JP2007025275A - Photosensitive composition, photosensitive film, permanent pattern and method for forming same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition which has particularly excellent exposure sensitivity, small surface tackiness, good laminating property, good handleability and excellent storage stability, and exhibits excellent plating resistance, chemical resistance, surface hardness and heat resistance after development, a photosensitive film using the composition, a high-definition permanent pattern and a method for efficiently forming the pattern. <P>SOLUTION: The photosensitive composition contains at least (A) an alkali-soluble resin, (B) a polymerizable compound including a ring consisting of C, S and O atoms, and having at least one aromatic ring having a vinyl group, (C) a photopolymerization initiator and (D) a heat crosslinking agent. The photosensitive film using the composition, the permanent pattern and the method for forming the pattern are also provided. In particular, the aromatic ring is preferably at least one selected from benzene, naphthalene and anthracene rings, and the aromatic ring is preferably a vinylbenzene ring. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention can form an image by UV exposure, is particularly excellent in sensitivity to the UV exposure, has a small surface tackiness, good laminating properties and handling properties, excellent storage stability, and excellent plating resistance after development. , A photosensitive composition that exhibits chemical resistance, surface hardness, heat resistance, and the like, a photosensitive film using the same, and a high-definition permanent pattern (protective film, interlayer insulating film, solder resist pattern, etc.) and its efficiency Relates to a typical forming method.

  In the field of printed wiring boards, components such as semiconductors, capacitors and resistors are soldered onto the printed wiring board. In this case, for example, in a soldering process such as IR reflow, in order to prevent solder from adhering to an unnecessary part of soldering, a permanent pattern corresponding to the unnecessary part of soldering is used as a protective film and an insulating film. The method of forming is adopted. A solder resist is preferably used as the permanent pattern of the protective film.

  Conventionally, as the solder resist, a thermosetting material is often used, and a method of printing by a screen printing method is generally used. However, in recent years, with the increase in the wiring density of printed wiring boards, the screen printing method has a limit in terms of resolution, and a photo solder resist for forming an image by a photolithography method has been actively used. . Among them, alkali development type photo solder resists that can be developed with a weak alkaline solution such as a sodium carbonate solution have become mainstream in terms of working environment and global environment conservation. In general, a manufacturing method is used in which a liquid solder resist is applied to one surface of a substrate on which wiring has been formed by screen printing, spray coating, dip coating, and the like, and then dried on the opposite surface.

As such an alkali development type photo solder resist, a compound (epoxy acrylate) in which an acid group for imparting an ethylenically unsaturated double bond and alkali developability to an epoxy compound as a main component is introduced, A composition containing an addition polymerizable compound (monomer) having a saturated double bond is generally used, and specifically disclosed in Patent Document 1. However, although the solder resist described in Patent Document 1 has a high surface hardness after post-baking and excellent chemical resistance, the surface tack remains and dust tends to adhere to increase the defect, or a photomask can be used. There is a problem of deteriorating handling properties such as contamination. Here, the tack remains on the surface because the epoxy acrylate, which is a binder soluble in an alkaline aqueous solution, has a low molecular weight of about several hundreds, and the monomer is usually a liquid or semi-solid having a high boiling point. it is conceivable that.
Moreover, the exposure sensitivity of such a solder resist is usually as low as 300 to 1,000 mJ / cm ^2, which is becoming a bottleneck in speeding up the production line, and further improvement in sensitivity is required. Increasing the amount of the monomer is effective for increasing the sensitivity, but if a large amount of monomers are added, the problem that the surface tack is further deteriorated occurs, and no solution has been found.

In recent years, high-density mounting has been rapidly progressing, and the problem of solder resist in realizing high-density mounting is that the substrate expansion and contraction in the photolithography process and the photomask film repeat the wet development and wet etching. Misalignment of wiring patterns and through-hole land patterns due to expansion and contraction based on temperature and humidity changes.
To prevent misalignment, measures have been taken so far, such as selecting lots with a low degree of deformation of the substrate, preparing multiple film masks that have been corrected in advance using various parameters, and using expensive glass masks. I came. In addition, in order to solve this misalignment problem, application of a laser direct imaging system (LDI) is progressing. Here, LDI is based on a technique of forming an exposure pattern corresponding to the deformation of the substrate by correction by high-speed processing of digital data.

The solder resist used for the LDI is required to have an exposure sensitivity of 100 mJ / cm ² or more in order to cope with a UV laser of 365 nm or 405 nm. For this reason, a film-type solder resist that can easily obtain high sensitivity is required. However, when the solder resist described in Patent Document 1 is formed into a film, the tackiness of the surface is strong, the support or the protective film and the photosensitive layer are difficult to peel off, the handling property is poor, and even at -20 ° C. or lower frozen storage. It can only be stored for a few months, and there is a problem of storage stability. In addition, there is a drawback that there is no sensitivity to laser light having a wavelength of 405 nm.

  On the other hand, Patent Document 2 discloses a solder using a binder soluble in a relatively high molecular weight alkaline aqueous solution having a molecular weight of 10,000 or more, having a small surface tackiness, excellent heat resistance, and relatively good storage stability. A resist is disclosed. However, the solder resist has a problem that the surface hardness is low and the laminating property is poor. Therefore, it is necessary to apply a liquid monomer as an undercoat layer in advance to the outermost layer of a printed wiring board on which wiring has been formed without generating bubbles, which has the disadvantage that the process becomes complicated and handling is inferior. is doing. The reason is that, as a result of using a copolymer component that forms a hard polymer such as methyl methacrylate and styrene (Tg of each homopolymer is 105 ° C. or higher and 100 ° C.), the cured film lacks flexibility and becomes brittle. Therefore, it is considered that the surface hardness does not increase, and sufficient fluidity cannot be obtained in the heating and laminating process under a vacuum condition, thereby causing bubble generation. Furthermore, there is a drawback that there is no sensitivity to laser light having a wavelength of 405 nm.

From the viewpoint of improving the exposure sensitivity, Patent Documents 3 to 6 disclose a photosensitive composition containing a polyfunctional monomer having a specific structure. However, the inventions described in these patent documents relate to the photosensitive composition used for the lithographic printing plate material, and do not disclose any solder resist, nor do they disclose surface hardness, plating properties, or the like. Further, there is no description that an epoxy acrylate is used as a binder and that a thermal crosslinking agent is used.
Patent Document 7 discloses a solder resist photosensitive composition using epoxy acrylate that contains a polyfunctional monomer having a specific structure to improve heat resistance, chemical resistance, and the like. ing. However, in this case, the sensitivity was 100 to 200 mJ / cm ² , which was inferior in exposure sensitivity.
In addition, from the viewpoint of mainly improving heat resistance and dielectric properties, photosensitive compositions using vinyl benzyl compounds or aromatic vinyl derivatives have been disclosed (see Patent Documents 8 to 11). There is no description of the resist, and there is no description of tackiness necessary for film formation. On the other hand, although the manufacturing method of these compounds is also disclosed (refer patent document 12), although there exists description about optical system materials, such as an optical disk, as these uses, there is no description about a photosensitive composition.
In addition, there are disclosures about monomers using these compounds and lithographic printing plate precursors (see Patent Document 13), but also in this case, there is no description about availability as a photosensitive film and solder resist.

  Therefore, exposure sensitivity is particularly excellent, surface tackiness is small, lamination and handling properties are good, storage stability is excellent, and excellent plating resistance, chemical resistance, surface hardness, heat resistance, etc. are exhibited after development. However, a photosensitive composition that can be suitably used for LDI, a photosensitive film using the same, and a permanent pattern and an efficient formation method thereof have not yet been sufficiently satisfactory. It is.

JP-A 61-243869 Japanese Patent Laid-Open No. 02-097502 JP 2001-290271 A JP 2004-294934 A JP 2003-215801 A JP 2004-301986 A Japanese Patent Laid-Open No. 04-217252 JP 2003-286315 A JP 2004-175950 A JP 2004-189901 A JP-A-01-165546 Japanese Patent Laid-Open No. 03-163039 Japanese Patent Application Laid-Open No. 2004-271692

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention can form an image by UV exposure, has particularly excellent sensitivity to the UV exposure, has a small surface tackiness, good laminating properties and handling properties, has excellent storage stability, and has excellent resistance after development. A photosensitive composition that exhibits plating properties, chemical resistance, surface hardness, heat resistance, and the like, a photosensitive film using the same, a high-definition permanent pattern (protective film, interlayer insulating film, solder resist pattern, etc.) and It aims at providing the efficient formation method.

Means for solving the problems are as follows. That is,
<1> (A) an alkali-soluble resin, (B) a polymerizable compound containing at least one aromatic ring having a vinyl group and containing a ring composed of C, S, and O atoms, and (C) a photopolymerization initiator. And (D) a thermal crosslinking agent. The photosensitive composition according to <1> includes a polymerizable compound having a ring composed of C, S, and O atoms having at least one aromatic ring having a vinyl group, and a thermal crosslinking agent. In the case where a permanent pattern is formed using the photosensitive composition, the exposure sensitivity is particularly excellent, the strength of the cured film is improved, and the plating resistance at the time of plating treatment is improved. A permanent pattern is obtained.
<2> The photosensitive composition according to <1>, wherein the aromatic ring is at least one selected from a benzene ring, a naphthalene ring, and an anthracene ring.
<3> (B) The molecular weight of the polymerizable compound having a ring composed of C, S, and O atoms having at least one aromatic ring having a vinyl group is from 100 to 1,000. 2>. The photosensitive composition according to any one of 2).
<4> (B) The molecular weight of the polymerizable compound having a ring composed of C, S, and O atoms having at least one aromatic ring having a vinyl group is from 200 to 1,000. 3>. The photosensitive composition according to any one of 3).
<5> (B) <1> to <4> wherein the molecular weight of the polymerizable compound having a ring composed of C, S, and O atoms having at least one aromatic ring having a vinyl group is 300 to 900. Or a photosensitive composition according to any one of the above.
<6> The photosensitive composition according to any one of <1> to <5>, wherein the aromatic ring is a vinylbenzene ring.
<7> (B) A polymerizable compound containing a ring composed of C, S, and O atoms, which has at least one aromatic ring having a vinyl group, is represented by the following general formula (1): <6> The photosensitive composition according to <6>.
However, in said general formula (1), Ar represents a substituted phenyl group. Z represents an organic linking chain containing an aromatic ring compound, and n represents an integer of 1 to 10. R ¹ represents either a hydrogen atom or a substituted alkyl group.
<8> (B) A fragrance having at least one aromatic ring having a vinyl group, containing a polymerizable compound including a polymerizable compound having a ring composed of C, S, and O atoms, and having the vinyl group Any one of <1> to <7>, wherein a content of the polymerizable compound having at least one ring and containing a ring composed of C, S, and O atoms in the polymerizable compound is 20 to 100% by mass. It is a photosensitive composition as described in above.
<9> (A) The photosensitive composition according to any one of <1> to <8>, wherein the alkali-soluble resin is an epoxy acrylate.
<10> The epoxy acrylate is a partially polybasic carboxylic acid, an unsaturated polybasic carboxylic acid, or any of a partial esterification reaction product and a total esterification reaction product of an epoxy resin compound and an unsaturated carboxylic acid. <9> The photosensitive composition according to <9>, which is an unsaturated group-containing polycarboxylic acid resin obtained by reacting with any of the above anhydrides.
<11> 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 photosensitive composition as described in said <9> which is a mixture with the at least 1 sort (s) of epoxy compound selected from a glycidyl ether type epoxy compound.
<12> The photosensitive composition according to <9>, wherein the epoxy resin compound is a novolac epoxy compound.
<13> The photosensitive composition according to any one of <10> to <12>, wherein the novolac type epoxy compound is any one of a cresol novolac type epoxy compound and a phenol novolac type epoxy compound.
<14> (C) The photopolymerization initiator is selected from halogenated hydrocarbon derivatives, phosphine oxides, hexaarylbiimidazoles, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, and metallocenes. The photosensitive composition according to any one of <1> to <13>, including at least one of the above.
<15> (D) The above <1, wherein the thermal crosslinking agent is at least one selected from an epoxy compound, an oxetane compound, a polyisocyanate compound, a compound obtained by reacting a polyisocyanate compound with a blocking agent, and a melamine derivative. > To <14>.
<16> The photosensitive composition according to <15>, wherein (D) the thermal crosslinking agent is an epoxy compound containing at least an epoxy group having an alkyl group at the β-position. In the photosensitive composition according to <16>, when the binder is an epoxy acrylate, the epoxy compound containing at least an epoxy group having an alkyl group at the β-position is used as the crosslinking agent. When a permanent pattern is formed using a conductive composition, the film strength of the effect film can be improved.

