JP2007199205A - Photosensitive composition, photosensitive film, permanent pattern forming method and pattern - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition which causes no reaction at low temperature or at ordinary temperature during storage, excels in storage stability, has small surface tackiness, ensures good laminating property and handleability when formed into a film, excels in peelability from a protective film and a support, has high sensitivity and excellent developability, exhibits excellent chemical resistance, surface hardness, heat resistance, dielectric characteristic and electric insulation after development, and can form a high-definition pattern. <P>SOLUTION: The photosensitive composition contains at least (A) a binder, (B) a polymerizable compound, (C) a photopolymerization initiator and (D) a solvent-soluble heat crosslinking agent having at least one of a softening point and a melting point being 50-250°C. A photosensitive film, a permanent pattern forming method and a pattern are also provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention does not cause a reaction at low temperature or normal temperature during storage, has excellent storage stability, small surface tackiness, good laminating property and handleability when formed into a film, protective film and support A photosensitive composition that has excellent peelability from the body, high sensitivity and excellent developability, and exhibits excellent chemical resistance, surface hardness, heat resistance, dielectric properties, electrical insulation, and the like after development, and uses the same The present invention relates to a photosensitive film, a high-definition permanent pattern (a protective film, an interlayer insulating film, a solder resist pattern, etc.) and an efficient formation method thereof.

  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 the 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 sodium carbonate solution are mainly used 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 side of a substrate on which wiring has been formed by screen printing, spray coating, dip coating, and the like, dried, and then applied to the opposite side and dried.

In addition, as the alkali development type photo solder resist as described above, 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 an ethylenically unsaturated double bond is generally used, and specifically disclosed in Patent Document 1. However, although the solder resist described in Patent Document 1 has high surface hardness after post-baking and excellent chemical resistance, the surface tack remains, dust tends to adhere, and defects increase, or the photomask is contaminated. There is a problem that the handleability is deteriorated. 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.

  In the field of advanced electronic equipment, high-speed propagation in a high-frequency environment is required. Especially in electronic equipment typified by electronic computers and mobile communication equipment, the processing speed and signal propagation speed are increased, and the bandwidth used. As the frequency increases, the laminated plate materials are required to have a low dielectric constant and a low dielectric loss tangent. The solder resist used in the production of printed wiring boards is also required to have a low dielectric constant and a low dielectric loss tangent. However, the current alkali developing type solder resist has poor dielectric properties in the high frequency region, and is not currently satisfactory in properties as a high frequency resin.

In addition, in the products that are generally marketed as the film-type solder resist, with this film formation, a binder and a monomer and a thermal cross-linking agent are mixed in the photosensitive layer. It is a problem that it is scarce.
On the other hand, as a curing accelerator for a thermosetting resin composition such as an epoxy resin composition, from the viewpoint of the storage stability, a reaction does not occur at the time of storage, but has a property of reacting and curing by heating, so-called potential. Proposals have been made using curing accelerators. For example, the proposal which mix | blended the salt which consists of 2-ethylhexylic acid zinc and a triethanolamine, and the salt which consists of a triethylenediamine and aliphatic carboxylic acid is made (refer nonpatent literature 1 and patent document 3). These are intended to reduce solubility, suppress reaction activity and improve storage stability by using a complex accelerator as a curing accelerator.
Further, an adduct obtained by reacting an epoxy resin with dimethylamine or sometimes an alkylamine (see Patent Documents 4 and 5), an adduct obtained by reacting an epoxy resin with a tertiary amine (see Patent Documents 6 and 7). Proposals using such as have also been made. Thus, the storage stability is improved by adding an amine compound to the epoxy resin to polymerize and insolubilize it.
However, in these documents, there is no disclosure used for a solder resist, a sufficiently satisfactory storage stability performance is obtained, and it acts as a curing accelerator or a thermal crosslinking agent that can be easily obtained using inexpensive raw materials. The compound has not yet been provided and further improvements are desired.

Moreover, what improved the storage stability by making the epoxy resin compound as a heat-crosslinking agent hardly soluble is disclosed (refer patent documents 8 and 9). However, in this case, the exposure sensitivity is as low as 300 to 500 mJ / cm ^3, and since it is poorly soluble, it tends to cause poor dispersion in the photosensitive layer, and good film hardness can be obtained, but developability and tackiness are good. There is a problem of worsening, and it has been difficult to balance storage stability with high sensitivity and developability.

