R ₁₄ , R _{11 to} R ₁₄ each independently represent a hydrogen atom or a monovalent substituent, and n is 0, 1 or 2 is represented. q represents 0, 1, 2 or 3.
The specific example (exemplary compound No. 1-62) of a compound represented by the said Structural formula (20) is shown.

In the structural formula (21), R ₁₈ and R ₁₉ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group.
Q ₁ to Q ₃ each independently represent an oxygen atom, a sulfur atom. Here, Q ₁ and Q ₂ are preferably oxygen atoms, and Q ₃ is preferably a sulfur atom.
L _{32 to} L ₃₄ each independently represents a methine group which may have a substituent, and when these represent a methine group having a substituent, the substituent is bonded to form an unsaturated aliphatic ring or A saturated heterocyclic ring may be formed.
Y ₂ represents an aromatic group or a heterocyclic group, and n ₁₂ represents 0, 1, 2, or 3.

R ₁₈ and R ₁₉ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. When R ₁₈ and R ₁₉ represent an aliphatic group, examples of the aliphatic group include an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group, and a substituted aralkyl group. Among them, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aralkyl group, or a substituted aralkyl group is preferable, and an alkyl group and a substituted alkyl group are particularly preferable. The aliphatic group may be a cyclic aliphatic group or a chain aliphatic group. The chain aliphatic group may have a branch.

  Examples of the alkyl group include linear, branched and cyclic alkyl groups, and the number of carbon atoms of the alkyl group is preferably 1 to 30, and more preferably 1 to 20. The preferred range of the number of carbon atoms in the alkyl part of the substituted alkyl group is the same as in the case of the alkyl group. Further, the alkyl group may be either a substituted alkyl group or an unsubstituted alkyl group. Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, dodecyl group, octadecyl group, cyclohexyl group, cyclopentyl group, neopentyl group, An isopropyl group, an isobutyl group, etc. are mentioned.

  Examples of the substituent of the substituted alkyl group include a carboxyl group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), a hydroxy group, and an alkoxycarbonyl group having 30 or less carbon atoms (for example, methoxycarbonyl). Group, ethoxycarbonyl group, benzyloxycarbonyl group), alkylsulfonylaminocarbonyl group having 30 or less carbon atoms, arylsulfonylaminocarbonyl group, alkylsulfonyl group, arylsulfonyl group, acylaminosulfonyl group having 30 or less carbon atoms, carbon number 30 The following alkoxy groups (for example, methoxy group, ethoxy group, benzyloxy group, phenoxyethoxy group, phenethyloxy group, etc.), alkylthio groups having 30 or less carbon atoms (for example, methylthio group, ethylthio group, methylthioethylthioethyl group, etc.) An aryloxy group having 30 or less carbon atoms (eg, phenoxy group, p-tolyloxy group, 1-naphthoxy group, 2-naphthoxy group, etc.), nitro group, alkyl group having 30 or less carbon atoms, alkoxycarbonyloxy group, aryloxy A carbonyloxy group, an acyloxy group having 30 or less carbon atoms (for example, acetyloxy group, propionyloxy group, etc.), an acyl group having 30 or less carbon atoms (for example, acetyl group, propionyl group, benzoyl group, etc.), carbamoyl group (for example, Carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.), sulfamoyl group (for example, sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group) Etc.), an aryl group having 30 or less carbon atoms For example, phenyl group, 4-chlorophenyl group, 4-methylphenyl group, α-naphthyl group, etc.), substituted amino group (for example, amino group, alkylamino group, dialkylamino group, arylamino group, diarylamino group, acylamino group) Etc.), substituted ureido groups, substituted phosphono groups, heterocyclic groups and the like. Here, the carboxyl group, the sulfo group, the hydroxy group, and the phosphono group may be in a salt state.

  Examples of the alkenyl group include linear, branched, and cyclic alkenyl groups. The number of carbon atoms of the alkenyl group is preferably 2 to 30, and more preferably 2 to 20. The preferred range of the number of carbon atoms in the alkenyl part of the substituted alkenyl group is the same as in the case of the alkenyl group. The alkenyl group may be a substituted alkenyl group or an unsubstituted alkenyl group. Examples of the substituent of the substituted alkenyl group include the same substituents as those of the substituted alkyl group.

  Examples of the aralkyl group include linear, branched, and cyclic aralkyl groups. The number of carbon atoms in the aralkyl group is preferably 7 to 35, and more preferably 7 to 25. The preferred range of the number of carbon atoms in the aralkyl part of the substituted aralkyl group is the same as in the case of the aralkyl group. Further, the aralkyl group may be any of an aralkyl group having a substituent and an unsubstituted aralkyl group. Examples of the substituent for the substituted aralkyl group include the same substituents as those for the substituted alkyl group.

When R ₁₈ and R ₁₉ represent an aromatic group, examples of the aromatic group include an aryl group and a substituted aryl group. As a carbon atom number of an aryl group, 6-30 are preferable and 6-20 are more preferable. The preferred range of the number of carbon atoms in the aryl part of the substituted aryl group is the same as that of the aryl group. Examples of the aryl group include a phenyl group, an α-naphthyl group, a β-naphthyl group, and the like. Examples of the substituent for the substituted aryl group include the same substituents as those for the substituted alkyl group.

When R ₁₈ and R ₁₉ represent a heterocyclic group, examples of the heterocyclic group include a heterocyclic group having a substituent and an unsubstituted heterocyclic group. The number of carbon atoms of the heterocyclic group is as follows: 4-13 are preferable. Examples of the heterocyclic group include nitrogen-containing, oxygen-containing, and sulfur-containing heterocycles, and more specifically, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, quinoline ring, isoquinoline ring, quinoxaline. Ring, acridine ring, furan ring, pyrrole ring, pyrazole ring, imidazole ring, pyrroline ring, oxazole ring, thiazole ring, oxadiazole ring, thiazoline ring, thiophene ring, indole ring and the like. Examples of the substituent of the heterocyclic group having a substituent include the same substituents as in the case of the substituted alkyl group.

Among the above, as R ₁₈ and R ₁₉ , an unsubstituted alkyl group (for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, octyl group, An octadecyl group or the like) or a substituted alkyl group. Among the substituted alkyl groups, a substituted oxyalkyl group (for example, methoxyethyl group, phenoxyethyl group and the like) and a substituted oxycarbonylalkyl group (for example, butoxycarbonylmethyl group, phenoxyethoxycarbonylmethyl group and the like) are particularly preferable. R ₁₈ and R ₁₉ may be bonded to other adjacent substituents to form a ring, and examples of the ring include a 5-membered or 6-membered heterocycle. .

L _{32 to} L ₃₄ in the structural formula (21) each independently represent a methine group which may have a substituent, and have an odd number of methine groups in the structure. When L _{32 to} L ₃₄ represent a methine group having a substituent, examples of the substituent include a substituted amino group (for example, an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, Acylamino groups, etc.), substituted oxy groups (eg, hydroxy groups, alkoxy groups, acyloxy groups, aryloxy groups, alkoxycarbonyloxy groups, aryloxycarbonyloxy groups, etc.), substituted mercapto groups (eg, alkyl mercapto groups, aryl mercapto groups) Etc.), a halogen atom, an aliphatic group, and an aromatic group, and the substituent may be bonded to form an unsaturated aliphatic ring or an unsaturated heterocyclic ring. A group ring is preferred. The ring to be formed is preferably a 5-membered ring or a 6-membered ring, and more preferably a cyclopentene ring or a cyclohexene ring. Examples of the halogen atom include a fluorine atom, a bromine atom, and a chlorine atom, and the aliphatic group and the aromatic group have the same meanings as in the case of the aliphatic group and the aromatic group in R ¹ and R ² . It is. Moreover, as a substituent of a substituted amino group, a substituted oxy group, and a substituted mercapto group, it is synonymous with the substituent of the substituted alkyl group represented by said R <_18> and R < ₁₉ > in the said Structural formula (21).

Examples of the methine group represented by L _{32 to} L ₃₄ include an unsubstituted methine group, or, when having a substituent, a group substituted with a halogen atom or an aliphatic group, or a substituent bonded to each other. Those in which a cyclopentene ring or a cyclohexene ring is formed are particularly preferable. The n ₁₂ represents 0, 1, 2, or 3.

Y ₂ represents an aromatic group or a heterocyclic group. Here, an aromatic group and a heterocyclic group are synonymous with the case of the aromatic group and heterocyclic group in said R <_18> and R < ₁₉ >, The preferable thing is also the same. Y ¹ is particularly preferably an aromatic group from the viewpoint of photosensitivity.

In the structural formula (22), R ₂₀ and R ₂₁ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, and Q _{4 to} Q ₆ each independently represent an oxygen atom or a sulfur atom. Represents. L _{35 to} L ₃₇ each independently represents a methine group which may have a substituent, and when these represent a methine group having a substituent, the substituent is bonded to form an unsaturated aliphatic ring or A saturated heterocyclic ring may be formed. Y ₃ represents the following group (1), and n ₁₃ represents 0, 1, 2, or 3.
These are synonymous with those in the structural formula (21).

In the group (1), R ₂₂ represents a hydrogen atom, an aliphatic group, or an aromatic group. Z ₁₂ represents an atomic group forming a 5-membered or 6-membered nitrogen-containing heterocycle, and the nitrogen-containing heterocycle may be condensed with an aromatic ring or a heterocycle, and the nitrogen-containing heterocycle, and The aromatic ring and heterocyclic ring condensed to the nitrogen-containing heterocyclic ring may have a substituent.
X ⁻ represents a group capable of forming an anion. Examples of the anion that can be formed by X ⁻ include halogen ion (Cl ⁻ , Br ⁻ , I ⁻ ), p-toluenesulfonic acid ion, ethyl sulfate ion, 1,5-disulfonaphthalenedione, PF ₆ ^-, BF ₄ ^-, and ClO ₄ ^-, and the like. X ⁻ may be a substituent substituting any substitutable position of the cation moiety.

Examples of the nitrogen-containing heterocycle include an oxazole ring, a thiazole ring, a selenazole ring, a pyrrole ring, a pyrroline ring, an imidazole ring, and a pyridine ring. A 5-membered ring is preferred over a 6-membered ring.
The nitrogen-containing heterocycle may be condensed with an aromatic ring (benzene ring, naphthalene ring) or a heterocycle (pyridine, pyrazine, etc.), and the nitrogen-containing heterocycle and the condensed ring are further substituted. You may have.

Examples of the dye having an acidic nucleus include other compounds such as a compound in which an aromatic ring (for example, phenyl group, naphthyl group, etc.) substituted with an amino group or an alkoxy group and an acidic nucleus are connected by a methine chain. It is done. The number of methine chains is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1. The acidic nucleus is preferably a 5-membered to 6-membered ring.
Examples of other compounds include compounds represented by the following (A) and (B).

As content of the pigment | dye which has the said acidic nucleus, 0.01-4 mass% is preferable with respect to all the components of the said pattern formation material, 0.02-2 mass% is more preferable, 0.05-1 mass% Is particularly preferred.
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.
In addition to the dye having an acidic nucleus, other sensitizers described later may be added as necessary.
These compounds not only improve the sensitivity of the photosensitive layer, but also have a function as a photopolymerization initiator that initiates polymerization of the monomer by photoexcitation.

-Other sensitizers-
There is no restriction | limiting in particular as said sensitizer, Although it can select suitably from well-known sensitizers, For example, a hetero condensed ring type compound is preferable. The hetero-fused ring compound means a polycyclic compound having a hetero element in the ring, and preferably contains a nitrogen atom in the ring. Examples of the hetero-fused ring compound include a hetero-fused ring ketone compound, a quinoline compound, and an acridine compound.
Specific examples of the hetero-fused ketone compound include acridone compounds such as, for example, acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone; 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-diethylami Coumarin, 3- (4-Diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazole-2- Thioxanthone compounds such as ircoumarin, 7-diethylamino-4-methylcoumarin, thioxanthone, isopropylthioxanthone, 2.4-diethylthioxanthone, 1-chloro-4-propyloxythioxanthone, Quantacure QTX, and JP-A-5-19475, JP-A-7- No. 271028, JP-A No. 2002-363206, JP-A No. 2002-363207, JP-A No. 2002-363208, JP-A No. 2002-363209, and the like, and other coumarins; The Among these, an acridone compound and a thioxanthone compound are particularly preferable.
Specific examples of the quinoline compound include quinoline, 9-hydroxy-1,2-dihydroquinolin-2-one, 9-ethoxy-1,2-dihydroquinolin-2-one, and 9-dibutylamino- 1,2-dihydroquinolin-2-one, 8-hydroxyquinoline, 8-mercaptoquinoline, quinoline-2-carboxylic acid, and the like.
Specific examples of the acridine compound include 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, acridine orange, chloroflavin, and acriflavine. Among these hetero condensed ring compounds, those containing a nitrogen element in the ring are more preferable. Preferred examples of the compound containing a nitrogen element in the ring include the acridine compound, a coumarin compound substituted with an amino group, and an acridone compound. Among these, the acridone, coumarin substituted with an amino group, 9-phenylacridine, and the like are more preferable, and among these, the acridone is particularly preferable.
Also known polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (for example, indocarbocyanine, thiacarbocyanine, oxacarbanine) Cyanine), merocyanines (for example, merocyanine, carbomerocyanine), thiazines (for example, thionine, methylene blue, toluidine blue), anthraquinones (for example, anthraquinone), squalium (for example, squalium), and the like.