<17> A photosensitive film comprising a support and a photosensitive layer obtained by laminating the photosensitive composition according to any one of <1> to <13> on the support. It is.
<18> 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 100 mJ / cm ² or less. It is the photosensitive film as described in said <17>.
<19> 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 of the drawing part The photosensitive film according to any one of <17> to <18>, wherein the photosensitive film is exposed with light passing through a microlens array in which microlenses having an aspheric surface capable of correcting an aberration due to distortion of the lens are arranged. In the photosensitive film according to <19>, 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.
<20> The photosensitive film according to any one of <17> to <19>, wherein the support includes a synthetic resin and is transparent.
<21> The photosensitive film according to any one of <17> to <20>, wherein the support has a long shape.
<22> The photosensitive film according to any one of <17> to <21>, which is long and wound in a roll shape.
<23> The photosensitive film according to any one of <17> to <22>, which has a protective film on the photosensitive layer.
<24> The photosensitive film according to any one of <17> to <23>, wherein the photosensitive layer has a thickness of 3 to 100 μm.

<25> The photosensitive composition according to any one of <1> to <16> is applied to a surface of a substrate, dried to form a photosensitive layer, and then exposed and developed. This is a permanent pattern forming method. In the permanent pattern forming method according to <25>, the photosensitive composition is applied to the surface of the substrate. The applied photosensitive composition is dried to form the photosensitive layer. The photosensitive layer is exposed. The exposed photosensitive layer is developed. As a result, exposure sensitivity, surface hardness, and plating resistance are high, and a permanent pattern optimal for a protective film, an insulating film, or a solder resist pattern is formed.
<26> The photosensitive film according to any one of <17> to <24> is laminated on the surface of the substrate under at least one of heating and pressing to form a photosensitive layer, and then exposed. , Developing a permanent pattern. In the permanent pattern forming method according to <26>, the photosensitive film is laminated on the surface of the base material under heating and pressure. The photosensitive layer in the laminated photosensitive film is exposed. The exposed photosensitive layer is developed. As a result, exposure sensitivity, surface hardness, and plating resistance are high, and a permanent pattern optimal for a protective film, an insulating film, or a solder resist pattern is formed.
<27> The permanent pattern forming method according to any one of <25> to <26>, wherein the base material is a printed wiring board on which wiring is formed. In the permanent pattern forming method according to <27>, since the base material is a printed wiring board on which wiring has been formed, by using the permanent pattern forming method, a multilayer wiring board or build-up of a semiconductor or a component can be used. High-density mounting on a wiring board or the like is possible.
<28> 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 100 mJ / cm ² or less. The permanent pattern forming method according to any one of <25> to <27>.
<29> The method for forming a permanent pattern according to any one of <25> to <28>, wherein the exposure is performed imagewise based on pattern information to be formed.
<30> The permanent pattern according to any one of <25> to <29>, 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.
<31> From <25> to <30, wherein 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.
<32> 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 <31>, wherein modulation is performed according to a signal.
<33> The light modulation means has n pixel parts, and forms any less than n pixel parts continuously arranged from the n pixel parts. The permanent pattern forming method according to any one of <31> to <32>, which is controllable according to pattern information. In the method for forming a permanent pattern according to <33>, any less than n pixel portions arranged continuously from n pixel portions in the light modulation unit are controlled according to pattern information. By doing so, the light from the light irradiation means is modulated at high speed.
<34> The method for forming a permanent pattern according to any one of <31> to <33>, wherein the light modulator is a spatial light modulator.
<35> The method for forming a permanent pattern according to <34>, wherein the spatial light modulation element is a digital micromirror device (DMD).
<36> The permanent pattern forming method according to any one of <33> to <35>, wherein the picture element portion is a micromirror.
<37> 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 <30> to <36>.
<38> The method for forming a permanent pattern according to <37>, wherein the aspherical surface is a toric surface. In the method for forming a permanent pattern according to <38>, 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.
<39> The method for forming a permanent pattern according to any one of <24> to <38>, wherein the exposure is performed through an aperture array. In the method for forming a permanent pattern according to <39>, 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.
<40> The method for forming a permanent pattern according to any one of <24> to <39>, 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 <40>, the exposure is performed at a high speed by performing exposure while relatively moving the modulated light and the photosensitive layer.
<41> The permanent pattern forming method according to any one of <24> to <40>, wherein the exposure is performed on a partial region of the photosensitive layer.
<42> The permanent pattern forming method according to any one of <30> to <41>, wherein the light irradiation unit can synthesize and irradiate two or more lights. In the method for forming a permanent pattern according to <42>, the light irradiation unit can synthesize and irradiate two or more lights, so that exposure is performed with exposure light having a deep focal depth. As a result, the exposure of the photosensitive layer is performed with extremely high definition. Thereafter, the photosensitive layer is developed to form a very fine permanent pattern.
<43> The above-described <30, wherein the light irradiation unit 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. > To <42>. In the method for forming a permanent pattern according to <43>, laser light emitted from each of the plurality of lasers is condensed by the collective optical system by the light irradiation unit and can be coupled to the multimode optical fiber. By doing so, exposure is performed with exposure light having a deep focal depth. As a result, the exposure of the photosensitive layer is performed with extremely high definition. Thereafter, the photosensitive layer is developed to form a very fine permanent pattern.
<44> The permanent pattern forming method according to any one of <24> to <43>, wherein the exposure is performed using laser light having a wavelength of 395 to 415 nm.
<45> After the development, the photosensitive layer is subjected to a curing process from <24> to <44
The permanent pattern forming method according to any one of the above. In the method for forming a permanent pattern described in <45>, after the development, the curing process is performed on the photosensitive layer. As a result, the film strength of the cured region of the photosensitive layer is increased.
<46> The method for forming a permanent pattern according to <45>, wherein the curing treatment is a post-treatment performed by at least one of exposure and heating. In the permanent pattern forming method described in <46>, in the exposure process, curing of the resin in the photosensitive composition is promoted, and plating resistance is also improved. In the heat treatment, the film strength of the cured film is increased.
<47> The method for forming a permanent pattern according to any one of <45> to <46>, 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 method for forming a permanent pattern described in <47>, in the entire surface exposure treatment, curing of the resin in the photosensitive composition is promoted, and plating resistance is also improved. Moreover, the film | membrane intensity | strength of a cured film is raised in the whole surface heat processing performed on the said temperature conditions.
<48> The method for forming a permanent pattern according to any one of <24> to <47>, wherein at least one of a protective film and an interlayer insulating film is formed. In the method for forming a permanent pattern according to <48>, at least one of the protective film and the interlayer insulating film is formed. Protected from.

<49> A permanent pattern formed by the method for forming a permanent pattern according to any one of <24> to <48>. Since the permanent pattern according to <49> is formed by the permanent pattern forming method, the permanent pattern has excellent plating resistance, chemical resistance, surface hardness, heat resistance, and the like, and has high definition. It is useful for high-density mounting of parts on multilayer wiring boards and build-up wiring boards.
<50> The permanent pattern according to <49>, which is at least one of a protective film, an interlayer insulating film, and a solder resist pattern. Since the permanent pattern described in <50> is at least one of a protective film and an interlayer insulating film, the wiring is protected from external impact, bending, and the like by the insulating property and heat resistance of the film. .

  According to the present invention, conventional problems can be solved, images can be formed by UV exposure, sensitivity to the UV exposure is particularly excellent, surface tackiness is small, laminating properties and handling properties are good, and storage stability Photosensitive composition that exhibits excellent plating resistance, chemical resistance, surface hardness, heat resistance, and the like after development, a photosensitive film using the same, and a high-definition permanent pattern and its efficient A forming method can be provided.

(Photosensitive composition)
The photosensitive composition of the present invention comprises (A) an alkali-soluble resin (binder) and (B) a polymerizable compound having a ring composed of C, S, and O atoms having at least one aromatic ring having a vinyl group. And (C) a photopolymerization initiator and (D) a thermal cross-linking agent, and if necessary, from C, S, and O atoms having at least one aromatic ring having a vinyl group In addition to the polymerizable compound containing a ring, it contains other polymerizable compounds, and further contains other components such as coloring pigments, extender pigments, thermal polymerization inhibitors, and surfactants as necessary.

[(A) Binder]
For example, the binder is preferably swellable in an alkaline aqueous solution, and more preferably soluble in an alkaline aqueous solution.
There is no restriction | limiting in particular as a binder which shows swelling property or solubility with respect to alkaline aqueous solution, Although it can select suitably according to the objective, For example, what has an acidic group is mentioned suitably.
The binder having an acidic group is not particularly limited and may be appropriately selected depending on the intended purpose. And epoxy acrylates described in JP-A-2-97513, JP-A-3-289656, JP-A-61-2243869, JP-A-2002-296976, and the like.
The binder includes at least one of (a ₁ ) epoxy acrylate compounds and (a ₂ ) at least one vinyl copolymer having a (meth) acryloyl group and an acidic group in the side chain. Preferably, other binders may be included as necessary.
The acidic group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among these, the availability of raw materials, etc. From the viewpoint, a carboxyl group is preferable.
The binder preferably contains at least one vinyl copolymer having a (meth) acryloyl group and an acidic group in the (a ₃ ) side chain, and may contain other binders as necessary. good.