  Therefore, no reaction occurs at low temperature or normal temperature during storage, excellent storage stability, small surface tackiness, good laminating and handling properties when formed into a film, from protective film and support A photosensitive composition that exhibits excellent releasability, high sensitivity and developability, and exhibits excellent chemical resistance, surface hardness, heat resistance, dielectric properties, electrical insulation, and the like after development, and photosensitivity using the same At present, no satisfactory film, high-definition permanent pattern and efficient formation method thereof have been provided yet.

JP-A 61-243869 Japanese Patent Laid-Open No. 02-097502 JP-A-11-246651 JP 56-155222 A Japanese Unexamined Patent Publication No. 57-1000012 JP 59-053526 A JP 2000-001526 A Japanese Patent No. 2774609 Japanese Patent No. 2707495 Nippon Oil & Fats, Takeshi Endo (Tokyo Tech) Network Polymer vol19, No. 4, P228-235, 1998

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention does not cause a reaction at low temperature or normal temperature during storage, is excellent in storage stability, has a small surface tackiness, has good laminating property and handleability when formed into a film, a protective film, A photosensitive composition having excellent peelability from a support, high sensitivity and excellent developability, and excellent chemical resistance, surface hardness, heat resistance, dielectric properties, electrical insulation, and the like after development, and It is an object of the present invention to provide a photosensitive film used, a high-definition permanent pattern (such as a protective film, an interlayer insulating film, and a solder resist pattern) and an efficient formation method thereof.

Means for solving the problems are as follows. That is,
<1> At least one of (A) a binder, (B) a polymerizable compound, (C) a photopolymerization initiator, (D) a softening point and a melting point is 50 to 250 ° C., and can be used as a solvent. And a thermal crosslinking agent that is soluble.
In the photosensitive composition according to <1>, a highly sensitive photosensitive layer having excellent dispersibility of the thermal crosslinking agent in the photosensitive layer is obtained, surface tackiness is small, developability, and storage stability. Etc. are good. By using such a photosensitive film, the photosensitive layer is exposed with high definition, and then the photosensitive layer is developed to obtain excellent surface hardness and resolution, and a high-definition pattern is formed. The
<2> (D) The photosensitive composition according to <1>, wherein at least one of a softening point and a melting point of the thermal crosslinking agent is 70 to 150 ° C.
<3> (D) <1> to <1>, wherein the thermal crosslinking agent is at least one selected from an epoxy compound, an oxetane compound, an isocyanate compound, a cyanate compound, a methylolated melamine compound, a bismaleimide compound, and an oxazoline compound. 2>. The photosensitive composition according to any one of 2).
<4> The photosensitive composition according to <3>, wherein the (D) thermal crosslinking agent is an epoxy compound.
<5> (D) The photosensitive composition according to <4>, wherein the thermal crosslinking agent is a β-modified epoxy compound.
<6> The photosensitive composition according to <5>, wherein (D) the thermal crosslinking agent is an epoxy group having an alkyl group at the β-position and at least a β-position alkyl group-modified epoxy compound.
<7> The photosensitive composition according to <6>, wherein (D) the thermal crosslinking agent is a β-position methyl group-modified epoxy compound containing at least an epoxy group having a methyl group at the β-position.
<8> The above <6, wherein the epoxy group having an alkyl group at the β-position is at least one selected from a β-methylglycidyl group, a β-ethylglycidyl group, a β-propylglycidyl group, and a β-butylglycidyl group. > To <7>.
<9> (D) The photosensitive composition according to any one of <1> to <8>, wherein the thermal crosslinking agent is hexamethylated methylolmelamine.
<10> (D) The thermal crosslinking agent has two or more oxirane rings having a substituent at the oxirane ring portion in one molecule, and is represented by any one of the following general formulas (1) and (2): <1> to the photosensitive composition according to any one of <9>.
However, in said general formula (1) and (2), P represents either a single bond, an oxygen atom, a carbonyl group, alkylene, and arylene. Q represents any of alkylene having 2 or more carbon atoms and arylene. A ^{1 to} A ^{5 each} represents a single bond, alkylene, or arylene, and X ^{1 to} X ⁵ each represents a single bond, an oxygen atom, a sulfur atom, an amino group, a carbonyl group, —COO—, —OCO—, It represents either alkylene or arylene. R ^{1 to} R ^{5 each} represents a halogen atom, an alkyl group, or an aryl group.
<11> (D) The photosensitive composition according to <10>, wherein the thermal crosslinking agent is a compound represented by the following structural formulas (i) to (ix).
<12> (D) The photosensitive composition according to any one of <1> to <11>, wherein the content of the thermal crosslinking agent is 1 to 50% by mass.
<13> The photosensitive composition according to any one of <1> to <12>, wherein the (A) binder includes at least an epoxy acrylate compound.
<14> (A) The photosensitive composition according to any one of <1> to <12>, wherein the binder includes at least one vinyl copolymer having an acidic group and an ethylenically unsaturated double bond. is there.
<15> The photosensitive composition according to any one of <1> to <12>, wherein (A) the binder includes an epoxy acrylate compound and a vinyl copolymer having an acidic group and an ethylenically unsaturated double bond. It is.
<16> (A) The photosensitive composition according to any one of <13> to <15>, wherein the binder is represented by the following structural formula (III).
However, in said structural formula (III), X represents either a hydrogen atom and the substituent containing an acidic group at least, Y represents either a methylene group, an isopropylidene group, and a sulfonyl group, and n is The integer of 1-20 is represented.
<17> (1) The above <1>, wherein the binder (A) is a copolymer obtained by reacting 0.1 to 1.2 equivalents of a primary amine compound with respect to the anhydride group of the maleic anhydride copolymer. To <16>.
<18> (A) The binder is (a) maleic anhydride, (b) an aromatic vinyl monomer, and (c) a vinyl monomer, the glass transition of the homopolymer of the vinyl monomer A copolymer obtained by reacting 0.1 to 1.0 equivalent of a primary amine compound with an anhydride group of a copolymer comprising a vinyl monomer having a temperature (Tg) of less than 80 ° C. The photosensitive composition according to any one of <1> to <17>.
<19> The photosensitive composition according to any one of <1> to <18>, wherein the polymerizable compound (B) includes at least one selected from monomers having a (meth) acryl group.
<20> (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 <19>, including at least one selected from the above.
<21> a sensitizer, wherein the sensitizer is at least selected from a condensed ring compound and an amine compound substituted with at least two aromatic hydrocarbon rings and aromatic heterocyclic rings The photosensitive composition according to any one of <1> to <20>, which is one type.