  Examples of the combination with the photopolymerization initiator and the sensitizer include, for example, an electron transfer-type initiator system described in JP-A No. 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 content of the sensitizer containing the dye having an acidic nucleus is preferably 0.05 to 30% by mass, more preferably 0.1 to 20% by mass with respect to all components in the pattern forming material. 0.2-10 mass% is especially preferable. When the content is less than 0.05% by mass, the sensitivity to active energy rays is reduced, the exposure process takes time, and productivity may be reduced. The sensitizer may be precipitated from the photosensitive layer.

-Thermal crosslinking agent-
The thermal crosslinking agent is not particularly limited and may be appropriately selected depending on the purpose. In order to improve the film strength after curing of the photosensitive layer formed using the pattern forming material, developability, etc. 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.
However, in said structural formula (i), R represents either a hydrogen atom or a C1-C6 alkyl group, and n represents the integer of 0-20.
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 from 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 pattern formation material solid content 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, for the purpose of improving the storage stability of the pattern forming material of the present invention, a compound obtained by reacting a blocking agent with the isocyanate group of the polyisocyanate and its derivative 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, acetooxime, 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 in the said pattern formation material solid content of the said thermal crosslinking agent, 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 the stability, photographic properties, and film properties of the target pattern forming material 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, phthalocyanine green, Victoria pure blue BO (CI. 42595), auramine (CI. 41000), fat Black HB (C.I. 26150), Monolite Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (C.I) Pigment 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 Spula (CI Pigment Red 1) Monasutoraru Fast 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 of the color pigment in the solid content of the pattern forming material can be determined in consideration of the exposure sensitivity and resolution of the photosensitive layer during permanent pattern formation, and varies depending on the type of the color pigment. However, generally 0.05-10 mass% is preferable, and 0.1-5 mass% is more preferable.

--External pigment--
If necessary, the pattern forming material may be an inorganic pigment 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. Or 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 pattern formation material, 0.01-10 mass% is more preferable, 0.1 mass%- 5% by mass is particularly preferred.

<Method for producing pattern forming material>
There is no restriction | limiting in particular as a manufacturing method of the said pattern formation material, According to the objective, it can select suitably, For example, photosensitive layers, such as a binder, polymeric compound, photoinitiator, etc. which were mentioned above on a support body. It is preferable to form a photosensitive layer by applying and drying a material contained in (hereinafter simply referred to as a photosensitive composition).
The coating and drying method is not particularly limited and can be appropriately selected depending on the purpose. For example, the photosensitive composition is dissolved, emulsified in water or a solvent on the surface of the support, Alternatively, it is preferable to prepare a photosensitive composition by dispersing, apply the solution, and dry.

  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 may be appropriately selected depending on the intended purpose. Examples thereof include a method of coating using a spin coater, a slit spin coater, a roll coater, a die coater, a curtain coater, and the like. It is done.
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.

<Protective film>
The pattern forming material may form a protective film on the photosensitive layer.
Examples of the protective film include those used for the support, 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.

  For example, the pattern forming material is preferably wound around a cylindrical core, wound into a long roll, and stored. There is no restriction | limiting in particular as length of the said elongate pattern formation material, For example, it can select suitably from the range of 10m-20,000m. Further, slitting may be performed so that the user can easily use, and a long body in the range of 100 m to 1,000 m may be formed into a roll. In this case, it is preferable that the support is wound up so as to be the outermost side. The roll-shaped pattern forming material may be slit into a sheet shape. 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.

<Formation of laminate>
When pattern formation is performed using the pattern forming material of the present invention, a laminate is formed by laminating a photosensitive layer of the pattern forming material on a substrate.

  The substrate is not particularly limited and can be appropriately selected from known materials having high surface smoothness to those having an uneven surface. A plate-like substrate (substrate) is preferred. Specifically, 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 can be given.

  There is no restriction | limiting in particular as a layer structure in the said laminated body, Although it can select suitably according to the objective, For example, the layer structure which has the said base material, the said photosensitive layer, and the said support body in this order is preferable. In addition, when the said pattern formation material has the protective film mentioned above, it is preferable to peel this protective film and to laminate | stack so that a photosensitive layer may overlap with the said base material.

The method for forming the laminate is not particularly limited and may be appropriately selected. The embodiment in which the photosensitive composition of the pattern forming material is applied on the substrate and dried to form a laminate, An embodiment in which the pattern forming material is laminated on the material while performing at least one of heating and pressing is preferable.
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 pattern forming material of the present invention is advantageous in that it can suppress a decrease in sensitivity of the photosensitive layer, and therefore can be exposed with light having a smaller energy amount, and the exposure speed increases, so that the processing speed increases.

<Application>
The pattern forming material of the present invention provides a highly sensitive photosensitive layer, is excellent in developability, has a good resist surface shape obtained after development, and can form a higher definition pattern. It can be widely used for forming permanent patterns such as display members such as color filters, pillar materials, rib materials, spacers, partition walls, holograms, micromachines, proofs, etc., and can be suitably used for the permanent pattern forming method of the present invention. it can.

(Pattern forming apparatus and permanent pattern forming method)
The pattern forming apparatus of the present invention includes the pattern forming material of the present invention, and has at least light irradiation means and light modulation means.

  The permanent pattern forming method of the present invention preferably includes at least an exposure step, and further includes a development step and a curing treatment step. In addition, the said pattern formation apparatus of this invention is clarified through description of the said permanent pattern formation method of this invention.

<Exposure process>
The said exposure process is a process of exposing with respect to the photosensitive layer in the pattern formation material of this invention. The pattern forming material and the base material of the present invention are as described above.

  The subject of the exposure is not particularly limited as long as it is the photosensitive layer in the pattern forming material, and can be appropriately selected according to the purpose. For example, as described above, the pattern forming material is formed on the substrate. It is preferably performed on a laminate formed by laminating while performing at least one of heating and pressurization.

  There is no restriction | limiting in particular as said exposure, According to the objective, it can select suitably, Digital exposure, analog exposure, etc. are mentioned, Among these, digital exposure is preferable.

  The digital exposure is not particularly limited and can be appropriately selected depending on the purpose.For example, a control signal is generated based on pattern formation information to be formed, and light modulated in accordance with the control signal is generated. It is preferable to use.

  The digital exposure means is not particularly limited and may be appropriately selected depending on the purpose. For example, the light irradiation means for irradiating light, and the light irradiation means for irradiating based on the pattern information to be formed. Examples thereof include light modulation means for modulating light.

-Light modulation means-
The light modulating means is not particularly limited as long as it can modulate light, and can be appropriately selected according to the purpose. For example, it preferably has n pixel portions.
The light modulation means having the n picture elements is not particularly limited and can be appropriately selected according to the purpose. For example, a spatial light modulation element is preferable.

  Examples of the spatial light modulator include a digital micromirror device (DMD), a MEMS (Micro Electro Mechanical Systems) type spatial light modulator (SLM), and modulates transmitted light by an electro-optic effect. An optical element (PLZT element), a liquid crystal optical shutter (FLC), etc. are mentioned, Among these, DMD is mentioned suitably.

Moreover, it is preferable that the said light modulation means has a pattern signal generation means which produces | generates a control signal based on the pattern information to form. In this case, the light modulation unit modulates light according to the control signal generated by the pattern signal generation unit.
There is no restriction | limiting in particular as said control signal, According to the objective, it can select suitably, For example, a digital signal is mentioned suitably.

Hereinafter, an example of the light modulation means will be described with reference to the drawings.
As shown in FIG. 1, in the DMD 50, a large number (for example, 1024 × 768) of micromirrors (micromirrors) 62, each constituting a pixel (pixel), are arranged in a lattice pattern on an SRAM cell (memory cell) 60. It is a mirror device arranged. In each pixel, a micromirror 62 supported by a support column is provided at the top, and a material having high reflectivity such as aluminum is deposited on the surface of the micromirror 62. In addition, the reflectance of the micromirror 62 is 90% or more, and the arrangement pitch is 13.7 μm as an example in both the vertical direction and the horizontal direction. 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 the entire structure is monolithic. ing.

  When a digital signal is written in the SRAM cell 60 of the DMD 50, the micromirror 62 supported by the support is tilted in a range of ± α degrees (for example, ± 12 degrees) with respect to the substrate side on which the DMD 50 is disposed with the diagonal line as the center. It is done. 2A shows a state where the micromirror 62 is tilted to + α degrees when the micromirror 62 is in the on state, and FIG. 2B shows a state where the micromirror 62 is tilted to −α degrees when the micromirror 62 is in the off state. Therefore, by controlling the inclination of the micro mirror 62 in each pixel of the DMD 50 as shown in FIG. 1 according to the pattern information, the laser light B incident on the DMD 50 is reflected in the inclination direction of each micro mirror 62. The

  FIG. 1 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 the controller 302 connected to the DMD 50. Further, a light absorber (not shown) is arranged in the direction in which the laser beam B reflected by the off-state micromirror 62 travels.

  Further, it is preferable that the DMD 50 is arranged with a slight inclination so that the short side forms a predetermined angle θ (for example, 0.1 ° to 5 °) with the sub-scanning direction. 3A shows the scanning trajectory of the reflected light image (exposure beam) 53 by each micromirror when the DMD 50 is not tilted, and FIG. 3B shows the scanning trajectory of the exposure beam 53 when the DMD 50 is tilted. Show.

In the DMD 50, a number of micromirror arrays in which a number of micromirrors are arranged in the longitudinal direction (for example, 1024) are arranged in a short direction (for example, 756 pairs). as shown, by tilting the DMD 50, the pitch P ₁ of the scanning locus of the exposure beams 53 from each micromirror (scan line), it becomes narrower than the pitch P ₂ of the scanning lines in the case of not tilting the DMD 50, significant resolution Can be improved. On the other hand, the inclination angle of the DMD 50 is small, the scanning width _{W 2} in the case of tilting the DMD 50, which is substantially equal to the scanning width _{W 1} when not inclined DMD 50.

Next, a method for increasing the modulation speed in the optical modulation means (hereinafter referred to as “high-speed modulation”) will be described.
It is preferable that the light modulation means can control any less than n pixel parts arranged continuously from the n picture elements according to pattern information. There is a limit to the data processing speed of the light modulation means, and the modulation speed per line is determined in proportion to the number of pixels to be used. By using, the modulation speed per line is increased.

Hereinafter, the high-speed modulation will be further described with reference to the drawings.
When the laser light B is irradiated from the fiber array light source 66 to the DMD 50, the laser light reflected when the micromirror of the DMD 50 is in the on state is imaged on the pattern forming material 150 by the lens systems 54 and 58. In this manner, the laser light emitted from the fiber array light source 66 is turned on / off for each pixel, and the pattern forming material 150 is exposed in approximately the same number of pixel units (exposure area 168) as the number of used pixel elements of the DMD 50. . Further, when the pattern forming material 150 is moved at a constant speed together with the stage 152, the pattern forming material 150 is sub-scanned in the direction opposite to the stage moving direction by the scanner 162, and a strip-shaped exposed region 170 is provided for each exposure head 166. Is formed.

  In this example, as shown in FIGS. 4A and 4B, in the DMD 50, 768 sets of micromirror arrays in which 1024 micromirrors are arranged in the main scanning direction are arranged in the subscanning direction. In this example, the controller 302 performs control so that only a part of the micromirror rows (for example, 1024 × 256 rows) is driven.

  In this case, a micromirror array arranged at the center of the DMD 50 as shown in FIG. 4 (A) may be used, and a micromirror arranged at the end of the DMD 50 as shown in FIG. 4 (B). A column may be used. In addition, when a defect occurs in some of the micromirrors, the micromirror array to be used may be appropriately changed depending on the situation, such as using a micromirror array in which no defect has occurred.