<(A ₁ ) 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. Further, commercially available products include Aronix M-5300, M-5400, M-5500 and M-5600 manufactured by Toa Synthetic Chemical Industry Co., Ltd., NK Esters CB-1 and CBX- manufactured by Shin-Nakamura Chemical Co., Ltd. 1. Kyoeisha Yushi Chemical Co., Ltd. HOA-MP and HOA-MS, Osaka Organic Chemical Industry Co., Ltd. biscoat # 2100, etc. can be used. These may be used individually by 1 type and may use 2 or more types together.

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

  In addition, compounds obtained by adding the polybasic acid anhydride to an epoxy acrylate having a fluorene skeleton (a compound having no carboxyl group) described in JP-A-5-70528 are also used as the epoxy acrylate of the present invention. Available.

  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.

<(A ₂ ) Vinyl Copolymer Having (Meth) acryloyl Group and Acid Group in Side Chain>
Examples of the vinyl copolymer having a (meth) acryloyl group and an acidic group in the side chain include (1) a vinyl monomer having an acidic group, and (2) a function that can be used for a polymer reaction described later, if necessary. A (co) polymer obtained by vinyl (co) polymerization of a vinyl monomer having a group and (3) other copolymerizable vinyl monomer if necessary, and (4) the (co) polymer It is obtained by polymer-reacting a compound having a (meth) acryloyl group with a functional group having reactivity with at least one of an acidic group in the coalescence or a functional group available for polymer reaction.
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.
As these commercially available products, for example, “Kaneka Resin AX; manufactured by Kaneka Chemical Industry Co., Ltd.”, “Cyclomer (CYCLOMER) A-200; manufactured by Daicel Chemical Industries, Ltd.”, “Cyclomer (CYCLOMER) M-” 200; manufactured by Daicel Chemical Industries, Ltd. "," SPCP1X, SPCP2X, SPCP3X; manufactured by Showa High Polymer Co., Ltd. "can be used.
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, normal propyl (meth) acrylate, isopropyl (meth) acrylate, normal butyl (meth) acrylate, and isobutyl (meth) acrylate. , Tertiary butyl (meth) acrylate, normal hexyl (meth) acrylate, cyclohexyl (meth) acrylate, tertiary butylcyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tertiary octyl (meth) acrylate, dodecyl (meta) ) 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, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclo Pentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, tri Examples thereof include bromophenyl (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, normal propanol, isopropanol, normal butanol, secondary butanol, tertiary butanol, normal hexanol, 2-ethylhexanol, normal decanol, normal). Dodecanol, normal octadecanol, cyclopentanol, cyclohexanol, benzyl alcohol, phenylethyl alcohol, etc.), phenols (eg, phenol, cresol, naphthol, etc.), Fluoroethanol, methoxyethanol, phenoxyethanol, chlorophenol, dichlorophenol, methoxyphenol, acetoxyphenol, etc. That.

  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, normalpropylamine, isopropylamine, normal butylamine, secondary butylamine, tertiary butylamine, hexylamine, 2-ethylhexyl). Amine, decylamine, dodecylamine, octadecylamine, dimethylamine, diethylamine, dibutylamine, dioctylamine), cyclic alkylamine (cyclopentylamine, cyclohexylamine, etc.), aralkylamine (benzylamine, phenethylamine, etc.), arylamine (aniline, Toluylamine, xylylamine, naphthylamine, etc.), combinations thereof (N-methyl-N-benzylamine, etc.), and further amines containing substituents ( Li fluoroalkyl ethyl amine, 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.

<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 these commercially available products, for example, “Kaneka Resin AX; manufactured by Kaneka Chemical Co., Ltd.”, “Cyclomer (CYCLOMER) A-200; manufactured by Daicel Chemical Industries, Ltd.”, “CYCLOMER (M)” 200; manufactured by Daicel Chemical Industries, Ltd. "can be used.
Furthermore, a reaction product of hydroxyalkyl acrylate or hydroxyalkyl methacrylate described in JP-A No. 50-59315 and any of polycarboxylic acid anhydride and epihalohydrin can be used.

  Further, a compound obtained by adding an acid anhydride to an epoxy acrylate having a fluorene skeleton described in JP-A-5-70528, a polyamide (imide) resin described in JP-A-11-288087, and JP-A-2-097502 Styrene or a styrene derivative and an acid anhydride copolymer containing an amide group described in JP-A No. 2003-20310 and a polyimide precursor described in JP-A No. 11-282155 can be used. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

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

  As other binders, polyamide (imide) resins described in JP-A No. 11-288087, polyimide precursors described in JP-A 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 binder such as the polyamide (imide) or polyimide precursor is preferably 3,000 to 500,000, and more preferably 5,000 to 100,000. When the molecular weight is less than 3,000, the tackiness of the surface of the photosensitive layer may become strong, and after curing of the photosensitive layer described later, the film quality may become brittle or the surface hardness may be deteriorated. If it exceeds 1,000, developability may deteriorate.

  As solid content in the said photosensitive composition solid content of the said binder, 5-80 mass% is preferable, 5-70 mass% is more preferable, 10-50 mass% is still more preferable. When the solid content is less than 5% by mass, the film strength of the photosensitive layer described later tends to be weak, and the tackiness of the surface of the photosensitive layer may be deteriorated. Sensitivity may decrease.

[(B) Polymerizable compound]
The polymerizable compound includes at least a polymerizable compound including a ring composed of C, S, and O atoms having at least one aromatic ring having a vinyl group, and if necessary, an aromatic ring having a vinyl group. And other polymerizable compounds other than the polymerizable compound containing a ring composed of C, S, and O atoms.
<Polymerizable compound containing a ring composed of C, S, and O atoms having at least one aromatic ring having a vinyl group>
There is no restriction | limiting in particular as a polymeric compound containing the ring which consists of C, S, and O atom which has at least one aromatic ring which has the said vinyl group, According to the objective, it can select suitably.
The aromatic ring having a vinyl group preferably includes at least one selected from a benzene ring, a naphthalene ring, and an anthracene ring, and among these, a benzene ring is preferable.
Among the benzene rings, a vinyl benzene ring is particularly preferable. Therefore, the polymerizable compound is a polymerizable compound including a ring composed of C, S, and O atoms having at least one vinyl benzyl group. Is preferred.

The polymerizable compound having a ring composed of C, S, and O atoms having at least one aromatic ring having a vinyl group is preferably a compound represented by the following general formula (1).
However, in said general formula (1), Ar represents a substituted phenyl group. Z represents an organic linking chain containing an aromatic ring compound, and n represents an integer of 1 to 10. R ¹ represents either a hydrogen atom or a substituted alkyl group.

In the general formula (1), as the substituted phenyl group representing Ar, the other four substituents of CH ₂ ═CHR— may be a hydrogen atom or have a substituent.

  Examples of the polymerizable compound containing a ring composed of C, S, and O atoms having at least one aromatic ring having a vinyl group represented by the general formula (1) include the following structural formulas (14) to (25). However, it is not limited to these.

In the structural formulas (14) to (25), R1 to R6 each represents a substituent selected from the group consisting of a vinylbenzyl ether group, a vinylbenzylthioether group, and a vinylbenzyloxycarbonyl group, Other than represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic residue.
R7 to R8 represent any of a hydrogen atom, an alkyl group, an aryl group, and a haloalkyl group. X represents any of a carbon atom, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, and a sulfone group. When X is other than a carbon atom, R7 to R8 do not exist.

  Specific examples of the compounds represented by the structural formulas (14) to (25) include those represented by the following structural formulas (26) to (48), but are not limited thereto. Absent.

  The solid content in the solid content of the photosensitive composition of the polymerizable compound having a ring composed of C, S, and O atoms having at least one aromatic ring having a vinyl group is 5 to 50% by mass. Is preferable, and 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.

<Other polymerizable compounds>
Other polymerizable compounds other than the polymerizable compound having a ring composed of C, S, and O atoms having at least one aromatic ring having a vinyl group are not particularly limited and are appropriately selected depending on the purpose. A compound having at least one addition-polymerizable group in the molecule and having a boiling point of 100 ° C. or higher at normal pressure is preferable, for example, selected from monomers having a (meth) acryl group At least one is preferably exemplified.

  There is no restriction | limiting in particular as a monomer which has the said (meth) acryl group, According to the objective, it can select suitably, For example, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) ) Monofunctional acrylates and monofunctional methacrylates such as acrylates; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentylglycol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hex (Meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, Polyfunctional alcohols such as glycerin tri (meth) acrylate, trimethylolpropane, glycerin, bisphenol, and the like, and (meth) acrylated after addition reaction of ethylene oxide and propylene oxide, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50 Urethane acrylates described in each publication such as JP-6034, JP-A-51-37193; JP-A-48-64183, JP-B-49-43191, JP-B-52 Polyester acrylates described in each publication of such No. 30490; an epoxy resin and (meth) polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of acrylic acid. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are particularly preferable.

  Solid content in the photosensitive composition solid content of a polymerizable compound having a ring composed of C, S, and O atoms having at least one aromatic ring having a vinyl group, and other polymerizable compounds Is preferably 5 to 50% by mass, and more preferably 10 to 40% by mass. 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.

In addition, the content of the polymerizable compound having a ring composed of C, S, and O atoms having at least one aromatic ring having a vinyl group is 20 to 100 mass with respect to the total weight of the polymerizable compound. % Is preferable, 30 to 90% by mass is more preferable, and 40 to 80% by mass is particularly preferable. Even if the content is less than 20% by mass, effects of addition can be obtained, but these effects cannot be improved greatly, the effect of improving the exposure sensitivity is small, and tackiness may be deteriorated.
The upper limit of the content may be 100% by mass, but it is more preferable that the upper limit is 90% by mass considering that the plating resistance may be lowered.
The molecular weight of the polymerizable compound containing a ring composed of C, S, and O atoms having at least one aromatic ring having a vinyl group is preferably 100 to 1,000, more preferably 200 to 1,000, 300 to 900 are particularly preferred.
When the molecular weight is less than 100, curability may be inferior, and when the molecular weight exceeds 1,000, a development residue may remain and developability may deteriorate.

[(C) Photopolymerization initiator]
Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), phosphine oxides, hexaarylbiimidazoles, oxime derivatives, organic peroxides. Thio compounds, ketone compounds, aromatic onium salts, metallocenes, and the like.

  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 Vinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, and 2- (4-benzofuran-2-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3 5-triazine etc. are mentioned.

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

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

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

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

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

  Examples of the phosphine oxide include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, and the like. Is mentioned.