<22> A support, a photosensitive layer obtained by laminating the photosensitive composition according to any one of <1> to <21> on the support, and a protective film on the photosensitive layer. It is a photosensitive film characterized by having.
In the photosensitive composition according to <22>, a high-sensitivity photosensitive layer is obtained, surface tackiness is small, peelability from a protective film or a support is excellent, developability, storage stability, and the like. It is good. By using such a photosensitive film, the photosensitive layer is exposed with high definition, and then the photosensitive layer is developed to obtain excellent surface hardness and resolution, and a high-definition pattern is formed. The
<23> 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 <22>.
<24> Any of <22> to <23>, wherein the peeling force between the photosensitive layer and the support when the support is peeled off at a pulling speed of 160 cm / min is 1 to 40 g per 4.5 cm length of the support A photosensitive film according to any one of the above.
<25> After 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 emission surface in the picture element portion The photosensitive film according to any one of <22> to <24>, wherein the photosensitive film is exposed with light passing through a microlens array in which microlenses having aspheric surfaces capable of correcting an aberration due to distortion of the lens are arranged.
In the photosensitive film according to <25>, 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 pattern is formed.
<26> The photosensitive film according to any one of <22> to <25>, wherein the support includes a synthetic resin and is transparent.
<27> The pattern forming material according to any one of <22> to <26>, wherein the support has a long shape.
<28> The photosensitive film according to any one of <22> to <27>, which is long and wound in a roll shape.
<29> The photosensitive film according to any one of <22> to <28>, wherein the photosensitive layer has a thickness of 1 to 100 μm.