  Since the data processing speed of the DMD 50 is limited and the modulation speed per line is determined in proportion to the number of pixels used, the modulation speed per line can be increased by using only a part of the micromirror array. Get faster. On the other hand, in the case of an exposure method in which the exposure head is continuously moved relative to the exposure surface, it is not necessary to use all the pixels in the sub-scanning direction.

  When the sub-scan of the pattern forming material 150 by the scanner 162 is finished and the rear end of the pattern forming material 150 is detected by the sensor 164, the stage 152 is moved upstream of the gate 160 along the guide 158 by the stage driving device 304. It returns to the origin on the side and is moved again along the guide 158 from the upstream side to the downstream side of the gate 160 at a constant speed.

  For example, in the case of using only 384 sets out of 768 sets of micromirror arrays, the modulation can be performed twice as fast per line as compared with the case of using all 768 sets. Also, when only 256 pairs are used in the 768 sets of micromirror arrays, modulation can be performed three times faster per line than when all 768 sets are used.

  As described above, according to the pattern forming method of the present invention, the micromirror array in which 1,024 micromirrors are arranged in the main scanning direction includes the DMD in which 768 sets are arranged in the subscanning direction. By controlling so that only a part of the micromirror rows are driven by the controller, the modulation rate per line becomes faster than when all the micromirror rows are driven.

  In addition, an example in which the DMD micromirror is partially driven has been described, but the length of the direction corresponding to the predetermined direction is reflected on the substrate longer than the length of the direction intersecting the predetermined direction according to the control signal. Even if a long and narrow DMD in which a large number of micromirrors capable of changing the surface angle are arranged in a two-dimensional manner is used, the number of micromirrors for controlling the angle of the reflecting surface is reduced. Can do.

  The exposure method is preferably performed while relatively moving the exposure light and the photosensitive layer, and in this case, it is preferable to use the high-speed modulation together. Thereby, high-speed exposure can be performed in a short time.

  In addition, as shown in FIG. 5, the entire surface of the pattern forming material 150 may be exposed by a single scan in the X direction by the scanner 162, and as shown in FIGS. 6A and 6B, the scanner 162. After the pattern forming material 150 is scanned in the X direction, the scanner 162 is moved one step in the Y direction, and scanning is performed in the X direction. Thus, the pattern forming material 150 is scanned a plurality of times. Alternatively, the entire surface may be exposed. In this example, the scanner 162 includes 18 exposure heads 166. Note that the exposure head includes at least the light irradiation unit and the light modulation unit.

  The exposure is performed on a partial area of the photosensitive layer to cure the partial area, and uncured areas other than the cured partial area are removed in a development step described later. A pattern is formed.

Next, an example of a pattern forming apparatus including the light modulation means will be described with reference to the drawings.
As shown in FIG. 7, the pattern forming apparatus including the light modulation means includes a flat plate stage 152 that holds a sheet-like pattern forming material 150 by adsorbing to the surface.
Two guides 158 extending along the stage moving direction are installed on the upper surface of the thick plate-like installation table 156 supported by the four legs 154. The stage 152 is arranged so that the longitudinal direction thereof faces the stage moving direction, and is supported by a guide 158 so as to be reciprocally movable. The pattern forming apparatus has a drive device (not shown) for driving the stage 152 along the guide 158.

  A U-shaped gate 160 is provided at the center of the installation table 156 so as to straddle the movement path of the stage 152. Each of the ends of the U-shaped gate 160 is fixed to both side surfaces of the installation table 156. A scanner 162 is provided on one side of the gate 160, and a plurality of (for example, two) detection sensors 164 for detecting the front and rear ends of the pattern forming material 150 are provided on the other side. . The scanner 162 and the detection sensor 164 are respectively attached to the gate 160 and fixedly arranged above the moving path of the stage 152. The scanner 162 and the detection sensor 164 are connected to a controller (not shown) that controls them.

As shown in FIGS. 8 and 9B, the scanner 162 includes a plurality of (for example, 14) exposure heads 166 arranged in a substantially matrix of m rows and n columns (for example, 3 rows and 5 columns). ing. In this example, four exposure heads 166 are arranged in the third row in relation to the width of the pattern forming material 150. In addition, when showing each exposure head arranged in the m-th row and the n-th column, it is expressed as an exposure head 166 _mn .

An exposure area 168 by the exposure head 166 has a rectangular shape with a short side in the sub-scanning direction. Accordingly, as the stage 152 moves, a strip-shaped exposed region 170 is formed in the pattern forming material 150 for each exposure head 166. In addition, when showing the exposure area by each exposure head arranged in the m-th row and the n-th column, it is expressed as an exposure area 168 _mn .

Further, as shown in FIGS. 9A and 9B, each of the exposure heads in each row arranged in a line so that the strip-shaped exposed regions 170 are arranged in the direction orthogonal to the sub-scanning direction without gaps. These are arranged with a predetermined interval (natural number times the long side of the exposure area, twice in this example) in the arrangement direction. Therefore, can not be exposed portion between the exposure area _{168 11} in the first row and the exposure area _{168 12,} it can be exposed by the second row of the exposure area _{168 21} and the exposure area _{168 31} in the third row.

As shown in FIGS. 10 and 11, each of the exposure heads 166 _{11 to} 166 _mn serves as the light modulation means (spatial light modulation element that modulates each pixel) according to the pattern information. A digital micromirror device (DMD) 50 manufactured by Texas Instruments, USA is provided. The DMD 50 is connected to a later-described controller 302 (see FIG. 12) having a data processing unit and a mirror drive control unit. The data processing unit of the controller 302 generates a control signal for driving and controlling each micromirror in the region to be controlled by the DMD 50 for each exposure head 166 based on the input pattern information. The area to be controlled will be described later. The mirror drive control unit controls the angle of the reflection surface of each micromirror of the DMD 50 for each exposure head 166 based on the control signal generated by the pattern information 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 66 including a laser emitting section in which emission ends (light emitting points) of an optical fiber are arranged in a line along a direction corresponding to the long side direction of the exposure area 168, a fiber A lens system 67 for correcting the laser light emitted from the array light source 66 and condensing it on the DMD, and a mirror 69 for reflecting the laser light transmitted through the lens system 67 toward the DMD 50 are arranged in this order. In FIG. 10, the lens system 67 is schematically shown.

  As shown in detail in FIG. 11, the lens system 67 is inserted into the optical path of the light passing through the condenser lens 71 and the condenser lens 71 that collects the laser light B as the illumination light emitted from the fiber array light source 66. A rod-shaped optical integrator (hereinafter referred to as a rod integrator) 72 and an imaging lens 74 disposed in front of the rod integrator 72, that is, on the mirror 69 side. The condensing lens 71, the rod integrator 72, and the imaging lens 74 cause the laser light emitted from the fiber array light source 66 to enter the DMD 50 as a light beam that is close to parallel light and has a uniform beam cross-sectional intensity. The shape and action of the rod integrator 72 will be described in detail later.

  The laser beam B emitted from the lens system 67 is reflected by the mirror 69 and irradiated to the DMD 50 via the TIR (total reflection) prism 70. In FIG. 10, the TIR prism 70 is omitted.

  An imaging optical system 51 that images the laser beam B reflected by the DMD 50 on the pattern forming material 150 is disposed on the light reflection side of the DMD 50. The imaging optical system 51 is schematically shown in FIG. 10, but as shown in detail in FIG. 11, the imaging optical system 51 includes a first imaging optical system including lens systems 52 and 54 and lens systems 57 and 58. The optical system includes a second imaging optical system, a microlens array 55 inserted between these imaging optical systems, and an aperture array 59.

The microlens array 55 is formed by two-dimensionally arranging a large number of microlenses 55a corresponding to the pixels of the DMD 50. In this example, as described later, only 1024 × 256 rows of the 1024 × 768 rows of micromirrors of the DMD 50 are driven, and accordingly, 1024 × 256 rows of microlenses 55a are arranged. The arrangement pitch of the micro lenses 55a is 41 μm in both the vertical and horizontal directions. As an example, the microlens 55a has a focal length of 0.19 mm, an NA (numerical aperture) of 0.11, and is formed from the optical glass BK7. The shape of the micro lens 55a will be described in detail later.
The beam diameter of the laser beam B at the position of each microlens 55a is 41 μm.

  The aperture array 59 is formed by forming a large number of apertures (openings) 59 a corresponding to the respective micro lenses 55 a of the micro lens array 55. The diameter of the aperture 59a is, for example, 10 μm.

  The first imaging optical system forms an image on the microlens array 55 by enlarging the image by the DMD 50 three times. The second imaging optical system enlarges the image that has passed through the microlens array 55 by 1.6 times, and forms and projects the image on the pattern forming material 150. Therefore, as a whole, the image formed by the DMD 50 is enlarged and enlarged by 4.8 times, and is imaged and projected on the pattern forming material 150.

  A prism pair 73 is disposed between the second imaging optical system and the pattern forming material 150. By moving the prism pair 73 in the vertical direction in FIG. 11, an image on the pattern forming material 150 is obtained. The focus can be adjusted. In the figure, the pattern forming material 150 is sub-scanned in the direction of arrow F.

The pixel portion is not particularly limited as long as it can receive and emit light from the light irradiation means, and can be appropriately selected according to the purpose. For example, the pattern forming method of the present invention When the pattern to be formed is an image pattern, it is a pixel, and when the light modulation means includes a DMD, it is a micromirror.
There is no restriction | limiting in particular as the number (the said n) of picture element parts which the said light modulation element has, It can select suitably according to the objective.
The arrangement of the picture element portions in the light modulation element is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably arranged in a two-dimensional form, and arranged in a lattice form. More preferably.

-Light irradiation means-
The light irradiation means is not particularly limited and may be appropriately selected depending on the purpose. For example, (ultra) high pressure mercury lamp, xenon lamp, carbon arc lamp, halogen lamp, copier, fluorescent tube, LED, etc. , A known light source such as a semiconductor laser, or a means capable of synthesizing and irradiating two or more lights. Among these, a means capable of synthesizing and irradiating two or more lights is preferable.
The light emitted from the light irradiation means is, for example, an electromagnetic wave that passes through the support and activates the photopolymerization initiator and sensitizer used when the light is irradiated through the support. In particular, ultraviolet to visible light, electron beam, X-ray, laser beam, and the like can be mentioned. Of these, laser beam is preferable, and a laser combining two or more lights (hereinafter, referred to as “combined laser”). More preferred. Even when light irradiation is performed after the support is peeled off, the same light can be used.

The wavelength of the light irradiated from the light irradiation means is not particularly limited as long as the exposed photosensitive layer is photosensitive and cured, but the wavelength of ultraviolet to visible light is, for example, 300 to 1500 nm. Is preferable, 320 to 800 nm is more preferable, and 330 nm to 650 nm is particularly preferable.
Moreover, as a wavelength of the said laser beam, 200-1500 nm is preferable, for example, 300-800 nm is more preferable, 330 nm-500 nm is still more preferable, 400-410 nm is especially preferable. Specifically, laser light with a wavelength of 405 nm emitted from a GaN-based semiconductor laser is most preferable.

  Examples of means capable of irradiating the combined laser include, for example, a plurality of lasers, a multimode optical fiber, and collective optics for condensing and coupling the laser beams respectively emitted from the plurality of lasers to the multimode optical fiber. Means having a system are preferred.

  Hereinafter, means (fiber array light source) capable of irradiating the combined laser will be described with reference to the drawings.

  As shown in FIG. 27 a, the fiber array light source 66 includes a plurality of (for example, 14) laser modules 64, and one end of the multimode optical fiber 30 is coupled to each laser module 64. An optical fiber 31 having the same core diameter as that of the multimode optical fiber 30 and a smaller cladding diameter than the multimode optical fiber 30 is coupled to the other end of the multimode optical fiber 30. As shown in detail in FIG. 27b, seven end portions of the multimode optical fiber 31 opposite to the optical fiber 30 are arranged along the main scanning direction orthogonal to the sub-scanning direction, and they are arranged in two rows to form a laser. An emission unit 68 is configured.

  As shown in FIG. 27b, the laser emitting portion 68 configured by the end portion of the multimode optical fiber 31 is sandwiched and fixed between two support plates 65 having a flat surface. In addition, a transparent protective plate such as glass is preferably disposed on the light emitting end face of the multimode optical fiber 31 for protection. The light exit end face of the multimode optical fiber 31 has high light density and is likely to collect dust and easily deteriorate. However, the protective plate as described above prevents the dust from adhering to the end face and deteriorates. Can be delayed.