Examples of the hexaarylbiimidazole include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-fluorophenyl)- 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis ( 2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (3-methoxyphenyl) ) Biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (4-methoxyphenyl) biimidazole, 2,2′-bis (4-methoxyphenyl) -4 , 4 ', 5,5'-tetraphenylbi Dazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-nitrophenyl) -4,4 ′, 5 , 5′-tetraphenylbiimidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-trifluoromethylphenyl) ) -4,4 ′, 5,5′-tetraphenylbiimidazole, compounds described in WO00 / 52529, and the like.
The biimidazoles are described in, for example, Bull. Chem. Soc. Japan, 33, 565 (1960); Org. It can be easily synthesized by the method disclosed in Chem, 36 (16) 2262 (1971).

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

Examples of the organic peroxide include 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone.
Examples of the thio compound include 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-benzoylmethylene-3-methylnaphthothiazoline, and the like.

  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′- Bis (dicyclohexylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4′-dimethylamino Benzophenone, 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, Jill dimethyl ketal), and the like.

Examples of the aromatic onium salt include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, tetraphenylphosphonium-hexafluorophosphate, and the like.
Examples of the metallocenes include bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, η5- And cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-).

  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.), JP-A-53-133428, JP-B-57-1819, Examples thereof include compounds described in JP-A-57-6096 and US Pat. No. 3,615,455.

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

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- Ircoumarin, 7-diethylamino-4-methylcoumarin, JP-A-5-19475, JP-A-7-271028, JP-A-2002-363206, JP-A-2002-363207, JP-A-2002-363208, JP-A-2002-363208 And coumarins such as coumarin compounds described in JP 2002-363209 A, and the like.
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 of the photopolymerization initiator and the sensitizer include, for example, an electron transfer start system described in JP-A-2001-305734 [(1) an electron donating initiator and a sensitizing dye, (2) A combination of an electron-accepting initiator and a sensitizing dye, (3) an electron-donating initiator, a sensitizing dye and an electron-accepting initiator (ternary initiation system)], and the like.

  As content of the said sensitizer, 0.05-30 mass% is preferable with respect to all the components in the said photosensitive composition material, 0.1-20 mass% is more preferable, 0.2-10 mass% % Is particularly preferred. When the content is less than 0.05% by mass, the sensitivity to active energy rays is reduced, the exposure process takes time, and productivity may be reduced. The sensitizer may be precipitated from the photosensitive layer.

The said photoinitiator may be used individually by 1 type, and may use 2 or more types together.
As a particularly preferable example of the photopolymerization initiator, a combination of the phosphine oxides, the halogenated hydrocarbon compound having the triazine skeleton, and an amine compound, which can be applied to laser light having a wavelength of 405 nm in the later-described exposure. Composite photoinitiators, hexaarylbiimidazole compounds, hexaarylbiimidazole compounds and hetero-fused compounds, or metallocenes.
Furthermore, a chain transfer agent (for example, a mercapto compound, more specifically 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, etc.) may be used in combination with these initiators.

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

[(D) 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 groups 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 resins, novolac type epoxy resins, bisphenol F type epoxy resins, hydrogenated bisphenols 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 groups 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 70% 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 (49), a β-alkyl glycidyl ether derived from a polymer obtained from the bisphenol compound and epichlorohydrin, and the following structural formula (50) Phenol compound-formaldehyde polycondensate poly-β-alkyl glycidyl ether is preferred.
However, in said structural formula (49), R represents either a hydrogen atom or a C1-C6 alkyl group, and n represents the integer of 0-20.
In the Structural Formula (50), 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 an epoxy compound having at least two oxirane groups 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.

Moreover, in order to accelerate the thermal curing of the epoxy compound or the oxetane compound, for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzyl Amines, amine compounds such as 4-methyl-N, N-dimethylbenzylamine; quaternary ammonium salt compounds such as triethylbenzylammonium chloride; blocked isocyanate compounds such as dimethylamine; imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, etc. Dazole derivative bicyclic amidine compounds and salts thereof; phosphorus compounds such as triphenylphosphine; guanamine compounds such as melamine, guanamine, acetoguanamine, benzoguanamine; 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2- Vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid addition S-triazine derivatives such as products can be used. These may be used alone or in combination of two or more. In addition, there is no restriction | limiting in particular as long as it can accelerate | stimulate the reaction of the said epoxy compound and the said oxetane compound, or these and a carboxyl group, Use the compound which can accelerate | stimulate thermosetting other than the above. Also good.
As solid content in the said photosensitive composition solid content of the said epoxy compound, the said oxetane compound, and the compound which can accelerate | stimulate thermosetting with these and carboxylic acid, it 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, 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 and trimethylolpropane, pentalysitol, glycerin, etc. An alkylene oxide adduct of the polyfunctional alcohol and an adduct of the bifunctional isocyanate; hexamethylene diisocyanate, hexamethylene-1,6-diisocyanate Cyclic trimers, such as sulphonate and derivatives thereof; and the like.

Furthermore, for the purpose of improving the preservability of the photosensitive composition of the present invention or the photosensitive film of the present invention, a compound obtained by reacting a blocking agent with the isocyanate group of the polyisocyanate and its derivative is used. May be.
Examples of the isocyanate group blocking agent include alcohols such as isopropanol and tertiary butanol; lactams such as ε-caprolactam; phenol, cresol, p-tertiary butylphenol, p-secondary butylphenol, p-secondary amylphenol, and p-octylphenol. Phenols such as p-nonylphenol; heterocyclic hydroxyl compounds such as 3-hydroxypyridine and 8-hydroxyquinoline; active methylene compounds such as dialkylmalonate, methylethylketoxime, acetylacetone, alkylacetoacetate oxime, acetoxime and cyclohexanone oxime And the like. 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.

  As solid content in the said photosensitive composition solid content of the said thermal crosslinking agent, 1-50 mass% is preferable and 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, it is possible to adjust properties such as the stability, photographic properties, and film properties of the intended photosensitive composition or photosensitive film.

-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, tertiary butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine. , Chloranil, naphthylamine, β-naphthol, 2,6-ditertiarybutyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tertiarybutylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid 4-toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, and 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.

-Color pigment-
There is no restriction | limiting in particular as said coloring pigment, According to the objective, it can select suitably, For example, Victoria pure blue BO (CI. 42595), auramine (CI. 41000), fat black HB (C.I. 26150), Monolite Yellow GT (C.I. Pigment Yellow 12), Permanent Yellow GR (C.I. 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 Supra (CI Pigment Red 81) Monast Le Fast Blue (C.I. Pigment Blue 15), Monolight 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.

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

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

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

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

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

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

  The photosensitive composition of the present invention has high exposure sensitivity, low surface tackiness, good laminating properties and handleability, excellent storage stability, and excellent plating resistance, chemical resistance, surface hardness after development. And develops heat resistance. For this reason, it is widely used for the formation of permanent patterns such as printed wiring boards (multi-layer wiring boards, build-up wiring boards, etc.), color filters, pillar materials, rib materials, spacers, partition walls and other display members, holograms, micromachines, and proofs. In particular, it can be suitably used for the photosensitive film, permanent pattern and method of forming the same of the present invention.

(Photosensitive film)
The photosensitive film of the present invention comprises at least a support and a photosensitive layer, preferably a protective film, and further includes a cushion layer, an oxygen barrier layer (PC layer) and the like as necessary. It has other layers.
The photosensitive film has a photosensitive layer formed by laminating the above-described photosensitive composition of the present invention on the support, and when the photosensitive layer is exposed and developed, the photosensitive layer is exposed. The minimum energy of light used for the exposure that does not change the thickness of the portion after the exposure and development is preferably 100 mJ / cm ² or less.

  The form of the photosensitive film is not particularly limited and may be appropriately selected depending on the purpose. For example, the photosensitive layer and the protective film are provided in this order on the support, On the support, the PC layer, the photosensitive layer, and the protective film are arranged in this order. On the support, the cushion layer, the PC layer, the photosensitive layer, and the protective film are arranged in this order. The form which has is mentioned. The photosensitive layer may be a single layer or a plurality of layers.

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

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

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

  There is no restriction | limiting in particular as a shape of the said support body, Although it can select suitably according to the objective, A long shape is preferable. There is no restriction | limiting in particular as the length of the said elongate support body, For example, the thing of the length of 10m-20,000m is mentioned.

(Photosensitive layer)
The photosensitive layer is formed by the photosensitive composition of the present invention.
There is no restriction | limiting in particular as a location provided in the said photosensitive film of the said photosensitive layer, Although it can select suitably according to the objective, Usually, it laminates | stacks on the said support body.
In the exposure process described later, the photosensitive layer modulates the light from the light irradiating means by means of a light modulating means having n picture element portions that receive and emit light from the light irradiating means, and then It is preferable that exposure is performed with light passing through a microlens array in which microlenses having aspherical surfaces capable of correcting aberration due to distortion of the exit surface at the portion are arranged.

When exposing and developing the photosensitive layer, 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. it is preferred, more preferably 0.5~80mJ / cm ^2, and particularly preferably 1.0~60mJ / cm ^2. If the minimum energy of light used for the exposure exceeds 100 mJ / cm ² , the tact time becomes long, which is not preferable.

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 thickness of the cured layer and the thickness of the photosensitive layer before the exposure are 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.

  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.

  As a method for forming the photosensitive layer, a photosensitive composition solution is prepared by dissolving, emulsifying or dispersing the photosensitive composition of the present invention in water or a solvent on the support, and the solution is directly applied. The method of laminating | stacking by apply | coating and drying is mentioned.

  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, normal-propanol, isopropanol, normal-butanol, secondary butanol, normal-hexanol etc. Alcohols; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone and other ketones; ethyl acetate, butyl acetate, acetic acid-normal-amyl, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxy Esters such as propyl acetate; aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene; carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, chloride Halogenated hydrocarbons such as tylene and monochlorobenzene; ethers such as tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethylsulfoxide, Examples include sulfolane. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.

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

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

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

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

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

The photosensitive film of the present invention has high exposure sensitivity, small surface tackiness, good laminating properties and handling properties, excellent storage stability, excellent plating resistance after development, chemical resistance, surface hardness, It has a photosensitive layer on which a photosensitive composition exhibiting heat resistance and the like is laminated. For this reason, it can be widely used for the formation of permanent patterns such as printed wiring boards, color filters, pillar materials, rib materials, spacers, partition walls, holograms, micromachines, proofs, and the like. It can be suitably used for the forming method.
In particular, since the thickness of the photosensitive film of the present invention is uniform, lamination to a substrate is performed more finely when forming a permanent pattern.

(Permanent pattern and permanent pattern forming method)
The permanent pattern of the present invention is obtained by the permanent pattern forming method of the present invention.
In the method for forming a permanent pattern of the present invention, as a first embodiment, the photosensitive composition of the present invention is applied to the surface of a substrate, dried to form a photosensitive layer, and then exposed and developed.
In addition, in the method for forming a permanent pattern of the present invention, as a second aspect, the photosensitive film of the present invention is laminated on the surface of the substrate under at least one of heating and pressing, and then exposed and developed. .
Hereinafter, the details of the permanent pattern of the present invention will be clarified through the description of the method for forming a permanent pattern of the present invention.