<30> The photosensitive film according to any one of <22> to <29> is provided,
A pattern forming apparatus comprising at least light irradiating means capable of irradiating light and light modulating means for modulating light from the light irradiating means and exposing the photosensitive layer of the photosensitive film. is there.
In the pattern forming apparatus according to <30>, the light irradiation unit irradiates light toward the light modulation unit. The light modulation unit modulates light received from the light irradiation unit. The light modulated by the light modulator is exposed to the photosensitive layer. For example, when the photosensitive layer is subsequently developed, a high-definition pattern is formed.
<31> The light modulation means further includes a pattern signal generation means for generating a control signal based on the pattern information to be formed, and the control signal generated by the pattern signal generation means is emitted from the light irradiation means. It is a pattern formation apparatus as described in said <29> modulated according to.
In the pattern forming apparatus according to <31>, since the light modulation unit includes the pattern signal generation unit, light emitted from the light irradiation unit corresponds to a control signal generated by the pattern signal generation unit. Modulated.
<32> The light modulation means has n pixel parts, and forms any less than n pixel elements continuously arranged from the n pixel parts. The pattern forming apparatus according to any one of <30> to <31>, which is controllable according to pattern information.
In the pattern forming apparatus according to <32>, any less than n pixel parts arranged continuously from the n pixel parts in the light modulation unit are controlled according to pattern information. Thereby, the light from the light irradiation means is modulated at high speed.
<33> The pattern forming apparatus according to any one of <30> to <32>, wherein the light modulation unit is a spatial light modulation element.
<34> The pattern forming apparatus according to <33>, wherein the spatial light modulation element is a digital micromirror device (DMD).
<35> The pattern forming apparatus according to any one of <32> to <34>, wherein the drawing element portion is a micromirror.
<36> The pattern forming apparatus according to any one of <30> to <35>, wherein the light irradiation unit can synthesize and irradiate two or more lights.
In the pattern forming apparatus according to <36>, since the light irradiation unit can synthesize and irradiate two or more lights, exposure is performed with exposure light having a deep focal depth. As a result, the exposure to the photosensitive film is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.
<37> The light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that condenses the laser light irradiated from each of the plurality of lasers and couples the laser light to the multimode optical fiber. <30> to the pattern forming apparatus according to any one of <36>.
In the pattern forming apparatus according to <37>, the light irradiation unit can condense the laser beams emitted from the plurality of lasers by the collective optical system and couple the laser beams to the multimode optical fiber. Thus, exposure is performed with exposure light having a deep focal depth. As a result, the exposure to the photosensitive film is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.

<38> The photosensitive composition according to any one of <1> to <21> is applied to the surface of a substrate, dried to form a photosensitive layer, and then exposed, developed, and heated. This is a method for forming a permanent pattern. In the method for forming a permanent pattern according to <38>, 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, and the developed photosensitive layer is heated. By heating the photosensitive layer, the crosslinking reaction of the thermal crosslinking agent is promoted, and the film strength of the cured region of the photosensitive layer is increased. As a result, a permanent pattern having a high surface hardness and optimal for a protective film, an interlayer insulating film, a solder resist pattern, and the like is formed. The heat treatment may be a whole surface heat treatment or a heat treatment in a pattern.
<39> The photosensitive film according to any one of <22> to <29> is laminated on the surface of the substrate under at least one of heating and pressurization, and then exposed, developed, and heated. This is a method for forming a permanent pattern. In the method for forming a permanent pattern according to <39>, the photosensitive film having the support and a photosensitive layer obtained by laminating a photosensitive composition on the support is at least either heated or pressurized. It is laminated | stacked on the surface of the said base material under this. As a result, the photosensitive layer is formed by being transferred onto the substrate. The photosensitive layer in the laminated photosensitive film is exposed. The exposed photosensitive layer is developed, and the developed photosensitive layer is heated. By heating the photosensitive layer, the crosslinking effect of the thermal crosslinking agent is promoted, and the film strength of the cured region of the photosensitive layer is increased. As a result, a permanent pattern that is excellent in heat resistance and chemical resistance, has high surface hardness, and is optimal for a protective film or insulating film is formed.
<40> For the photosensitive layer,
A light irradiating means, and n (where n is a natural number of 2 or more) two-dimensionally arranged picture elements that receive and emit light from the light irradiating means, and according to the pattern information, An exposure head provided with a light modulation means capable of controlling a picture element portion, the exposure head being arranged so that a column direction of the picture element portion forms a predetermined set inclination angle θ with respect to a scanning direction of the exposure head Using the head
With respect to the exposure head, the usable pixel part designating means designates the pixel part to be used for N double exposure (where N is a natural number of 2 or more) among the usable graphic elements.
For the exposure head, the pixel part control means controls the pixel part so that only the pixel part specified by the used pixel part specifying means is involved in exposure,
The permanent pattern forming method according to any one of <38> to <39>, wherein the photosensitive layer is exposed and developed by moving the exposure head relative to a scanning direction.
In the method for forming a permanent pattern according to <40>, N exposure (N is a natural number of 2 or more) among the usable pixel parts by the used pixel part designating unit for the exposure head. The pixel part to be used is specified, and the pixel part is controlled by the pixel part control unit so that only the pixel part specified by the used pixel part specifying unit is involved in exposure. . By performing exposure by moving the exposure head relative to the photosensitive layer in the scanning direction, the exposure head is formed on the exposed surface of the photosensitive layer due to a shift in the mounting position or mounting angle of the exposure head. Variations in the resolution of the pattern and unevenness in density are leveled. As a result, the photosensitive layer is exposed with high definition, and then the photosensitive layer is developed to form a high-definition permanent pattern.
<41> The method for forming a permanent pattern according to any one of <37> to <38>, wherein the support includes a synthetic resin and is transparent.
<42> The method for forming a permanent pattern according to any one of <39> to <41>, wherein the support has a long shape.
<43> The method for forming a permanent pattern according to any one of <39> to <42>, wherein the photosensitive film is long and wound in a roll.
<44> The method for forming a permanent pattern according to any one of <38> to <43>, wherein the photosensitive layer has a thickness of 3 to 100 μm.
<45> The permanent pattern forming method according to any one of <38> to <44>, wherein the base material is a printed wiring board on which wiring is formed. In the permanent pattern forming method according to <45>, since the base material is a printed wiring board on which wiring is formed, a multilayer wiring board or build-up of a semiconductor or a component can be performed by using the permanent pattern forming method. High-density mounting on a wiring board or the like is possible.