  In this example, in order to arrange the emission ends of the optical fibers 31 with a small cladding diameter in a line without any gaps, the multimode optical fiber 30 is placed between two adjacent multimode optical fibers 30 at a portion with a large cladding diameter. Two exit ends of the optical fiber 31 coupled to the two multimode optical fibers 30 adjacent to each other at the portion where the cladding diameter is large are the exit ends of the optical fiber 31 coupled to the stacked and stacked multimode optical fibers 30. Are arranged so as to be sandwiched between them.

  For example, as shown in FIG. 28, an optical fiber 31 having a length of 1 to 30 cm and having a small cladding diameter is coaxially connected to the tip portion of the multimode optical fiber 30 having a large cladding diameter on the laser light emission side. Can be obtained by linking them together. In the two optical fibers, the incident end face of the optical fiber 31 is fused and joined to the outgoing end face of the multimode optical fiber 30 so that the central axes of both optical fibers coincide. As described above, the diameter of the core 31 a of the optical fiber 31 is the same as the diameter of the core 30 a of the multimode optical fiber 30.

  In addition, a short optical fiber in which an optical fiber having a short cladding diameter and a large cladding diameter is fused to an optical fiber having a short cladding diameter and a large cladding diameter may be coupled to the output end of the multimode optical fiber 30 via a ferrule or an optical connector. Good. By detachably coupling using a connector or the like, the tip portion can be easily replaced when an optical fiber having a small cladding diameter is broken, and the cost required for exposure head maintenance can be reduced. Hereinafter, the optical fiber 31 may be referred to as an emission end portion of the multimode optical fiber 30.

  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.

  In general, in the laser light in the infrared region, the propagation loss increases as the cladding diameter of the optical fiber is reduced. For this reason, a suitable cladding diameter is determined according to the wavelength band of the laser beam. However, the shorter the wavelength, the smaller the propagation loss. In the case of laser light having a wavelength of 405 nm emitted from a GaN-based semiconductor laser, the cladding thickness {(cladding diameter−core diameter) / 2} is set to an infrared light having a wavelength band of 800 nm. The propagation loss hardly increases even if it is about ½ of the case of propagating infrared light and about ¼ of the case of propagating infrared light in the 1.5 μm wavelength band for communication. Therefore, the cladding diameter can be reduced to 60 μm.

  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 array 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, preferably 60 μm or less. More 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 includes a combined laser light source (fiber array 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.

  As shown in FIGS. 30 and 31, the combined laser light source is housed in a box-shaped package 40 having an upper opening together with other optical elements. The package 40 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, and the heat block 10, a condensing lens holder 45 that holds the condensing lens 20, and the multimode optical fiber 30 are disposed on the top surface of the base plate 42. A fiber holder 46 that holds the incident end 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. 31, in order to avoid complication of the figure, only the GaN-based semiconductor laser LD7 among the plurality of GaN-based semiconductor lasers is numbered, and only the collimator lens 17 among the plurality of collimator lenses is numbered. is doing.

  FIG. 32 shows a front shape of a mounting portion of the collimator lenses 11 to 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. 32).

  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 in which the divergence angles in a direction parallel to and perpendicular to the active layer are 10 ° and 30 °, respectively. 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.

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

  In addition, since the light emitting means for illuminating the DMD uses a high-intensity fiber array light source in which the output ends of the optical fibers of the combined laser light source are arranged in an array, it has a high output and a deep depth of focus. A pattern forming apparatus can be realized. Furthermore, since the output of each fiber array light source is increased, the number of fiber array light sources required to obtain a desired output is reduced, and the cost of the pattern forming apparatus can be reduced.

  In addition, since the cladding diameter at the exit end of the optical fiber is smaller than the cladding diameter at the entrance end, the diameter of the light emitting portion is further reduced, and the brightness of the fiber array light source can be increased. Thereby, a pattern forming apparatus having a deeper depth of focus can be realized. For example, even in the case of ultra-high resolution exposure with a beam diameter of 1 μm or less and a resolution of 0.1 μm or less, a deep depth of focus can be obtained, and high-speed and high-definition exposure is possible. Therefore, it is suitable for a thin film transistor (TFT) exposure process that requires high resolution.

  The light irradiating means is not limited to a fiber array light source including a plurality of the combined laser light sources, and for example, emits laser light incident from a single semiconductor laser having one light emitting point. A fiber array light source in which fiber light sources including optical fibers are arrayed can be used.

  Further, as the light irradiation means having a plurality of light emitting points, for example, as shown in FIG. 33, a laser in which a plurality of (for example, seven) chip-shaped semiconductor lasers LD1 to LD7 are arranged on the heat block 100. An array can be used. A chip-shaped multicavity laser 110 in which a plurality of (for example, five) light emitting points 110a shown in FIG. 34A is arranged in a predetermined direction is known. Since the multicavity laser 110 can arrange the light emitting points with high positional accuracy as compared with the case where the chip-shaped semiconductor lasers are arranged, it is easy to multiplex the laser beams emitted from the respective light emitting points. However, as the number of light emitting points increases, the multicavity laser 110 is likely to be bent at the time of laser manufacturing. Therefore, the number of light emitting points 110a is preferably 5 or less.

  As the light irradiation means, the multi-cavity laser 110 or a plurality of multi-cavity lasers 110 on the heat block 100 in the same direction as the arrangement direction of the light emitting points 110a of each chip as shown in FIG. An arrayed multi-cavity laser array can be used as a laser light source.

  The combined laser light source is not limited to one that combines laser beams emitted from a plurality of chip-shaped semiconductor lasers. For example, as shown in FIG. 21, a combined laser light source including a chip-shaped multicavity laser 110 having a plurality of (for example, three) light emitting points 110a can be used. This combined laser light source is configured to include a multi-cavity laser 110, one multi-mode optical fiber 130, and a condensing lens 120. The multi-cavity laser 110 can be composed of, for example, a GaN-based laser diode having an oscillation wavelength of 405 nm.

  In the above configuration, each of the laser beams B emitted from each of the plurality of light emitting points 110 a of the multicavity laser 110 is collected by the condenser lens 120 and enters the core 130 a of the multimode optical fiber 130. The laser light incident on the core 130a propagates in the optical fiber, is combined into one, and is emitted.

  A plurality of light emitting points 110 a of the multicavity laser 110 are arranged in parallel within a width substantially equal to the core diameter of the multimode optical fiber 130, and a focal point substantially equal to the core diameter of the multimode optical fiber 130 is formed as the condenser lens 120. By using a convex lens of a distance or a rod lens that collimates the outgoing beam from the multi-cavity laser 110 only in a plane perpendicular to the active layer, the coupling efficiency of the laser beam B to the multi-mode optical fiber 130 can be increased. it can.

  As shown in FIG. 35, a multi-cavity laser 110 having a plurality of (for example, three) emission points is used, and a plurality of (for example, nine) multi-cavity lasers 110 are equidistant from each other on the heat block 111. A combined laser light source including the laser array 140 arranged in (1) can be used. The plurality of multi-cavity lasers 110 are arranged and fixed in the same direction as the arrangement direction of the light emitting points 110a of each chip.

  This combined laser light source includes a laser array 140, a plurality of lens arrays 114 arranged corresponding to each multi-cavity laser 110, and a single rod arranged between the laser array 140 and the plurality of lens arrays 114. The lens 113, one multimode optical fiber 130, and a condenser lens 120 are provided. The lens array 114 includes a plurality of microlenses corresponding to the emission points of the multicavity laser 110.

  In the above configuration, each of the laser beams B emitted from each of the plurality of light emitting points 110a of the plurality of multi-cavity lasers 110 is collected in a predetermined direction by the rod lens 113, and then each microlens of the lens array 114. It becomes parallel light. The collimated laser beam L is condensed by the condensing lens 120 and enters the core 130a of the multimode optical fiber 130. The laser light incident on the core 130a propagates in the optical fiber, is combined into one, and is emitted.

  Still another example of the combined laser light source will be described. In this combined laser light source, as shown in FIGS. 36A and 36B, a heat block 182 having an L-shaped cross section in the optical axis direction is mounted on a substantially rectangular heat block 180, and two heats are provided. A storage space is formed between the blocks. On the upper surface of the L-shaped heat block 182, a plurality of (for example, two) multi-cavity lasers 110 in which a plurality of light emitting points (for example, five) are arranged in an array form the light emitting points 110a of each chip. It is arranged and fixed at equal intervals in the same direction as the arrangement direction.

  A concave portion is formed in the substantially rectangular heat block 180, and a plurality of (for example, two) light emitting points (for example, five) are arranged in an array on the upper surface of the space side of the heat block 180. The multi-cavity laser 110 is arranged such that its emission point is located on the same vertical plane as the emission point of the laser chip arranged on the upper surface of the heat block 182.

  On the laser beam emission side of the multi-cavity laser 110, a collimator lens array 184 in which collimator lenses are arranged corresponding to the light emission points 110a of the respective chips is arranged. In the collimating lens array 184, the length direction of each collimating lens coincides with the direction in which the laser beam divergence angle is large (fast axis direction), and the width direction of each collimating lens is in the direction in which the divergence angle is small (slow axis direction). They are arranged to match. Thus, by collimating and integrating the collimating lenses, the space utilization efficiency of the laser light can be improved, the output of the combined laser light source can be increased, and the number of parts can be reduced and the cost can be reduced. .

  Further, on the laser light emitting side of the collimating lens array 184, there is one multimode optical fiber 130 and a condensing lens 120 that condenses and couples the laser light to the incident end of the multimode optical fiber 130. Has been placed.

  In the above-described configuration, each of the laser beams B emitted from each of the plurality of light emitting points 110a of the plurality of multicavity lasers 110 arranged on the laser blocks 180 and 182 is collimated by the collimating lens array 184 and condensed. The light is condensed by the lens 120 and enters the core 130 a of the multimode optical fiber 130. The laser light incident on the core 130a propagates in the optical fiber, is combined into one, and is emitted.

  As described above, the combined laser light source can achieve particularly high output by the multistage arrangement of multicavity lasers and the array of collimating lenses. By using this combined laser light source, a higher-intensity fiber array light source or bundle fiber light source can be configured, so that it is particularly suitable as a fiber light source constituting the laser light source of the pattern forming apparatus of the present invention.

  It should be noted that a laser module in which each of the combined laser light sources is housed in a casing and the emission end of the multimode optical fiber 130 is pulled out from the casing can be configured.

  In addition, the other end of the multimode optical fiber of the combined laser light source is coupled with another optical fiber having the same core diameter as the multimode optical fiber and a cladding diameter smaller than the multimode optical fiber. However, for example, a multimode optical fiber having a cladding diameter of 125 μm, 80 μm, 60 μm or the like may be used without coupling another optical fiber to the emission end.

Here, the pattern forming method of the present invention will be further described.
In each exposure head 166 of the scanner 162, laser light B1, B2, B3, B4, B5, B6 emitted in a divergent light state from each of the GaN-based semiconductor lasers LD1 to LD7 constituting the combined laser light source of the fiber array light source 66. , And B7 are collimated by corresponding collimator lenses 11-17. The collimated laser beams B <b> 1 to B <b> 7 are collected by the condenser lens 20 and converge on the incident end face of the core 30 a of the multimode optical fiber 30.

  In this example, the collimator lenses 11 to 17 and the condenser lens 20 constitute a condensing optical system, and the condensing optical system and the multimode optical fiber 30 constitute a multiplexing optical system. That is, the laser beams B1 to B7 collected as described above by the 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, the light arranged in an array For each of the fibers 31, a combined laser beam B with an output of 180 mW (= 30 mW × 0.85 × 7) can be obtained. Therefore, the output from the laser emitting unit 68 in which the six optical fibers 31 are arranged in an array is about 1 W (= 180 mW × 6).

  In the laser emitting portion 68 of the fiber array light source 66, light emission points with high luminance are arranged in a line along 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 that a desired output cannot be obtained unless multiple rows are arranged. Since the laser light source 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. Since a multimode optical fiber having a numerical aperture (NA) of 0.2 is used, if an output of about 1 W (watt) is to be obtained, 48 multimode optical fibers (8 × 6) must be bundled. Narazu, the area of the light emitting region 0.62 mm ² because it is (0.675mm × 0.925mm), the luminance at laser emitting portion 68 is ^{1.6 × 10 6 (W / m} 2), 1 present optical fiber The luminance per hit is 3.2 × 10 ⁶ (W / m ² ).

On the other hand, when the light irradiating means is a means capable of irradiating a combined laser, an output of about 1 W can be obtained with six multimode optical fibers, and the area of the light emitting region at the laser emitting portion 68 can be obtained. Is 0.0081 mm ² (0.325 mm × 0.025 mm), the luminance at the laser emitting portion 68 is 123 × 10 ⁶ (W / m ² ), which is about 80 times higher than the conventional luminance. be able to. Further, the luminance per optical fiber is 90 × 10 ⁶ (W / m ² ), and the luminance can be increased by about 28 times compared to the conventional one.