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

  The substrate is a laminate in which a photosensitive layer made of the photosensitive composition is formed on the substrate as the first aspect, and the photosensitive layer in the photosensitive film is overlapped as the second aspect. Thus, a laminated body can be formed and used. That is, by exposing the photosensitive layer in the laminated body to be described later, the exposed region can be cured, and a permanent pattern can be formed by development to be described later.

-Laminate-
There is no restriction | limiting in particular as a formation method of the said laminated body, Although it can select suitably according to the objective, As said 1st aspect, it forms by apply | coating and drying the said photosensitive composition on the said base material. And a method of laminating the photosensitive film on the surface of the substrate under at least one of heating and pressurization.

In the method for forming a photosensitive layer according to the first aspect, a photosensitive layer is formed by applying and drying the photosensitive composition on the substrate.
There is no restriction | limiting in particular as the method of the said application | coating and drying, According to the objective, it can select suitably, For example, application | coating of the said photosensitive composition solution performed when forming the photosensitive layer in the said photosensitive film. For example, a method of applying the photosensitive composition solution using a spin coater, a slit spin coater, a roll coater, a die coater, a curtain coater, or the like can be given.

There is no restriction | limiting in particular as a formation method of the laminated body of a said 2nd aspect, Although it can select suitably according to the objective, At least any one of a heating and pressurization of the said photosensitive film on the said base material is carried out. It is preferable to laminate while performing. In addition, when the said photosensitive film has the said protective film, it is preferable to peel this protective film and to laminate | stack so that the said photosensitive layer may overlap with the said base material.
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.

[Exposure process]
The exposure step is a step of exposing the photosensitive layer.

  The object of exposure is not particularly limited as long as it is a material having a photosensitive layer, and can be appropriately selected according to the purpose. For example, the photosensitive composition or the photosensitive film on a substrate is used. It is preferable to be performed on the laminated body in which is formed.

  There is no restriction | limiting in particular as exposure to the said laminated body, According to the objective, it can select suitably, For example, you may expose the said photosensitive layer through the said support body, cushion layer, and PC layer, After peeling the support, the photosensitive layer may be exposed through the cushion layer and the PC layer. After peeling the support and cushion layer, the photosensitive layer is exposed through the PC layer. Alternatively, the photosensitive layer may be exposed after the support, the cushion layer and the PC layer are peeled off.

  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, light irradiation means for irradiating light, light emitted from the light irradiation means based on pattern information to be formed And a light modulation means for modulating the light intensity.

<Light modulation means>
The light modulation 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.

The light modulation means preferably includes pattern signal generation means for generating a control signal based on pattern information to be formed. 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, the DMD 50 has a large number of micromirrors 62 (for example, 1,024 × 768) constituting each pixel (pixel) on an SRAM cell (memory cell) 60. It is a mirror device arranged in a shape. In each pixel, a micromirror 62 supported by a support column is provided at the top, and a material having high reflectance 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. The on / off control of each micromirror 62 is performed by a controller 302 (see FIG. 12) 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 large number (for example, 1,024) of micromirrors are arranged in the longitudinal direction are arranged in a short direction (for example, 756 sets). as shown in), by inclining the DMD 50, the pitch P ₂ of the scanning locus of the exposure beams 53 from each micromirror (scan line), it becomes narrower than the pitch P ₁ of the scanning line in the case of not tilting the DMD 50, the resolution Can be greatly 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 unit can control any less than n number of pixel parts arranged continuously from the n number of 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 DMD 50 is irradiated with the laser beam B from the fiber array light source 66, the laser beam reflected when the micromirror of the DMD 50 is in an on state is imaged on the photosensitive layer 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 photosensitive layer 150 is exposed in approximately the same number of pixel units (exposure area 168) as the number of pixels used in the DMD 50. Further, when the photosensitive layer 150 is moved at a constant speed together with the stage 152, the photosensitive layer 150 is sub-scanned in the direction opposite to the stage moving direction by the scanner 162, and a strip-shaped exposed area 170 is formed for each exposure head 166. Is done.

  In this example, as shown in FIGS. 4A and 4B, the DMD 50 has 768 pairs of micromirror arrays in which 1,024 micromirrors are arranged in the main scanning direction. However, in this example, the controller 302 (see FIG. 12) performs control so that only a part of micromirror rows (for example, 1,024 × 256 rows) are 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 photosensitive layer 150 by the scanner 162 is finished and the rear end of the photosensitive layer 150 is detected by the sensor 164, the stage 152 is moved to the uppermost stream side of the gate 160 along the guide 158 by the stage driving device 304. It returns to a certain origin, and again moves 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. In this case, it is preferable to use the exposure light in combination with the high-speed modulation. Thereby, high-speed exposure can be performed in a short time.

  In addition, as shown in FIG. 5, the entire surface of the photosensitive layer 150 may be exposed by a single scan in the X direction by the scanner 162, and as shown in FIGS. After scanning the photosensitive layer 150 in the X direction, the scanner 162 is moved one step in the Y direction, and scanning in the X direction is repeated, so that the entire surface of the photosensitive layer 150 is scanned by a plurality of scans. You may make it expose. 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 permanent 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 the stacked body having the photosensitive layer 150 on the surface thereof.
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 photosensitive layer 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 photosensitive layer 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 photosensitive layer 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 the controller 302 (see FIG. 12) including 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.

  Further, an imaging optical system 51 that images the laser beam B reflected by the DMD 50 on the photosensitive layer 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 will be described later, only 1,024 × 256 rows of the 1,024 × 768 rows of micromirrors of the DMD 50 are driven, and accordingly, the microlens 55a has 1,024 × 256 correspondingly. Arranged in columns. 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 photosensitive layer 150. Therefore, as a whole, the image by the DMD 50 is magnified 4.8 times and is formed and projected on the photosensitive layer 150.

  A prism pair 73 is disposed between the second imaging optical system and the photosensitive layer 150, and the prism pair 73 is moved in the vertical direction in FIG. 11 to focus the image on the photosensitive layer 150. Can be adjusted. In the figure, the photosensitive layer 150 is sub-scanned in the direction of arrow F.

The picture element 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, by the permanent pattern forming method of the present invention When the formed permanent pattern 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 according to the purpose. 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 means capable of synthesizing and irradiating two or more lights. Among these, means capable of synthesizing and irradiating two or more lights are 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 laser beam obtained by combining two or more beams (hereinafter, referred to as “combined laser beam”). ) Is more preferable. Even when light irradiation is performed after the support is peeled off, the same light can be used.

The wavelength of the ultraviolet to visible light is preferably, for example, 300 to 1,500 nm, more preferably 320 to 800 nm, and particularly preferably 330 nm to 650 nm.
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, 395 nm-415 nm is especially preferable.

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

  Hereinafter, means (fiber array light source) capable of irradiating the combined laser beam 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. Further, 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.

  Also, a short optical fiber in which an optical fiber having a short length and a large cladding diameter is fused to an optical fiber having a small 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 through 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 formed, which is particularly suitable as a fiber light source constituting the laser light source of the pattern forming apparatus.

  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 permanent 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 the combined laser light, an output of about 1 W can be obtained with six multimode optical fibers, and the light emitting area of the laser emitting portion 68 can be obtained. Since the area 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. Can be planned. 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, the diameter of the light emitting region of the fiber array light source 66 in the sub-scanning direction is small, so that the light flux that passes through the lens system 67 and enters the DMD 50 , And 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 photosensitive film 150 having the photosensitive layer 150 adsorbed on the surface thereof is moved at a constant speed along the guide 158 from the upstream side to the downstream side of the gate 160 by a driving device (not shown). When the leading edge of the photosensitive layer 150 is detected by the detection sensor 164 attached to the gate 160 when 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. 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 forms an image on the exposed surface 56 of the photosensitive layer 150 by the lens systems 54 and 58. Is done. In this manner, the laser light emitted from the fiber array light source 66 is turned on / off for each pixel, and the photosensitive layer 150 is exposed in approximately the same number of pixel units (exposure area 168) as the number of pixels used in the DMD 50. Further, when the photosensitive layer 150 is moved at a constant speed together with the stage 152, the photosensitive layer 150 is sub-scanned in the direction opposite to the stage moving direction by the scanner 162, and a strip-shaped exposed area 170 is formed for each exposure head 166. Is done.

<Microlens array>
The exposure is preferably performed through the microlens array with the modulated light, 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 a result of measuring the flatness of the reflection 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 permanent 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 permanent pattern forming method of the present invention, as described above with reference to FIG. 4, the 1,024 × 256 rows of micromirrors 62 of the DMD 50 are driven, and the microlens array 55 is correspondingly driven. Is constructed by arranging 256 rows of 1,024 microlenses 55a arranged in the horizontal direction 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 FIG. 20A to FIG. 20D, in the permanent pattern forming method of the present invention, the microlens 55a has a focal length in the cross section parallel to the y direction in the cross section parallel to the x direction. By using a toric lens smaller than the focal length, distortion of the beam shape in the vicinity of the condensing position is suppressed. If so, a higher-definition image without distortion can be exposed on the photosensitive layer 150. It can also be seen that the embodiment shown in FIGS. 19a to 19d has a wider region with a smaller beam diameter, that is, a greater depth of focus.

  In addition, when the magnitude relation 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 composed of a toric lens that is smaller than the focal length, similarly, a higher-definition image without distortion can be exposed on the photosensitive layer 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 permanent 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 permanent pattern forming method of the present invention using a spatial light modulation element other than the DMD, the spatial When there is distortion on the surface of the picture element portion of the light 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 permanent 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 quantity 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 permanent 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 part near the optical axis is larger than the light quantity in the peripheral part by reducing the core diameter of the multimode 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 next numerical value is a “power exponent” with 10 as the base. The numerical value represented by the exponential function with the base 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. Preferred examples include an aqueous salt solution. 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 permanent pattern forming method of the present invention preferably further includes a curing treatment step.
The curing treatment step is a step of performing a curing treatment on the photosensitive layer in the formed permanent pattern after the development step is performed.

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

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

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

[Other processes]
There is no restriction | limiting in particular as said other process, Although selecting suitably from the process in well-known pattern formation is mentioned, For example, an etching process, a plating process, etc. are mentioned. These may be used alone or in combination of two or more.