  Here, with reference to FIGS. 37A and 37B, the difference in depth of focus between the conventional exposure head and the exposure head of the present embodiment will be described. The diameter of the light emission region of the bundled fiber light source of the conventional exposure head in the sub-scanning direction is 0.675 mm, and the diameter of the light emission region of the fiber array light source of the exposure head in the sub-scanning direction is 0.025 mm. As shown in FIG. 37A, in the conventional exposure head, since the light emitting area of the light irradiating means (bundle-shaped fiber light source) 1 is large, the angle of the light beam incident on the DMD 3 is increased, and as a result, the scanning surface 5 is moved. The angle of the incident light beam increases. For this reason, the beam diameter tends to increase with respect to the light condensing direction (shift in the focus direction).

  On the other hand, as shown in FIG. 37B, in the exposure head in the pattern forming apparatus of the present invention, the diameter of the light emitting region of the fiber array light source 66 in the sub-scanning direction is small, so that it passes through the lens system 67 and enters the DMD 50. As a result, the angle of the light beam incident on the scanning surface 56 is reduced. That is, the depth of focus becomes deep. In this example, the diameter of the light emitting region in the sub-scanning direction is about 30 times that of the conventional one, and a depth of focus substantially corresponding to the diffraction limit can be obtained. Therefore, it is suitable for exposure of a minute spot. This effect on the depth of focus is more prominent and effective as the required light quantity of the exposure head is larger. In this example, the size of one pixel projected on the exposure surface is 10 μm × 10 μm. The DMD is a reflective spatial light modulator, but FIGS. 37A and 37B are developed views for explaining the optical relationship.

  Pattern information corresponding to the exposure pattern is input to a controller (not shown) connected to the DMD 50 and temporarily stored in a frame memory in the controller. This pattern information is data representing the density of each pixel constituting the image as binary values (whether or not dots are recorded).

  The stage 152 having the pattern forming material 150 adsorbed on the surface thereof is moved at a constant speed from the upstream side to the downstream side of the gate 160 along the guide 158 by a driving device (not shown). When the leading edge of the pattern forming material 150 is detected by the detection sensor 164 attached to the gate 160 while the stage 152 passes under the gate 160, the pattern information stored in the frame memory is sequentially read out for a plurality of lines. Then, a control signal is generated for each exposure head 166 based on the pattern information read by the data processing unit. Then, each of the micromirrors of the DMD 50 is controlled on and off for each exposure head 166 based on the generated control signal by the mirror drive control unit.

  When the DMD 50 is irradiated with laser light from the fiber array light source 66, the laser light reflected when the micromirror of the DMD 50 is in the on state is coupled onto the exposed surface 56 of the pattern forming material 150 by the lens systems 54 and 58. Imaged. In this manner, the laser light emitted from the fiber array light source 66 is turned on / off for each pixel, and the pattern forming material 150 is exposed in the number of pixel units (exposure area 168) substantially equal to the number of used pixel elements of the DMD 50. . Further, when the pattern forming material 150 is moved at a constant speed together with the stage 152, the pattern forming material 150 is sub-scanned in the direction opposite to the stage moving direction by the scanner 162, and a strip-shaped exposed region 170 is provided for each exposure head 166. Is formed.

-Micro lens array-
The exposure is preferably performed using the modulated light through a microlens array, and may be performed through an aperture array, an imaging optical system, or the like.

  The microlens array is not particularly limited and may be appropriately selected according to the purpose. For example, microlenses having an aspheric surface capable of correcting aberration due to distortion of the exit surface in the pixel portion are arranged. A thing is mentioned suitably.

  There is no restriction | limiting in particular as said aspherical surface, Although it can select suitably according to the objective, For example, a toric surface is preferable.

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

FIG. 13A shows each of DMD 50, light irradiation means 144 for irradiating the DMD 50 with laser light, lens systems (imaging optical systems) 454, 458, and DMD 50 for enlarging and imaging the laser light reflected by the DMD 50. A microlens array 472 in which a large number of microlenses 474 are arranged corresponding to the picture element portion, an aperture array 476 in which a large number of apertures 478 are provided corresponding to each microlens of the microlens array 472, and a laser that has passed through the aperture An exposure head composed of lens systems (imaging optical systems) 480 and 482 for forming an image of light on an exposed surface 56 is shown.
Here, FIG. 14 shows the result of measuring the flatness of the reflecting surface of the micromirror 62 constituting the DMD 50. In the figure, the same height positions of the reflecting surfaces are shown connected by contour lines, and the pitch of the contour lines is 5 nm. Note that the x direction and the y direction shown in the figure are two diagonal directions of the micromirror 62, and the micromirror 62 rotates around the rotation axis extending in the y direction as described above. 15A and 15B show the height position displacement of the reflecting surface of the micromirror 62 along the x direction and the y direction, respectively.

  As shown in FIGS. 14 and 15, there is distortion on the reflection surface of the micromirror 62, and when attention is paid particularly to the center of the mirror, distortion in one diagonal direction (y direction) is different from that in the other diagonal line. It is larger than the distortion in the direction (x direction). For this reason, the problem that the shape in the condensing position of the laser beam B condensed with the micro lens 55a of the micro lens array 55 may be distorted may occur.

  In the pattern forming method of the present invention, in order to prevent the above problem, the microlens 55a of the microlens array 55 has a special shape different from the conventional one. Hereinafter, this point will be described in detail.

  FIGS. 16A and 16B respectively show the front and side shapes of the entire microlens array 55 in detail. These drawings also show the dimensions of each part of the microlens array 55, and the unit thereof is mm. In the pattern forming method of the present invention, as described above with reference to FIG. 4, the 1024 × 256 rows of micromirrors 62 of the DMD 50 are driven. A row of 1024 microlenses 55a arranged in the direction is arranged in parallel in the vertical direction. In FIG. 9A, the arrangement order of the microlens array 55 is indicated by j in the horizontal direction and k in the vertical direction.

  17A and 17B show the front shape and the side shape of one microlens 55a in the microlens array 55, respectively. In FIG. 9A, the contour lines of the micro lens 55a are also shown. The end surface of each microlens 55a on the light emitting side has an aspherical shape that corrects aberration due to distortion of the reflecting surface of the micromirror 62. More specifically, the micro lens 55a is a toric lens, and has a radius of curvature Rx = −0.125 mm in a direction optically corresponding to the x direction and a radius of curvature Ry = − in a direction corresponding to the y direction. 0.1 mm.

  Therefore, the condensing state of the laser beam B in the cross section parallel to the x direction and the y direction is roughly as shown in FIGS. 18A and 18B, respectively. That is, when the cross section parallel to the x direction is compared with the cross section parallel to the y direction, the radius of curvature of the microlens 55a is smaller and the focal length is shorter in the latter cross section. .

  19A, 19B, 19D, and 19D show simulation results of the beam diameter in the vicinity of the condensing position (focal position) of the microlens 55a when the microlens 55a has the above shape. For comparison, FIGS. 20a, 20b, 20c, and 20d show the results of a similar simulation when the microlens 55a has a spherical shape with a radius of curvature Rx = Ry = −0.1 mm. In addition, the value of z in each figure has shown the evaluation position of the focus direction of the micro lens 55a with the distance from the beam emission surface of the micro lens 55a.

The surface shape of the microlens 55a used for the simulation is calculated by the following calculation formula.

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

  19A to 19D and FIGS. 20A to 20D, in the pattern forming method of the present invention, the microlens 55a is focused on the micro lens 55a with a focal length in a cross section parallel to the y direction. By using a toric lens smaller than the distance, distortion of the beam shape in the vicinity of the condensing position is suppressed. If so, the pattern forming material 150 can be exposed to a higher-definition image without distortion. In addition, it can be seen that in the present embodiment shown in FIGS. 21 a to 21 d, the region where the beam diameter is small is wider, that is, the depth of focus is larger.

  In addition, when the magnitude relationship of the distortion of the center part in the x direction and the y direction of the micromirror 62 is opposite to the above, the focal length in the cross section parallel to the x direction is in the cross section parallel to the y direction. If the microlens is made up of a toric lens that is smaller than the focal length, similarly, a higher-definition image without distortion can be exposed to the pattern forming material 150.

  In addition, the aperture array 59 disposed in the vicinity of the condensing position of the microlens array 55 is disposed such that only light having passed through the corresponding microlens 55a is incident on each aperture 59a. That is, by providing this aperture array 59, it is possible to prevent light from adjacent microlenses 55a not corresponding to each aperture 59a from entering, and to increase the extinction ratio.

  Originally, if the diameter of the aperture 59a of the aperture array 59 installed for the above purpose is reduced to some extent, an effect of suppressing the distortion of the beam shape at the condensing position of the microlens 55a can be obtained. However, in such a case, the amount of light blocked by the aperture array 59 is increased, and the light use efficiency is reduced. On the other hand, when the microlens 55a has an aspherical shape, the light utilization efficiency is kept high because the light is not blocked.

  In the pattern forming method of the present invention, the microlens 55a may have a secondary aspherical shape or a higher order (4th, 6th,...) Aspherical shape. By adopting the higher order aspherical shape, the beam shape can be further refined.

  In the embodiment described above, the end surface on the light emission side of the micro lens 55a is an aspherical surface (toric surface). However, one of the two light passing end surfaces is a spherical surface and the other is a cylindrical surface. Thus, the microlens array can be configured to obtain the same effect as the above embodiment.

  Furthermore, in the embodiment described above, the microlens 55a of the microlens array 55 has an aspherical shape that corrects aberration due to distortion of the reflecting surface of the micromirror 62. Such an aspherical shape is adopted. Instead, the same effect can be obtained even if each microlens constituting the microlens array has a refractive index distribution that corrects aberration due to distortion of the reflection surface of the micromirror 62.

  An example of such a microlens 155a is shown in FIG. (A) and (B) of the same figure respectively show the front shape and side shape of the micro lens 155a, and the external shape of the micro lens 155a is a parallel plate shape as shown in the figure. The x and y directions in the figure are as described above.

  23A and 23B schematically show the condensing state of the laser beam B in the cross section parallel to the x direction and the y direction by the micro lens 155a. The microlens 155a has a refractive index distribution that gradually increases outward from the optical axis O. In the drawing, the broken line shown in the microlens 155a indicates that the refractive index is predetermined from the optical axis O. The position changed with the pitch is shown. As shown in the figure, when the cross section parallel to the x direction and the cross section parallel to the y direction are compared, the ratio of the refractive index change of the microlens 155a is larger in the latter cross section, and the focal length is larger. It is shorter. Even when a microlens array composed of such a gradient index lens is used, it is possible to obtain the same effect as when the microlens array 55 is used.

  In addition, in the microlens whose surface shape is aspherical like the microlens 55a previously shown in FIGS. 17 and 18, the refractive index distribution as described above is given together, and both by the surface shape and the refractive index distribution. The aberration due to the distortion of the reflection surface of the micromirror 62 may be corrected.

  In the above embodiment, the aberration due to the distortion of the reflection surface of the micromirror 62 constituting the DMD 50 is corrected. However, in the pattern forming method of the present invention using the spatial light modulator other than the DMD, the spatial light is also corrected. If there is distortion on the surface of the picture element portion of the modulation element, the present invention can be applied to correct the aberration caused by the distortion and prevent the beam shape from being distorted.

Next, the imaging optical system will be further described.
In the exposure head, when the laser beam is irradiated from the light irradiation means 144, the cross-sectional area of the beam line reflected in the ON direction by the DMD 50 is enlarged several times (for example, two times) by the lens systems 454 and 458. The The enlarged laser light is condensed by each microlens of the microlens array 472 so as to correspond to each pixel part of the DMD 50 and passes through the corresponding aperture of the aperture array 476. The laser light that has passed through the aperture is imaged on the exposed surface 56 by the lens systems 480 and 482.

  In this imaging optical system, the laser light reflected by the DMD 50 is magnified several times by the magnifying lenses 454 and 458 and projected onto the exposed surface 56, so that the entire image area is widened. At this time, if the microlens array 472 and the aperture array 476 are not arranged, as shown in FIG. 13B, one pixel size (spot size) of each beam spot BS projected onto the exposed surface 56 is set. MTF (Modulation Transfer Function) characteristics representing the sharpness of the exposure area 468 are reduced depending on the size of the exposure area 468.

  On the other hand, when the microlens array 472 and the aperture array 476 are arranged, the laser light reflected by the DMD 50 is condensed corresponding to each pixel part of the DMD 50 by each microlens of the microlens array 472. Accordingly, as shown in FIG. 13C, even when the exposure area is enlarged, the spot size of each beam spot BS can be reduced to a desired size (for example, 10 μm × 10 μm), and the MTF characteristics are obtained. It is possible to perform high-definition exposure while preventing a decrease in the image quality. The exposure area 468 is tilted because the DMD 50 is tilted and arranged in order to eliminate the gap between the pixels.

  In addition, the aperture array can shape the beam so that the spot size on the surface to be exposed 56 is constant even if the beam is thick due to the aberration of the micro lens. Thus, crosstalk between adjacent picture elements can be prevented by passing through the aperture array.

  Further, by using a high-intensity light source, which will be described later, as the light irradiating means 144, the angle of the light beam incident on each microlens of the microlens array 472 from the lens 458 becomes small. The incident can be prevented. That is, a high extinction ratio can be realized.

-Other optical systems-
In the pattern forming method of the present invention, it may be used in combination with other optical systems appropriately selected from known optical systems, for example, a light amount distribution correcting optical system composed of a pair of combination lenses.
The light amount distribution correcting optical system changes the light flux width at each exit position so that the ratio of the light flux width at the peripheral portion to the light flux width at the central portion close to the optical axis is smaller on the exit side than on the incident side. When the DMD is irradiated with the parallel light beam from the light irradiation means, the light amount distribution on the irradiated surface is corrected so as to be substantially uniform. Hereinafter, the light quantity distribution correcting optical system will be described with reference to the drawings.

  First, as shown in FIG. 24A, the case where the entire luminous flux widths (total luminous flux widths) H0 and H1 are the same for the incident luminous flux and the outgoing luminous flux will be described. In FIG. 24A, the portions denoted by reference numerals 51 and 52 virtually indicate the entrance surface and the exit surface in the light quantity distribution correction optical system.

  In the light quantity distribution correcting optical system, it is assumed that the light flux widths h0 and h1 of the light beam incident on the central portion near the optical axis Z1 and the light flux incident on the peripheral portion are the same (h0 = hl). The light quantity distribution correcting optical system expands the light flux width h0 of the incident light flux at the central portion with respect to the light having the same light flux width h0, h1 on the incident side, and conversely changes the incident light flux at the peripheral portion. On the other hand, the light beam width h1 is reduced. That is, the width h10 of the outgoing light beam at the center and the width h11 of the outgoing light beam at the periphery are set to satisfy h11 <h10. In terms of the ratio of the luminous flux width, the ratio “h11 / h10” of the luminous flux width in the peripheral portion to the luminous flux width in the central portion on the emission side is smaller than the ratio (h1 / h0 = 1) on the incident side ( (H11 / h10) <1).

  By changing the light flux width in this way, the light flux in the central part, which normally has a large light quantity distribution, can be utilized in the peripheral part where the light quantity is insufficient, and the overall light utilization efficiency is not reduced. In addition, the light quantity distribution on the irradiated surface is made substantially uniform. The degree of uniformity is, for example, such that the unevenness in the amount of light in the effective area is within 30%, preferably within 20%.

  The operations and effects of the light quantity distribution correcting optical system are the same when the entire luminous flux width is changed between the incident side and the exit side (FIGS. 24B and 24C).

  FIG. 24B shows a case where the entire light flux width H0 on the incident side is “reduced” to the width H2 and emitted (H0> H2). Even in such a case, the light quantity distribution correcting optical system has the same light beam width h0, h1 on the incident side, and the light beam width h10 in the central part is larger than that in the peripheral part on the emission side. Conversely, the luminous flux width h11 at the peripheral part is made smaller than that at the central part. Considering the reduction rate of the light beam, the reduction rate with respect to the incident light beam in the central part is made smaller than that in the peripheral part, and the reduction rate with respect to the incident light beam in the peripheral part is made larger than that in the central part. Also in this case, the ratio “H11 / H10” of the light flux width in the peripheral portion to the light flux width in the central portion is smaller than the ratio (h1 / h0 = 1) on the incident side ((h11 / h10) <1). .

  FIG. 24C shows a case where the entire light flux width H0 on the incident side is “enlarged” by the width Η3 and emitted (H0 <H3). Even in such a case, the light quantity distribution correcting optical system has the same light beam width h0, h1 on the incident side, and the light beam width h10 in the central part is larger than that in the peripheral part on the emission side. Conversely, the luminous flux width h11 at the peripheral part is made smaller than that at the central part. Considering the expansion rate of the light beam, the expansion rate for the incident light beam in the central portion is made larger than that in the peripheral portion, and the expansion rate for the incident light beam in the peripheral portion is made smaller than that in the central portion. Also in this case, the ratio “h11 / h10” of the light flux width in the peripheral portion to the light flux width in the central portion is smaller than the ratio (h1 / h0 = 1) on the incident side ((h11 / h10) <1). .

  As described above, the light quantity distribution correcting optical system changes the light beam width at each emission position, and the ratio of the light beam width in the peripheral part to the light beam width in the central part near the optical axis Z1 is larger on the outgoing side than on the incident side. Since the light having the same luminous flux width on the incident side is larger on the outgoing side, the luminous flux width in the central portion is larger than that in the peripheral portion, and the luminous flux width in the peripheral portion is smaller than that in the central portion. Become smaller. As a result, it is possible to make use of the light beam at the center part to the peripheral part, and it is possible to form a light beam cross-section with a substantially uniform light amount distribution without reducing the light use efficiency of the entire optical system.

Next, an example of specific lens data of a pair of combination lenses used as the light quantity distribution correcting optical system will be shown. In this example, lens data in the case where the light amount distribution in the cross section of the emitted light beam is a Gaussian distribution as in the case where the light irradiation means is a laser array light source is shown. When one semiconductor laser is connected to the incident end of the single mode optical fiber, the light quantity distribution of the emitted light beam from the optical fiber becomes a Gaussian distribution. The pattern forming method of the present invention can be applied to such a case. Further, the present invention can be applied to a case where the light amount in the central portion near the optical axis is larger than the light amount in the peripheral portion, for example, by reducing the core diameter of the multi-mode optical fiber and approaching the configuration of the single mode optical fiber.
Table 1 below shows basic lens data.

  As can be seen from Table 1, the pair of combination lenses is composed of two rotationally symmetric aspherical lenses. If the light incident side surface of the first lens disposed on the light incident side is the first surface and the light exit side surface is the second surface, the first surface is aspherical. In addition, when the surface on the light incident side of the second lens disposed on the light emitting side is the third surface and the surface on the light emitting side is the fourth surface, the fourth surface is aspherical.

In Table 1, the surface number Si indicates the number of the i-th surface (i = 1 to 4), the curvature radius ri indicates the curvature radius of the i-th surface, and the surface interval di indicates the i-th surface and the i + 1-th surface. The distance between surfaces on the optical axis is shown. The unit of the surface interval di value is millimeter (mm). The refractive index Ni indicates the value of the refractive index with respect to the wavelength of 405 nm of the optical element having the i-th surface.
Table 2 below shows the aspheric data of the first surface and the fourth surface.

  The aspheric data is expressed by a coefficient in the following formula (A) that represents the aspheric shape.

In the above formula (A), each coefficient is defined as follows.
Z: Length of a perpendicular line (mm) drawn from a point on the aspheric surface at a height ρ from the optical axis to the tangent plane (plane perpendicular to the optical axis) of the apex of the aspheric surface
ρ: Distance from optical axis (mm)
K: Conic coefficient C: Paraxial curvature (1 / r, r: Paraxial radius of curvature)
ai: i-th order (i = 3 to 10) aspheric coefficient In the numerical values shown in Table 2, the symbol “E” indicates that the subsequent numerical value is a “power exponent” with 10 as the base. The numerical value represented by the exponential function with the base of 10 is multiplied by the numerical value before “E”. For example, “1.0E-02” indicates “1.0 × 10 ⁻² ”.

  FIG. 26 shows a light amount distribution of illumination light obtained by the pair of combination lenses shown in Tables 1 and 2. The horizontal axis indicates coordinates from the optical axis, and the vertical axis indicates the light amount ratio (%). For comparison, FIG. 25 shows a light amount distribution (Gaussian distribution) of illumination light when correction is not performed. As can be seen from FIG. 25 and FIG. 26, the light amount distribution correction optical system corrects the light amount distribution that is substantially uniform as compared with the case where correction is not performed. Thereby, it is possible to perform exposure with uniform laser light without reducing the use efficiency of light, without causing any unevenness.

<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. By the entire surface exposure, curing of the resin in the pattern forming material for forming the photosensitive layer is accelerated, 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 pattern forming material is decomposed, and the film quality is weak and brittle. There is.
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 exhibits a function as a protective film or an insulating film (interlayer insulating film), 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. When the permanent pattern formed by the permanent pattern forming method is the protective film, the interlayer insulating film, and the solder resist pattern, the wiring can be protected from external impact and bending, and in particular, the interlayer insulation In the case of a film, it is useful for high-density mounting of semiconductors and components on, for example, a multilayer wiring board or a build-up wiring board.

  Since the permanent pattern forming method of the present invention can form a permanent pattern with high definition and efficiency by suppressing distortion of an image formed on the photosensitive layer, high-definition exposure is required. In particular, it can be suitably used for forming high-definition permanent patterns.

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

Example 1
-Composition of photosensitive composition-
A photosensitive composition (solution) was prepared based on the following composition.
[Composition of photosensitive composition]
-63.0 parts by mass of barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., B30)-Epoxy acrylate compound (PR-300, concentration 67%, Showa Polymer Co., Ltd., binder) 24.5 parts by mass-SPC- 2X (concentration 60%, manufactured by Showa Polymer Co., Ltd., vinyl copolymer having a (meth) acryloyl group and a carboxyl group in the side chain, binder) 13.8 parts by mass, represented by the following structural formula (23) Epoxy compound (thermal crosslinking agent) 16.7 parts by mass Dipentaerythritol hexaacrylate (polymerizable compound) 5.5 parts by mass Dye having acidic nucleus represented by the following structural formula (24) (sensitizer) 0.42 parts by mass · 2,2-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (photopolymerization initiator) 7.89 parts by mass · N-phenylglycine 0.4 Part by weight-Hydroquinone monomethyl ether 0.056 parts by weight-Dicyandiamide 0.4 parts by weight-2MA-OK (manufactured by Shikoku Chemicals Co., Ltd.) 0.3 parts by weight-Phthalocyanine green 0.42 parts by weight-F780F (Dainippon Ink) 30% by weight methyl ethyl ketone solution
0.066 parts by mass / methyl ethyl ketone 60.00 parts by mass The barium sulfate dispersion was composed of 22 parts by mass of barium sulfate (manufactured by Sakai Chemical Co., Ltd., B30) and 67% by mass of diethylene glycol monomethyl ether acetate of PR-300 12 Mass parts and 29 parts by mass of methyl ethyl ketone were mixed in advance, and then dispersed with a motor mill M-200 (manufactured by Eiger) for 3.5 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 1.0 mm. Prepared.

The maximum absorption wavelength is 410 nm.

-Preparation of pattern forming material-
The obtained photosensitive composition solution was coated on a 16 μm thick PET (polyethylene terephthalate) film (Toray, 16QS52) as the support and dried to form a 35 μm thick photosensitive layer. . Next, a 12 μm-thick polypropylene film was laminated as a protective film on the photosensitive layer to produce the pattern forming material.

-Formation of permanent pattern-
-Preparation of 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 (MVLP500, manufactured by Meiki Seisakusho Co., Ltd.) was used on the copper clad laminate while peeling off the protective film from the photosensitive film so that the photosensitive layer of the pattern forming material was in contact with the copper clad laminate. Lamination was performed to prepare a laminate in which the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) were laminated in this order.
The pressure bonding conditions were a pressure bonding temperature of 90 ° C., a pressure bonding pressure of 0.4 MPa, and a laminating speed of 1 m / min.

--Exposure process--
A pattern in which holes with different diameters are formed from a polyethylene terephthalate film (support) side with a laser beam having a wavelength of 405 nm from the side of the polyethylene terephthalate film (support) with respect to the photosensitive layer in the prepared laminate. Were irradiated and exposed so that a portion of the photosensitive layer was cured.

[Pattern forming apparatus]
27 to 32 as the light irradiating means, and 768 pairs of micromirror arrays in which 1024 micromirrors are arranged in the main scanning direction shown in FIG. 4 as the light modulating means are arranged in the sub-scanning direction. The microlens array 472 in which the DMD 50 controlled to drive only 1024 × 256 rows and the microlenses 474 whose one surface is a toric surface shown in FIG. A pattern forming apparatus having optical systems 480 and 482 for forming an image of light passing through the array on the photosensitive layer was used.