<Etching process>
The etching step can be performed by a method appropriately selected from known etching methods.
There is no restriction | limiting in particular as an etching liquid used for the said etching process, Although it can select suitably according to the objective, For example, when the said metal layer is formed with copper, a cupric chloride solution, Examples thereof include a ferric chloride solution, an alkali etching solution, and a hydrogen peroxide-based etching solution. Among these, a ferric chloride solution is preferable from the viewpoint of an etching factor.
A permanent pattern can be formed on the surface of the substrate by removing the pattern after performing the etching process in the etching step. In the present invention, by adding a polymerizable compound having at least one vinyl group having a substituted methyl group at the α-position, the chemical resistance is improved, and the permanent pattern is prevented from being damaged or chipped by the etching solution. Thus, a high-definition permanent pattern can be obtained.
There is no restriction | limiting in particular as said permanent pattern, According to the objective, it can select suitably, For example, a wiring pattern etc. are mentioned suitably.
<Plating process>
The plating step can be performed by a method appropriately selected from known plating processes.
Examples of the plating treatment in the case of a solder resist include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high flow solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel sulfamate, and the like. Examples of the method include gold plating such as nickel plating, hard gold plating, and soft gold plating.
In the plating process, in the present invention, by adding a polymerizable compound having at least one vinyl group having a substituted methyl group at the α-position, the plating resistance is improved, and the pattern is damaged or chipped by the plating solution. Is prevented, and the plating process can be performed with high precision and a uniform line width.
A permanent pattern can be formed on the surface of the substrate by removing the pattern after plating by the plating step, and further removing unnecessary portions by etching or the like as necessary.

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. At this time, by adding a polymerizable compound having at least one vinyl group having a substituted methyl group at the α-position, the plating resistance is improved, and damage or chipping of the permanent pattern due to plating solution or solder is prevented. High-definition gold plating or soldering is performed with a uniform line width. Then, a semiconductor or a component is mounted on the soldered portion. At this time, the permanent pattern by the hardened layer having improved film hardness functions 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. If the permanent pattern formed by the permanent pattern forming method is the protective film or the interlayer insulating film, the wiring can be protected from external impact and bending, and if it is a solder resist pattern, the cured film Improvement of film hardness and chemical resistance makes it excellent in durability that can be stored for a long time, and in particular, in the case of the interlayer insulating film, for example, semiconductors such as multilayer wiring boards and build-up wiring boards Useful for high-density mounting of parts.

The permanent pattern forming method of the present invention can be widely used for forming various patterns because the pattern can be formed at a high speed, and can be particularly suitably used for forming a wiring pattern.
The permanent pattern formed by the permanent pattern forming method of the present invention has excellent film hardness, insulating properties, heat resistance, chemical resistance, etc., and is suitable as a protective film, an interlayer insulating film or a solder resist pattern. Can be used.

  Examples of the present invention will be described below, but the present invention is not limited to the following examples.

Example 1
-Preparation of photosensitive composition-
A photosensitive composition (solution) was prepared based on the following composition.
[Composition of photosensitive composition solution]
Barium sulfate dispersion 50.00 parts by mass PCR-1157H (manufactured by Nippon Kayaku Co., Ltd., epoxy acrylate, 61.8% by mass ethylene glycol monoethyl ether acrylate solution) 81.70 parts by mass Dipentaerythritol hexaacrylate (DPHA) 7. 00 parts by mass Polymerizable compound 1 containing at least one aromatic ring having a vinyl group represented by the following structural formula (45) and comprising a ring composed of C, S, and O atoms 7.00 parts by mass IRGACURE819
(Manufactured by Ciba Specialty Chemicals) 6.82 parts by mass Epoxy resin 1 represented by the following structural formula (51) 25.00 parts by mass Dicyandiamide 0.13 parts by mass Hydroquinone monomethyl ether 0.024 parts by mass Phthalocyanine green 42 parts by mass

Epoxy resin 1 (epoxy equivalent: 214 g / eq., Viscosity: 62,000 mPa · s)

The barium sulfate dispersion was composed of 30 parts by weight of barium sulfate (manufactured by Sakai Chemical Co., Ltd., B30), 34.29 parts by weight of the 61.8% by weight ethylene glycol monoethyl ether acrylate solution of PCR-1157H, After 35.71 parts by mass of methoxy-2-propylacetate was mixed in advance, a motor mill M-200 (manufactured by Eiger) was used and zirconia beads having a diameter of 1.0 mm were used and a peripheral speed of 9 m / s was 3.5. Prepared by time dispersion.
The content of the polymerizable compound 1 containing at least one aromatic ring having a vinyl group represented by the structural formula (45) and containing a ring composed of C, S, and O atoms in the polymerizable compound is 50 The content of DPHA is 50% by mass.

-Production of photosensitive film-
The obtained photosensitive composition solution was applied onto a PET (polyethylene terephthalate) film having a thickness of 20 μm as the support and dried to form a photosensitive layer having a thickness of 35 μm. Next, a polypropylene film having a thickness of 12 μm was laminated as a protective film on the photosensitive layer to produce a photosensitive film.
The tackiness of the surface of the photosensitive layer in the obtained photosensitive film was evaluated based on the following criteria. The results are shown in Table 3.
〔Evaluation criteria〕
○: Strong tackiness was not recognized on the surface of the photosensitive layer.
Δ: Slight tackiness was observed on the surface of the photosensitive layer.
X: Strong tackiness was recognized on the surface of the photosensitive layer.

-Formation of permanent pattern-
--- Production 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 on the photosensitive film so that the photosensitive layer of the photosensitive film was in contact with the copper clad laminate. Lamination was performed to produce 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.
When the protective film on the photosensitive film was peeled off, the surface of the photosensitive layer did not have strong tackiness, and the peeling itself could be performed smoothly.

--Exposure process--
Using a laser exposure device, 405 nm laser light is irradiated from the polyethylene terephthalate film (support) side to the photosensitive layer in the produced laminate so that a pattern in which holes having different diameters are formed is obtained. Then, a portion of the photosensitive layer was cured.

--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 60 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.

  The formed permanent pattern was evaluated for exposure sensitivity, resolution, pencil hardness, exposure speed, heat resistance, and plating resistance. The results are shown in Table 3.

<Exposure sensitivity>
In the obtained permanent pattern, the thickness of the cured region of the remaining photosensitive layer was measured. Subsequently, a sensitivity curve is obtained by plotting the relationship between the irradiation amount of the laser beam and the thickness of the cured layer. From the sensitivity curve thus obtained, the thickness of the cured region on the wiring was 15 μm, and the amount of light energy when the surface of the cured region was a glossy surface was the amount of light energy required to cure the photosensitive layer.
As a result, the amount of light energy necessary for curing the photosensitive layer was 55 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. As a result, the minimum pore diameter showing the resolution was 70 μm.

<Pencil hardness>
The pencil hardness of the printed wiring board on which the permanent pattern had been formed was measured based on JIS K-5400.
As a result, the pencil hardness was 5H. Further, when visually observed, the cured film in the permanent pattern was not peeled, blistered or discolored.

<Exposure speed>
Using a 405 nm laser exposure apparatus, the speed at which the exposure light and the photosensitive layer were relatively moved was changed, and the speed at which the permanent pattern was formed was determined. Exposure was performed from the polyethylene terephthalate film (support) side with respect to the photosensitive layer in the produced laminated body. It should be noted that an efficient permanent pattern can be formed at a higher setting speed. The 405 nm laser exposure apparatus had a light modulation means composed of the DMD, and the exposure speed was 13 mm / sec.

<Plating resistance>
The obtained permanent pattern was degreased to roughen the surface, and then palladium sulfate was added to perform catalyst addition. Next, after immersing the permanent pattern in a nickel sulfate / dilute sulfuric acid solution at 70 ° C. for 40 minutes to perform plating, the cured film in the permanent pattern was visually turned up and peeled off, based on the following criteria: The plating resistance was evaluated. The results are shown in Table 3.
〔Evaluation criteria〕
(Double-circle): It turns over to a cured film, there is no peeling, and it is very excellent in plating resistance.
○: Discoloration occurs in a part of the cured film, but this is not a problem for practical use and has excellent plating resistance.
Δ: The cured film is turned over and the plating resistance is poor.
X: Floating (peeling) is observed in the cured film, and the plating resistance is extremely poor.

<Heat resistance>
About the obtained cured film, it cooled after heating at 200 degreeC for 5 minutes, and heat resistance was evaluated based on the following reference | standard. In Example 1, the cured film was not swollen, peeled off or discolored and exhibited excellent heat resistance.
〔Evaluation criteria〕
○: No swelling, peeling or discoloration of the cured film was observed.
Δ: Although there was no swelling or peeling of the cured film, partial discoloration was observed.
X: Swelling and peeling were observed in the cured film.

Moreover, the storage stability of the produced photosensitive film was evaluated as follows. The results are also shown in Table 3.
<Storage stability>
The produced photosensitive film was stored for 2 days under accelerated conditions of 60 ° C. drying. Two days later, the exposure sensitivity and resolution were measured, and storage stability was evaluated based on the following criteria. The exposure sensitivity was 55 mJ / cm ² , the resolution was 70 μm, and the storage stability was excellent.
〔Evaluation criteria〕
○: Almost no change in exposure sensitivity and resolution and excellent storage stability △: Exposure sensitivity and resolution are reduced, development becomes difficult, and storage stability is poor ×: Exposure sensitivity and resolution are significantly reduced, storage stability Very inferior or cannot be stored

(Example 2)
In Example 1, the addition amount of the polymerizable compound 1 represented by the structural formula (45) is 2.80 parts by mass (the content in the polymerizable compound is 20% by mass), and the addition amount of DPHA is 11.20. A photosensitive composition was prepared in the same manner as in Example 1 except that the content was set to part by mass (content in the polymerizable compound was 80% by mass).

-Production of photosensitive film-
A photosensitive film was produced in the same manner as in Example 1 using the obtained photosensitive composition. Slight tackiness was recognized on the surface of the photosensitive layer in the photosensitive film, but this is not a problem in practice. The tackiness on the surface of the photosensitive layer was evaluated by the same method as in Example 1. The results are shown in Table 3.

-Formation of permanent pattern-
A permanent pattern was formed by the same method as in Example 1 using the obtained photosensitive film. When the surface of the permanent pattern was visually observed, no bubbles were generated on the surface of the cured film in the permanent pattern.

With respect to the obtained permanent pattern, the exposure sensitivity, resolution, pencil hardness, heat resistance, and plating resistance were measured by the same method as in Example 1. As a result, the exposure sensitivity was 75 mJ / cm ² , the resolution was 65 μm, and the pencil hardness was 4H to 5H. Further, when visual observation was performed before the plating treatment, the cured film in the permanent pattern did not show peeling, blistering, or discoloration. Further, when visual observation was performed after the plating treatment, discoloration occurred in a part of the cured film in the permanent pattern, but there was no practical problem and the plating resistance was excellent. Moreover, although the cured film did not swell or peel off, discoloration was partially observed and good heat resistance was exhibited.

Moreover, the storage stability of the photosensitive film was also evaluated. The exposure sensitivity after storage of the photosensitive film was 75 mJ / cm ² , the resolution was 70 μm, and the storage stability was excellent. The results are shown in Table 3.