The toric surface of the microlens described below was used.
First, in order to correct the distortion on the exit surface of the microlens 474 as the picture element portion of the DMD 50, the strain on the exit surface was measured. The results are shown in FIG. In FIG. 14, the same height positions of the reflecting surfaces are shown connected by contour lines, and the pitch of the contour lines is 5 nm. Note that the x direction and the y direction shown in the figure are two diagonal directions of the micromirror 62, and the micromirror 62 rotates around a rotation axis extending in the y direction. 15A and 15B show the height position displacement of the reflecting surface of the micromirror 62 along the x direction and the y direction, respectively.

  As shown in FIGS. 14 and 15, there is distortion on the reflection surface of the micromirror 62, and when attention is paid particularly to the center of the mirror, distortion in one diagonal direction (y direction) is different from that in the other diagonal line. It can be seen that the distortion is larger than the distortion in the direction (x direction). Therefore, it can be seen that the shape of the laser beam B collected by the microlens 55a of the microlens array 55 is distorted in this state.

  FIGS. 16A and 16B show the front shape and the side shape of the entire microlens array 55 in detail. In these drawings, the dimensions of each part of the microlens array 55 are also entered, and the unit thereof is mm. As described above with reference to FIG. 4, the 1024 × 256 micromirrors 62 of the DMD 50 are driven. Correspondingly, the microlens array 55 has 1024 microlenses arranged in the horizontal direction. The 55a rows are arranged in parallel in 256 rows in the vertical direction. In FIG. 9A, the arrangement order of the microlens array 55 is indicated by j in the horizontal direction and k in the vertical direction.

  17A and 17B show a front shape and a side shape of one microlens 55a in the microlens array 55, respectively. In FIG. 9A, the contour lines of the micro lens 55a are also shown. The end surface of each microlens 55a on the light emitting side has an aspherical shape that corrects aberration due to distortion of the reflecting surface of the micromirror 62. More specifically, the micro lens 55a is a toric lens, and has a radius of curvature Rx = −0.125 mm in a direction optically corresponding to the x direction and a radius of curvature Ry = − in a direction corresponding to the y direction. 0.1 mm.

  Therefore, the condensing state of the laser beam B in the cross section parallel to the x direction and the y direction is roughly as shown in FIGS. 18A and 18B, respectively. That is, when the cross section parallel to the x direction is compared with the cross section parallel to the y direction, the radius of curvature of the microlens 55a is smaller and the focal length is shorter in the latter cross section. I understand that.

  19A, 19B, 19C, and 19D show simulation results of the beam diameter in the vicinity of the condensing position (focal position) of the microlens 55a when the microlens 55a has the above shape. For comparison, FIGS. 20a, 20b, 20c, and 20d show the results of a similar simulation when the microlens 55a has a spherical shape with a radius of curvature Rx = Ry = −0.1 mm. In addition, the value of z in each figure has shown the evaluation position of the focus direction of the micro lens 55a with the distance from the beam emission surface of the micro lens 55a.

The surface shape of the microlens 55a used for the simulation is calculated by the following calculation formula.

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

  As is apparent when comparing FIGS. 19a to 19d and FIGS. 20a to 20d, the microlens 55a includes a toric lens in which the focal length in the cross section parallel to the y direction is smaller than the focal length in the cross section parallel to the x direction. As a result, distortion of the beam shape in the vicinity of the condensing position is suppressed. As a result, a higher-definition pattern without distortion can be exposed on the photosensitive layer 150. Further, it can be seen that the present embodiment shown in FIGS. 20a to 20d has a wider region with a smaller beam diameter, that is, a greater depth of focus.

  In addition, the aperture array 59 disposed in the vicinity of the condensing position of the microlens array 55 is disposed such that only light having passed through the corresponding microlens 55a is incident on each aperture 59a. That is, by providing this aperture array 59, it is possible to prevent light from adjacent microlenses 55a not corresponding to each aperture 59a from entering, and to increase the extinction ratio.

--Development process--
After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) is peeled off from the laminate, and a 1% by mass aqueous sodium carbonate solution is used as an alkaline developer on the entire surface of the photosensitive layer on the copper clad laminate. Developed at 30 ° C. for 60 seconds to dissolve and remove uncured regions. Thereafter, it was washed with water and dried to form a permanent pattern.

-Curing process-
The entire surface of the laminate on which the permanent pattern was formed was heated at 160 ° C. for 30 minutes to cure the surface of the permanent pattern and increase the film strength. When the permanent pattern was visually observed, no bubbles were observed on the surface of the permanent pattern.
Further, the printed wiring board on which the permanent pattern had been 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. And the pencil hardness was measured about the permanent pattern after this flux removal based on JISK-5400.
As a result, the pencil hardness was 5H or more. As a result of visual observation, no peeling, blistering, or discoloration of the cured film in the permanent pattern was observed.

The total light transmittance and haze value of the support were measured.
The laminated body was evaluated for variations in sensitivity, resolution, resist surface shape, and resist pattern width. The results are shown in Table 3.

<Total light transmittance>
The total light transmittance at 405 nm of the support was measured using an apparatus incorporating an integrating sphere in a spectrophotometer (manufactured by Shimadzu Corporation, UV-2400). The results are shown in Table 3.

<Haze value>
In the measurement method of the total light transmittance, parallel line transmittance was measured in the same manner as the measurement method of the total light transmittance except that the integrating sphere was not used. Next, the following calculation formula, diffuse light transmittance = the total light transmittance−the parallel light transmittance, is calculated, and further, the following calculation formula, haze value = diffuse light transmittance / total light transmittance × 100. , By calculating. The results are shown in Table 3.

<Minimum development time>
The polyethylene terephthalate film (support) is peeled off from the prepared laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. is sprayed on the entire surface of the photosensitive layer on the copper clad laminate at a pressure of 0.15 MPa. The time required from the start of spraying of the aqueous sodium solution until the photosensitive layer on the copper clad laminate was dissolved and removed was measured, and this was taken as the shortest development time.
As a result, the shortest development time was 20 seconds.
<Measurement of exposure sensitivity>
The photosensitive layer of the pattern forming material in the laminate described above prepared from the support side, a patterning device, which is described above, from 0.1 mJ / cm ² to 200 mJ / cm ² at ^{2 1/2} times the interval Were irradiated with light having different amounts of light energy to cure a part of the photosensitive layer. After standing at room temperature for 10 minutes, the support was peeled off from the laminate, and a 1% by mass aqueous sodium carbonate solution at 30 ° C. was applied to the entire surface of the photosensitive layer on the copper clad laminate at a spray pressure of 0.15 MPa. Spraying was performed for twice the shortest development time determined above, and the uncured area was dissolved and removed, and the thickness of the remaining cured area was measured. Subsequently, the relationship between the light irradiation amount and the thickness of the cured layer was plotted to obtain a sensitivity curve. From the sensitivity curve, the amount of light energy when the thickness of the cured region was the same 35 μm as the photosensitive layer before exposure was determined as the amount of light energy necessary for curing the photosensitive layer.
As a result, the amount of light energy necessary for curing the photosensitive layer was 35 mJ / cm ² .

<Resolution>
The surface of the obtained printed circuit board on which the permanent pattern was formed was observed with an optical microscope, and the minimum hole diameter with no residual film in the hole portion of the cured layer pattern was measured. The smaller the numerical value, the better the resolution. The results are shown in Table 3.

<Resist surface shape>
The pattern surface (50 μm × 50 μm) formed in the resolution measurement was photographed with a scanning electron microscope (SEM), and the shape of the formed resist surface was evaluated according to the following evaluation criteria. The results are shown in Table 3.
-Evaluation criteria-
A: There are no defects at all, or there are 1 to 5 defects, and the shape of the formed pattern is not affected.
B: There are 6-10 defects, but the shape of the formed pattern is not affected.
C: There are 11 to 20 defects, and the defects can cause a shape abnormality on the end face of the pattern.
D: There are 21 or more defects, and the defects cause shape abnormalities on the end face of the pattern.

<Variation of resist pattern width>
The laminate was allowed to stand at room temperature (23 ° C., 55% RH) for 10 minutes. From the obtained polyethylene terephthalate (support) of the laminate, the pattern forming apparatus is used to irradiate 20 patterns each having a 70 μm width × 300 μm length hole at the bottom. And a part of the photosensitive layer was cured. The exposure amount at this time is an exposure amount that is twice the exposure amount obtained by the sensitivity measurement.
This was developed as described above to dissolve and remove uncured regions. The obtained pattern was observed with an optical microscope, the width of the bottom of the formed pattern was measured, the difference between the maximum value and the minimum value of this width was determined, and this was regarded as the variation in the width of the resist pattern. The smaller the width variation value, the better the width reproducibility, which is preferable. The results are shown in Table 3.

(Example 2)
In Example 1, a pattern forming material and a laminate were produced in the same manner as in Example 1 except that the composition of the photosensitive composition was changed to the following composition.
[Composition of photosensitive composition]
Barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., B30) dispersion 24.75 parts by mass Styrene / maleic anhydride / butyl acrylate copolymer (molar ratio 40/32/28) and benzylamine (anhydrous of the copolymer) 35 mass% methyl ethyl ketone solution of addition reaction product with 1.0 equivalent to physical group) 13.36 parts by mass of R712 (manufactured by Nippon Kayaku Co., Ltd., bifunctional acrylic monomer) 3.06 parts by mass of the structural formula ( 23) Epoxy compound (thermal crosslinking agent) 9.0 parts by mass, dipentaerythritol hexaacrylate (polymerizable compound) 4.59 parts by mass, MW30HM (manufactured by Sanwa Chemical Co., Hexamethoxymethylol Melamine)
5.00 parts by mass Dye having an acidic nucleus represented by the following structural formula (25) (sensitizer) 1.26 parts by mass IRGACURE OXE01 (oxime derivative, manufactured by Ciba Specialty Chemicals) 4.5 mass Part · N-phenylglycine 0.2 parts by mass · 30% by mass methyl ethyl ketone solution of F780F (Dainippon Ink Co., Ltd.)
0.066 parts by mass / hydroquinone monomethyl ether 0.024 parts by mass / methyl ethyl ketone 8.60 parts by mass The total light transmittance and haze value of the support were measured. The results are shown in Table 3.
The laminate was evaluated for sensitivity, resolution, resist surface shape, and resist pattern line width variation. The results are shown in Table 3.

The maximum absorption wavelength is 416 nm.

(Example 3)
In Example 1, the same procedure as in Example 1 was conducted except that the dye having an acidic nucleus represented by the structural formula (24) was replaced with the dye having an acidic nucleus represented by the following structural formula (26). Thus, a pattern forming material and a laminate were manufactured.
The total light transmittance and haze value of the support were measured. The results are shown in Table 3.
The laminate was evaluated for sensitivity, resolution, resist surface shape, and resist pattern line width variation. The results are shown in Table 3.

The maximum absorption wavelength is 435 nm.

Example 4
In Example 1, the support was replaced with a 16 μm PET (polyethylene terephthalate) film (Mitsubishi Polyester, R340G), and the dye having an acidic nucleus represented by the structural formula (24) was replaced by the following structural formula (27). A pattern forming material and a laminate were produced in the same manner as in Example 1 except that the dye having an acidic nucleus represented by
The total light transmittance and haze value of the support were measured. The results are shown in Table 3.
The laminate was evaluated for sensitivity, resolution, resist surface shape, and resist pattern line width variation. The results are shown in Table 3.

The maximum absorption wavelength is 410 nm.

(Example 5)
In Example 1, the support was replaced with a 16 μm PET (polyethylene terephthalate) film (A1517, manufactured by Toyobo Co., Ltd.), and the dye having an acidic nucleus represented by the structural formula (24) was represented by the following structural formula (28). A pattern forming material and a laminate were produced in the same manner as in Example 1 except that the dye having the favored nucleus represented was replaced.
The total light transmittance and haze value of the support were measured. The results are shown in Table 3.
The laminate was evaluated for sensitivity, resolution, resist surface shape, and resist pattern line width variation. The results are shown in Table 3.

The maximum absorption wavelength is 440 nm.

(Example 6)
In Example 1, a pattern forming material and a laminate were produced in the same manner as in Example 1 except that the support was replaced with a 16 μm PET film (manufactured by Toray Industries, Inc., 16FB50).
The total light transmittance and haze value of the support were measured. The results are shown in Table 3.
The laminate was evaluated for sensitivity, resolution, resist surface shape, and resist pattern line width variation. The results are shown in Table 3.