(Example 3)
-Preparation of photosensitive composition-
In Example 1, the addition amount of the polymerizable compound 1 represented by the structural formula (45) was 10.50 parts by mass (the content in the polymerizable compound was 75% by mass), and the addition amount of DPHA was 3.50. A photosensitive composition was prepared in the same manner as in Example 1 except that the content was changed to part by mass (content in the polymerizable compound: 25% by mass).

-Production of photosensitive film-
A photosensitive film was produced in the same manner as in Example 1 using the obtained photosensitive composition. Strong tackiness was not recognized on the surface of the photosensitive layer in the photosensitive film. The tackiness was evaluated by the same method as in Example 1. The results are shown in Table 3.

-Formation of permanent pattern-
A permanent pattern was formed using the obtained photosensitive film. When the surface of the permanent pattern was visually observed, no bubbles were generated on the surface of the cured film in the permanent pattern.

With respect to the obtained permanent pattern, the exposure sensitivity, resolution, pencil hardness, heat resistance, and plating resistance were measured by the same method as in Example 1. As a result, the exposure sensitivity was 85 mJ / cm ² , the resolution was 75 μm, and the pencil hardness was 4H to 5H. Further, when visual observation was performed before the plating treatment, the cured film in the permanent pattern did not show peeling, blistering, or discoloration. Further, when visual observation was performed after the plating treatment, the cured film in the permanent pattern was not turned over and peeled off, and the plating resistance was excellent. Further, the cured film did not swell, peel or discolor, and exhibited excellent heat resistance.

Moreover, the storage stability of the photosensitive film was also evaluated. The exposure sensitivity after storage of the photosensitive film was 85 mJ / cm ² , the resolution was 80 μm, and the storage stability was excellent. The results are shown in Table 3.

Example 4
-Preparation of photosensitive composition-
In Example 1, the addition amount of the polymerizable compound 1 represented by the structural formula (45) is 12.60 parts by mass (the content is 90% by mass in the polymerizable compound), and the addition amount of DPHA is 1.40. A photosensitive composition was prepared in the same manner as in Example 1 except that the content was 10 parts by mass (the content in the polymerizable compound was 10% by mass).

-Production of photosensitive film-
A photosensitive film was produced in the same manner as in Example 1 using the obtained photosensitive composition. Strong tackiness was not recognized on the surface of the photosensitive layer in the photosensitive film. The tackiness was evaluated by the same method as in Example 1. The results are shown in Table 3.

-Formation of permanent pattern-
Using the obtained photosensitive film, a permanent pattern was formed by the same method as in Example 1. In Example 4, when the surface of the permanent pattern was visually observed, the surface of the cured film in the permanent pattern was obtained. There were no bubbles.

About the obtained permanent pattern, the exposure sensitivity, resolution, pencil hardness, and plating resistance were measured by the same method as in Example 1. As a result, the exposure sensitivity was 95 mJ / cm ² , the resolution was 75 μm, and the pencil hardness was 4H to 5H. Further, when visual observation was performed before the plating treatment, the cured film in the permanent pattern did not show peeling, blistering, or discoloration. Moreover, when visual observation was performed after the plating treatment, there was discoloration in a part of the cured film in the permanent pattern as compared with Examples 1 to 3, but there was no practical problem and good plating resistance was exhibited. Moreover, although discoloration was recognized partially in the cured film, it did not swell and peel off and showed good heat resistance.

Moreover, the storage stability of the photosensitive film was also evaluated. The exposure sensitivity after storage of the photosensitive film was 100 mJ / cm ² , the resolution was 85 μm, and the storage stability was good. The results are shown in Table 3.

(Example 5)
In Example 1, the polymerizable compound 1 represented by the structural formula (45) is a C, S, and O atom having at least one aromatic ring having a vinyl group represented by the following structural formula (46). A photosensitive composition was prepared in the same manner as in Example 1 except that the polymerizable compound 2 containing a ring consisting of

-Production of photosensitive film-
A photosensitive film was produced in the same manner as in Example 1 using the obtained photosensitive composition. Strong tackiness was not recognized on the surface of the photosensitive layer in the photosensitive film. The tackiness on the surface of the photosensitive layer was evaluated by the same method as in Example 1. The results are shown in Table 4.

-Formation of permanent pattern-
A permanent pattern was formed by the same method as in Example 1 using the obtained photosensitive film. When the surface of the permanent pattern was visually observed, no bubbles were generated on the surface of the cured film in the permanent pattern.

With respect to the obtained permanent pattern, the exposure sensitivity, resolution, pencil hardness, heat resistance, and plating resistance were measured by the same method as in Example 1. As a result, the exposure sensitivity was 60 mJ / cm ² , the resolution was 80 μm, and the pencil hardness was 5H to 6H. Further, when visual observation was performed before the plating treatment, the cured film in the permanent pattern did not show peeling, blistering, or discoloration. Further, when visual observation was performed after the plating treatment, the cured film in the permanent pattern was not turned over or peeled off, and extremely excellent plating resistance was exhibited. Further, the cured film did not swell, peel or discolor, and exhibited excellent heat resistance.

Moreover, the storage stability of the photosensitive film was also evaluated. The exposure sensitivity after storage of the photosensitive film was 60 mJ / cm ² , the resolution was 80 μm, and the storage stability was excellent. The results are shown in Table 4.

(Example 6)
-Preparation of photosensitive composition-
In Example 1, the polymerizable compound 1 represented by the structural formula (45) is a C, S, and O atom having at least one aromatic ring having a vinyl group represented by the following structural formula (47). A photosensitive composition was prepared in the same manner as in Example 1 except that the polymerizable compound 3 containing a ring composed of

-Production of photosensitive film-
A photosensitive film was produced in the same manner as in Example 1 using the obtained photosensitive composition. Strong tackiness was not recognized on the surface of the photosensitive layer in the photosensitive film. The tackiness was evaluated by the same method as in Example 1. The results are shown in Table 4.

-Formation of permanent pattern-
A permanent pattern was formed by the same method as in Example 1 using the obtained photosensitive film. When the surface of the permanent pattern was visually observed, no bubbles were generated on the surface of the cured film in the permanent pattern.

With respect to the obtained permanent pattern, the exposure sensitivity, resolution, pencil hardness, heat resistance, and plating resistance were measured by the same method as in Example 1. As a result, the exposure sensitivity was 50 mJ / cm ² , the resolution was 65 μm, and the pencil hardness was 5H to 6H. Further, when visual observation was performed before the plating treatment, the cured film in the permanent pattern did not show peeling, blistering, or discoloration. Moreover, when visual observation was performed after the plating treatment, the cured film in the permanent pattern was not turned over or peeled off, and excellent plating resistance was exhibited. Further, the cured film did not swell, peel or discolor, and exhibited excellent heat resistance.

Moreover, the storage stability of the photosensitive film was also evaluated. The exposure sensitivity after storage of the photosensitive film was 50 mJ / cm ² , the resolution was 65 μm, and the storage stability was excellent. The results are shown in Table 4.

(Example 7)
-Preparation of photosensitive composition-
In Example 1, the polymerizable compound 1 represented by the structural formula (45) is a C, S, and O atom having at least one aromatic ring having a vinyl group represented by the following structural formula (43). A photosensitive composition was prepared in the same manner as in Example 1 except that the polymerizable compound 4 containing a ring consisting of

-Production of photosensitive film-
A photosensitive film was produced in the same manner as in Example 1 using the obtained photosensitive composition. Strong tackiness was not recognized on the surface of the photosensitive layer in the photosensitive film. The tackiness was evaluated by the same method as in Example 1. The results are shown in Table 4.

-Formation of permanent pattern-
A permanent pattern was formed by the same method as in Example 1 using the obtained photosensitive film. When the surface of the permanent pattern was visually observed, no bubbles were generated on the surface of the cured film in the permanent pattern.

With respect to the obtained permanent pattern, the exposure sensitivity, resolution, pencil hardness, heat resistance, and plating resistance were measured by the same method as in Example 1. As a result, the exposure sensitivity was 50 mJ / cm ² , the resolution was 60 μm, and the pencil hardness was 6H. Further, when visual observation was performed before the plating treatment, the cured film in the permanent pattern did not show peeling, blistering, or discoloration. Moreover, when visual observation was performed after the plating treatment, the cured film in the permanent pattern was not turned over or peeled off, and excellent plating resistance was exhibited. Further, the cured film did not swell, peel or discolor, and exhibited excellent heat resistance.

Moreover, the storage stability of the photosensitive film was also evaluated. The exposure sensitivity after storage of the photosensitive film was 55 mJ / cm ² , the resolution was 60 μm, and the storage stability was excellent. The results are shown in Table 4.

(Example 8)
-Preparation of photosensitive composition-
In Example 1, the polymerizable compound 1 represented by the structural formula (45) is a C, S, and O atom having at least one aromatic ring having a vinyl group represented by the following structural formula (44). A photosensitive composition was prepared in the same manner as in Example 1 except that the polymerizable compound 5 containing a ring consisting of

-Production of photosensitive film-
A photosensitive film was produced in the same manner as in Example 1 using the obtained photosensitive composition. Strong tackiness was not recognized on the surface of the photosensitive layer in the photosensitive film. The tackiness was evaluated by the same method as in Example 1. The results are shown in Table 4.

-Formation of permanent pattern-
A permanent pattern was formed by the same method as in Example 1 using the obtained photosensitive film. When the surface of the permanent pattern was visually observed, no bubbles were generated on the surface of the cured film in the permanent pattern.

With respect to the obtained permanent pattern, the exposure sensitivity, resolution, pencil hardness, heat resistance, and plating resistance were measured by the same method as in Example 1. As a result, the exposure sensitivity was 60 mJ / cm ² , the resolution was 65 μm, and the pencil hardness was 5H. Further, when visual observation was performed before the plating treatment, the cured film in the permanent pattern did not show peeling, blistering, or discoloration. Moreover, when visual observation was performed after the plating treatment, the cured film in the permanent pattern was not turned over or peeled off, and excellent plating resistance was exhibited. Further, the cured film did not swell, peel or discolor, and exhibited excellent heat resistance.

Moreover, the storage stability of the photosensitive film was also evaluated. The exposure sensitivity after storage of the photosensitive film was 60 mJ / cm ² , the resolution was 65 μm, and the storage stability was excellent. The results are shown in Table 4.

Example 9
In Example 1, the exposure sensitivity, resolution, pencil hardness, exposure speed, heat resistance, and plating resistance were evaluated in the same manner as in Example 2 except that the exposure apparatus was replaced with the pattern forming apparatus described below. The results are shown in Table 5.

<< Pattern Forming Apparatus >>
27-32 as the light irradiating means, and a micromirror array in which 1,024 micromirrors are arranged in the main scanning direction shown in FIG. 4 as the light modulating means, 768 in the sub-scanning direction. A microlens array 472 in which the DMD 50 controlled to drive only 1,024 × 256 rows among the arrayed array and the microlens 474 whose one surface is a toric surface shown in FIG. 13 are arrayed. And a pattern forming apparatus having optical systems 480 and 482 for forming an image of light passing through the microlens array on the photosensitive layer.