(Example 7)
In Example 1, a pattern forming material and a laminate were produced in the same manner as in Example 1 except that the support was replaced with a 16 μm PET film (G2 manufactured by Teijin DuPont).
The total light transmittance and haze value of the support were measured. The results are shown in Table 3.
The laminate was evaluated for sensitivity, resolution, resist surface shape, and resist pattern line width variation. The results are shown in Table 3.

(Comparative Example 1)
In Example 1, a pattern forming material and a laminate were obtained in the same manner as in Example 1 except that the dye having an acidic nucleus represented by the structural formula (24) was replaced with 4,4′-bisdiethylaminobenzophenone. The body was manufactured. The maximum absorption wavelength of 4,4′-bisdiethylaminobenzophenone is 365 nm.
The total light transmittance and haze value of the support were measured. The results are shown in Table 3.
The laminate was evaluated for sensitivity, resolution, resist surface shape, and resist pattern line width variation. The results are shown in Table 3.

(Comparative Example 2)
In Example 1, the support is replaced with a 16 μm PET (polyethylene terephthalate) film (G2 manufactured by Teijin DuPont), and the dye having an acidic nucleus represented by the structural formula (24) is 4,4′- A pattern forming material and a laminate were produced in the same manner as in Example 1 except that bisdiethylaminobenzophenone was used.
The total light transmittance and haze value of the support were measured. The results are shown in Table 3.
The laminate was evaluated for sensitivity, resolution, resist surface shape, and resist pattern line width variation. The results are shown in Table 3.

  From the results of Table 3, the pattern forming materials of Examples 1 to 7 in which the photosensitive layer contains a binder, a polymerizable compound, a thermal crosslinking agent, and a dye having an acidic nucleus as a sensitizer are excellent in exposure sensitivity and resolution. As a result, it was found that a high-definition permanent pattern having a high resist surface shape was formed. In particular, in Examples 1 to 6 in which the haze value of the support was 5.0% or less, it was found that the exposure sensitivity was improved and a higher-definition permanent pattern was formed. On the other hand, it was found that in Comparative Examples 1 and 2 in which a dye having an acidic nucleus was not used as a sensitizer, the resist surface shape was inferior, and the resist line width variation was large.

  Since the pattern forming material of the present invention is excellent in exposure sensitivity, has a good resist surface shape, and can form a higher definition pattern, a printed wiring board, a color filter It can be widely used for forming permanent patterns such as display members such as columns, ribs, spacers, partition walls, holograms, micromachines, and proofs, and can be suitably used for the permanent pattern forming method of the present invention. The permanent pattern forming method of the present invention uses the pattern forming material of the present invention, so that a permanent plate such as a printed wiring board, a color filter, a column material, a rib material, a spacer, a partition, a display member, a hologram, a micromachine, a proof, etc. It can be suitably used for pattern production and the like, and can be particularly suitably used for forming a high-definition wiring pattern.

FIG. 1 is an example of a partially enlarged view showing a configuration of a digital micromirror device (DMD). 2A and 2B are examples of explanatory diagrams for explaining the operation of the DMD. FIGS. 3A and 3B are examples of plan views showing the arrangement of the exposure beam and the scanning line in a case where the DMD is not inclined and in a case where the DMD is inclined. 4A and 4B are examples of diagrams illustrating examples of DMD usage areas. FIG. 5 is an example of a plan view for explaining an exposure method in which the pattern forming material is exposed by one scanning by the scanner. 6A and 6B are examples of plan views for explaining an exposure method for exposing a pattern forming material by a plurality of scans by a scanner. FIG. 7 is an example of a schematic perspective view illustrating an appearance of an example of the pattern forming apparatus. FIG. 8 is an example of a schematic perspective view illustrating the configuration of the scanner of the pattern forming apparatus. FIG. 9A is an example of a plan view showing an exposed region formed in the pattern forming material, and FIG. 9B is an example of a diagram showing an array of exposure areas by each exposure head. FIG. 10 is an example of a perspective view showing a schematic configuration of an exposure head including light modulation means. FIG. 11 is an example of a sectional view in the sub-scanning direction along the optical axis showing the configuration of the exposure head shown in FIG. FIG. 12 is an example of a controller that controls DMD based on pattern information. FIG. 13A is an example of a cross-sectional view along the optical axis showing the configuration of another exposure head having a different coupling optical system, and FIG. 13B shows the exposure when a microlens array or the like is not used. FIG. 13C is an example of a plan view showing a light image projected on a surface to be exposed when a microlens array or the like is used. FIG. 14 is an example of a diagram showing the distortion of the reflection surface of the micromirror constituting the DMD with contour lines. FIGS. 15A and 15B are examples of graphs showing the distortion of the reflection surface of the micromirror in the two diagonal directions of the mirror. FIG. 16 is an example of a front view (A) and a side view (B) of a microlens array used in the pattern forming apparatus. FIG. 17 is an example of a front view (A) and a side view (B) of a microlens constituting a microlens array. FIG. 18 is an example of a schematic diagram illustrating a condensing state by a microlens in one cross section (A) and another cross section (B). FIG. 19a is an example of a diagram showing a result of simulating the beam diameter in the vicinity of the condensing position of the microlens. FIG. 19B is an example of a diagram showing the same simulation result as that in FIG. 19A at another position. FIG. 19c is an example of a diagram showing the same simulation result as in FIG. 19a at another position. FIG. 19d is an example of a diagram showing the same simulation result as in FIG. 19a at another position. FIG. 20a is an example of a diagram showing the result of simulating the beam diameter in the vicinity of the condensing position of the microlens in the conventional pattern forming method. FIG. 20b is an example of a diagram showing the same simulation result as in FIG. 20a at another position. FIG. 20c is an example of a diagram showing the same simulation result as in FIG. 20a for another position. FIG. 20d is an example of a diagram illustrating simulation results similar to those in FIG. 20a at different positions. FIG. 21 is an example of a plan view showing another configuration of the combined laser light source. FIG. 22 shows an example of a front view (A) and an example of a side view (B) of the microlens constituting the microlens array. FIG. 23 is an example of a schematic diagram illustrating a light condensing state by the microlens of FIG. 22 in one cross section (A) and another cross section (B). 24A, 24B, and 24C are examples of explanatory diagrams about the concept of correction by the light amount distribution correction optical system. FIG. 25 is an example of a graph showing the light amount distribution when the light irradiation means has a Gaussian distribution and the light amount distribution is not corrected. FIG. 26 is an example of a graph showing the light amount distribution after correction by the light amount distribution correcting optical system. 27A (A) is a perspective view showing the configuration of the fiber array light source, FIG. 27A (B) is an example of a partially enlarged view of FIG. 27A, and FIGS. 27A (C) and (D) are lasers. It is an example of the top view which shows the arrangement | sequence of the light emission point in an emission part. FIG. 27 b is an example of a front view showing the arrangement of light emitting points in the laser emission part of the fiber array light source. FIG. 28 is an example of a diagram illustrating a configuration of a multimode optical fiber. FIG. 29 is an example of a plan view showing the configuration of the combined laser light source. FIG. 30 is an example of a plan view showing the configuration of the laser module. FIG. 31 is an example of a side view showing the configuration of the laser module shown in FIG. 32 is a partial side view showing the configuration of the laser module shown in FIG. FIG. 33 is an example of a perspective view showing a configuration of a laser array. FIG. 34A is an example of a perspective view showing a configuration of a multi-cavity laser, and FIG. 34B is a perspective view of a multi-cavity laser array in which the multi-cavity lasers shown in FIG. It is an example. FIG. 35 is an example of a plan view showing another configuration of the combined laser light source. FIG. 36A is an example of a plan view showing another configuration of the combined laser light source, and FIG. 36B is an example of a cross-sectional view along the optical axis of FIG. FIGS. 37A and 37B are examples of cross-sectional views along the optical axis showing the difference between the depth of focus in the conventional exposure apparatus and the depth of focus by the pattern forming method (pattern forming apparatus) of the present invention.

Explanation of symbols

LD1-LD7 GaN-based semiconductor laser 10 Heat block 11-17 Collimator lens 20 Condensing lens 30-31 Multimode optical fiber 44 Collimator lens holder 45 Condensing lens holder 46 Fiber holder 50 Digital micromirror device (DMD)
52 Lens system 53 Reflected light image (exposure beam)
54 Lens of second imaging optical system 55 Micro lens array 56 Surface to be exposed (scanning surface)
55a Micro lens 57 Lens of second imaging optical system 58 Lens of second imaging optical system 59 Aperture array 64 Laser module 66 Fiber array light source 67 Lens system 68 Laser emitting unit 69 Mirror 70 Prism 71 Condensing lens 72 Rod integrator 73 Combined lens 74 Imaging lens 100 Heat block 110 Multi cavity laser 111 Heat block 113 Rod lens 120 Condensing lens 130 Multimode optical fiber 130a Core 140 Laser array 144 Light irradiation means 150 Pattern forming material 152 Stage 155a Micro lens 156 Installation base 158 Guide 160 Gate 162 Scanner 164 Sensor 166 Exposure head 168 Exposure area 170 Exposed area 180 Heat block 1 84 Collimating lens array 302 Controller 304 Stage driving device 454 Lens system 468 Exposure area 472 Micro lens array 474 Micro lens 476 Aperture array 478 Aperture 480 Lens system

Claims (22)

Having at least a photosensitive layer obtained using a photosensitive composition containing at least a binder, a polymerizable compound, a photopolymerization initiator, a thermal crosslinking agent, and a dye having an acidic nucleus as a sensitizer; In addition, when the photosensitive layer is exposed and developed, the minimum energy of light used for the exposure that does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development is 0.1 to 100 mJ / cm ² . A pattern forming material characterized by that.   The pattern forming material according to claim 1, wherein the dye having an acidic nucleus is a merocyanine dye.   The pattern forming material according to claim 1, wherein the pigment having an acidic nucleus is a rhodacyanine pigment.   The pattern forming material according to claim 1, which has at least a support and a photosensitive layer on the support, and the haze value of the support is 5.0% or less.   The pattern forming material according to claim 4, wherein the total light transmittance of the support is 86% or more.   The pattern forming material according to claim 4, wherein the haze value of the support and the wavelength of light when determining the total light transmittance of the support are 405 nm.   The pattern formation material in any one of Claim 1 to 6 in which a binder shows either swelling property or solubility with respect to alkaline aqueous solution.   The pattern forming material according to claim 1, wherein the binder comprises an epoxy acrylate compound.   The pattern forming material according to any one of claims 1 to 8, wherein the binder comprises a vinyl copolymer having a (meth) acryloyl group and an acidic group in a side chain.   The pattern forming material according to any one of claims 1 to 9, wherein the binder contains at least one kind of an epoxy acrylate compound and at least one kind of vinyl copolymer having a (meth) acryloyl group and an acidic group in a side chain.   The thermal crosslinking agent is at least one selected from an epoxy resin compound, an oxetane compound, a polyisocyanate compound, a compound obtained by reacting a polyisocyanate compound with a blocking agent, and a melamine derivative. The pattern forming material according to 1.   The pattern forming material according to claim 11, wherein the thermal crosslinking agent is an alkylated methylol melamine.   The photopolymerization initiator is selected from halogenated hydrocarbon derivatives, phosphine oxides, hexaarylbiimidazoles, oxime derivatives, organic peroxides, thio compounds, ketone compounds, acyl phosphine oxide compounds, aromatic onium salts and ketoxime ethers. The pattern forming material according to claim 1, comprising at least one selected from the group consisting of: The pattern forming material according to claim 1 is provided,
A pattern forming apparatus comprising: a light irradiating means capable of irradiating light; and a light modulating means for modulating light from the light irradiating means and exposing the photosensitive layer in the pattern forming material.   The permanent pattern formation method characterized by including exposing at least with respect to this photosensitive layer in the pattern formation material in any one of Claims 1-13.   The permanent pattern forming method according to claim 15, wherein the exposure is performed by using a light generated by generating a control signal based on pattern information to be formed and modulating in accordance with the control signal.   The exposure is performed through a microlens array in which microlenses having aspherical surfaces capable of correcting aberrations due to distortion of the exit surface of the picture element portion in the light modulation means after the light is modulated by the light modulation means. The permanent pattern formation method in any one of 15-16.   The permanent pattern forming method according to claim 17, wherein the aspherical surface is a toric surface.   The permanent pattern forming method according to claim 15, wherein the exposure is performed using laser light having a wavelength of 350 to 415 nm.   The permanent pattern forming method according to claim 15, wherein the photosensitive layer is developed after the exposure.   21. The permanent pattern forming method according to claim 15, wherein after the development, the photosensitive layer is cured. The permanent pattern formation method according to claim 15, wherein at least one of a protective film, an interlayer insulating film, and a solder resist pattern is formed.