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, 1,024 × 256 rows of micromirrors 62 of the DMD 50 are driven. Correspondingly, the microlens array 55 has 1,024 in the horizontal direction. The microlenses 55a arranged side by side are arranged 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. Moreover, it turns out that the area | region where a beam diameter is small is wider, ie, the depth of focus is larger in this embodiment shown to FIG.

  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.

(Comparative Example 1)
In Example 1, a polymerizable compound 1 containing a ring composed of C, S, and O atoms having at least one aromatic ring having a vinyl group represented by the structural formula (45) is represented by the following structural formula (52 The epoxy compound 1 of the structural formula (51) is replaced with RE805 (epoxy resin, manufactured by Nippon Kayaku Co., Ltd.) 25 as a thermal cross-linking agent instead of the polymerizable compound 6 having a vinyl group and having no aromatic ring. A photosensitive composition was prepared in the same manner as in Example 1 except that the amount was changed to 0.0 parts by mass.

-Production of photosensitive film-
A photosensitive film was produced in the same manner as in Example 1 using the obtained photosensitive composition. Strong tackiness was recognized on the surface of the photosensitive layer in the photosensitive film. The tackiness was evaluated by the same method as in Example 1. The results are shown in Table 5.

-Formation of permanent pattern-
A permanent pattern was formed by the same method as in Example 1 using the obtained photosensitive film. When the surface of the permanent pattern was visually observed, no bubbles were generated on the surface of the cured film in the permanent pattern.

With respect to the obtained permanent pattern, the exposure sensitivity, resolution, pencil hardness, heat resistance, and plating resistance were measured by the same method as in Example 1. As a result, the exposure sensitivity was 220 mJ / cm ² , the resolution was 70 μm, and the pencil hardness was 4H. Further, when visual observation was performed before the plating treatment, the cured film in the permanent pattern did not show peeling, blistering, or discoloration. Further, when visual observation was performed after the plating treatment, discoloration occurred in a part of the cured film, but this was not a problem for practical use and was excellent in plating resistance. Moreover, although the cured film was not swollen or peeled off, discoloration was partially observed and the heat resistance was slightly inferior.

  Moreover, the storage stability of the photosensitive film was also evaluated. When the photosensitive film was stored for 1 day under accelerated conditions of 50 ° C. drying, it was difficult to develop and the storage stability was poor. The results are shown in Table 6.

(Comparative Example 2)
In Comparative Example 1, a photosensitive composition was prepared in the same manner as in Example 1 except that RE805, which is a thermal crosslinking agent, was not used.

-Production of photosensitive film-
A photosensitive film was produced in the same manner as in Example 1 using the obtained photosensitive composition. Strong tackiness was recognized on the surface of the photosensitive layer in the photosensitive film. The tackiness was evaluated by the same method as in Example 1. The results are shown in 5.

-Formation of permanent pattern-
A permanent pattern was formed by the same method as in Example 1 using the obtained photosensitive film. When the surface of the permanent pattern was visually observed, no bubbles were generated on the surface of the cured film in the permanent pattern.

With respect to the obtained permanent pattern, the exposure sensitivity, resolution, pencil hardness, heat resistance, and plating resistance were measured by the same method as in Example 1. As a result, the exposure sensitivity was 220 mJ / cm ² , the resolution was 70 μm, and the pencil hardness was 3H. Further, when visual observation was performed before the plating treatment, the cured film in the permanent pattern did not show peeling, blistering, or discoloration. Moreover, when visual observation was performed after the plating treatment, the cured film in the permanent pattern was turned up and the plating resistance was poor. Further, swelling and peeling were observed in the cured film, and the heat resistance was poor.

  Moreover, the storage stability of the photosensitive film was also evaluated. When the photosensitive film was stored for 1 day under accelerated conditions of 50 ° C. drying, it was difficult to develop and the storage stability was poor. The results are shown in Table 6.

From the result of Tables 3-6, the photosensitive composition of Examples 1-9 containing the polymerizable compound containing the ring which consists of a C, S, and O atom which has at least one aromatic ring which has a vinyl group was used. The photosensitive layer in the photosensitive film produced in this way has an exposure sensitivity of 100 mJ / cm ² or less, particularly excellent exposure sensitivity, small surface tackiness, excellent storage stability and resolution, and uses the photosensitive film. It was confirmed that the surface hardness and plating resistance of the cured layer in the permanent pattern formed in this way were also good. In particular, in Examples 1, 3, and 5 to 8, the content of the polymerizable compound having a ring composed of C, S, and O atoms having at least one aromatic group having a vinyl group in the polymerizable compound is 40 Since it was -80 mass%, it was recognized that exposure sensitivity is high and heat resistance is also excellent.
In Example 9, since a high-intensity light source and a pattern forming apparatus capable of high-speed modulation were used, it was confirmed that the resolution and the exposure speed were excellent, and it was confirmed that a high-definition permanent pattern was formed.
On the other hand, in Comparative Examples 1 and 2 which do not include a polymerizable compound including a ring composed of C, S, and O atoms having at least one aromatic ring having a vinyl group, the exposure sensitivity and storage stability are extremely high. It was inferior and heat resistance was also inferior. In particular, in Comparative Example 2 in which no thermal crosslinking agent was added, the heat resistance was extremely inferior.

The photosensitive composition of the present invention and the photosensitive film using the photosensitive composition are particularly excellent in exposure sensitivity, small surface tackiness, good laminating properties and handling properties, excellent storage stability, It exhibits excellent plating resistance, chemical resistance, surface hardness, heat resistance, etc. after development. For this reason, it is widely used for the formation of permanent patterns such as printed wiring boards (multi-layer wiring boards, build-up wiring boards, etc.), color filters, pillar materials, rib materials, spacers, partition walls, and other display members, holograms, micromachines, and proofs. be able to.
The permanent pattern of the present invention has excellent surface hardness, insulation, heat resistance and the like, and can be suitably used as a protective film and an interlayer insulation film.

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 photosensitive layer is exposed by one scanning by the scanner. 6A and 6B are examples of plan views for explaining an exposure method for exposing a photosensitive layer 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 on the photosensitive layer, 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 the result of simulating the beam diameter in the vicinity of the condensing position of the microlens of the present invention. 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). FIG. 24 is an example of an explanatory diagram about the concept of correction by the light quantity 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 permanent 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 image forming optical system 58 Lens of second image forming optical system 59 Aperture array 64 Laser module 66 Fiber array light source 67 Lens system 68 Laser emitting portion 69 Mirror 70 Prism 73 Combination 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 Photosensitive layer 152 Stage 155a Micro lens 156 Installation table 158 Guide 160 Gate 162 Scanner 164 Sensor 166 Exposure head 168 Exposure area 170 Exposed area 180 Heat block 184 Collimating lens array 302 Controller 30 4 Stage Drive Device 454 Lens System 468 Exposure Area 472 Micro Lens Array 476 Aperture Array 478 Aperture 480 Lens System

Claims (24)

  (A) an alkali-soluble resin, (B) a polymerizable compound containing a ring composed of C, S, and O atoms having at least one aromatic ring having a vinyl group, (C) a photopolymerization initiator, D) A heat-crosslinking agent.   The photosensitive composition according to claim 1, wherein the aromatic ring is at least one selected from a benzene ring, a naphthalene ring, and an anthracene ring.   The photosensitive composition according to claim 1, wherein the aromatic ring is a vinylbenzene ring. (B) The polymerizable compound containing a ring composed of C, S, and O atoms having at least one aromatic ring having a vinyl group is represented by the following general formula (1). Photosensitive composition.
However, in said general formula (1), Ar represents a substituted phenyl group. Z represents an organic linking chain containing an aromatic ring compound, and n represents an integer of 1 to 10. R ¹ represents either a hydrogen atom or a substituted alkyl group.   (B) a polymerizable compound containing at least one aromatic ring having a vinyl group and a polymerizable compound containing a ring composed of C, S, and O atoms, and having at least an aromatic ring having the vinyl group The photosensitive composition according to any one of claims 1 to 4, wherein the content of the polymerizable compound containing one ring containing C, S, and O atoms in the polymerizable compound is 20 to 100% by mass. object.   (A) Alkali-soluble resin is epoxy acrylate, The photosensitive composition in any one of Claim 1 to 5.   (C) The photopolymerization initiator is at least one selected from halogenated hydrocarbon derivatives, phosphine oxides, hexaarylbiimidazoles, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, and metallocenes. The photosensitive composition in any one of Claim 1 to 6 containing a seed | species.   (D) The thermal crosslinking agent is at least one selected from an epoxy compound, an oxetane compound, a polyisocyanate compound, a compound obtained by reacting a polyisocyanate compound with a blocking agent, and a melamine derivative. The photosensitive composition in any one.   The photosensitive composition according to claim 8, wherein (D) the thermal crosslinking agent is an epoxy compound containing at least an epoxy group having an alkyl group at the β-position.   A photosensitive film comprising: a support; and a photosensitive layer obtained by laminating the photosensitive composition according to claim 1 on the support. 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 when the photosensitive layer is exposed and developed is 100 mJ / cm ² or less. The photosensitive film of description.   The photosensitive layer modulates the light from the light irradiating means by the light modulating means having n picture elements for receiving and emitting the light from the light irradiating means. The photosensitive film according to claim 10, wherein the photosensitive film is exposed with light passing through a microlens array in which microlenses having aspherical surfaces capable of correcting aberrations are arranged.   The photosensitive film according to claim 10, further comprising a protective film on the photosensitive layer.   A method for forming a permanent pattern, comprising: applying the photosensitive composition according to any one of claims 1 to 9 to a surface of a substrate; drying the coating to form a photosensitive layer; and exposing and developing the photosensitive layer.   A photosensitive film according to any one of claims 10 to 13 is laminated on the surface of a substrate under at least one of heating and pressing to form a photosensitive layer, and then exposed and developed. A permanent pattern forming method.   The permanent pattern forming method according to claim 14, wherein the base material is a printed wiring board on which wiring has been formed. 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 when the photosensitive layer is exposed and developed is 100 mJ / cm ² or less. The permanent pattern formation method in any one of from 16.   The permanent pattern formation method according to claim 14, wherein the exposure is performed imagewise based on pattern information to be formed.   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 14 to 18.   The method for forming a permanent pattern according to claim 19, wherein the aspherical surface is a toric surface.   The permanent pattern forming method according to claim 14, wherein after the development, the photosensitive layer is subjected to a curing process.   The permanent pattern formation method according to claim 21, wherein the curing process is a post-process performed by at least one of exposure and heating.   It forms with the permanent pattern formation method in any one of Claim 14 to 22, The permanent pattern characterized by the above-mentioned. The permanent pattern according to claim 23, wherein the permanent pattern is at least one of a protective film, an interlayer insulating film, and a solder resist pattern.