<46> The exposure is performed by a plurality of exposure heads, and the used drawing element specifying means is related to the exposure of the head-to-head connection region, which is an overlapping exposure region on the exposed surface formed by the plurality of exposure heads. The permanent pattern forming method according to any one of <38> to <45>, wherein, among the element parts, the image element part used for realizing N double exposure in the inter-head connection region is designated. In the method for forming a permanent pattern according to <46>, the exposure is performed by a plurality of exposure heads, and the used pixel portion designating means is an overlapping exposure region on the exposed surface formed by the plurality of exposure heads. Of the picture element parts involved in the exposure of the connection area between the heads, by specifying the picture element part used for realizing the N-fold exposure in the connection area between the heads, the mounting position of the exposure head, Variations in the resolution and density unevenness of the pattern formed in the connecting area between the heads on the exposed surface of the photosensitive layer due to the mounting angle deviation are leveled. As a result, the photosensitive layer is exposed with high definition, and then the photosensitive layer is developed to form a high-definition permanent pattern.
<47> The exposure is performed by a plurality of exposure heads, and the used picture element specifying means is involved in exposure other than the inter-head connection region which is an overlapping exposure region on the exposed surface formed by the plurality of exposure heads. The permanent pattern forming method according to the above <46>, wherein the image element portion used for realizing N double exposure in an area other than the inter-head connection area in the image element section is designated. In the method for forming a permanent pattern according to <47>, exposure is performed by a plurality of exposure heads, and a used pixel portion designating unit is an overlapping exposure region on an exposed surface formed by the plurality of exposure heads. Mounting of the exposure head by designating the picture element part used for realizing N double exposure in areas other than the inter-head connection area among the image element parts related to exposure other than the inter-head connection area Variations in the resolution and density unevenness of the pattern formed in areas other than the joint area between the heads on the exposed surface of the photosensitive layer due to a shift in position and mounting angle are leveled. As a result, the photosensitive layer is exposed with high definition, and then the photosensitive layer is developed to form a high-definition permanent pattern.
<48> When the set inclination angle θ is N for N multiple exposures, the number s of pixel parts in the column direction, the interval p in the column direction of the pixel parts, and the exposure head tilted, the relative row direction pitch δ of pixel parts in the direction perpendicular to the scanning direction, the following equation with respect to theta _ideal satisfying spsinθ _ideal ≧ Nδ, which is set so as to satisfy the relation of θ ≧ θ _ideal <40> to <47>.
<49> The method for forming a permanent pattern according to any one of <40> to <48>, wherein N in N-exposure is a natural number of 3 or more. In the method for forming a permanent pattern described in <49>, multiple drawing is performed when N in N double exposure is a natural number of 3 or more. As a result, due to the effect of filling, variations in the resolution and density unevenness of the pattern formed on the exposed surface of the photosensitive layer due to a shift in the mounting position and mounting angle of the exposure head are more precisely leveled.

<50> Use pixel part designation means,
A light spot position detecting means for detecting a light spot position as a pixel unit that is generated by the picture element unit and constitutes an exposure area on the exposed surface;
<40> to <49>, further comprising: a pixel part selection unit that selects a pixel part to be used for realizing N double exposure based on a detection result by the light spot position detection unit. This is a permanent pattern forming method.
<51> The permanent pattern forming method according to any one of <39> to <50>, wherein the used pixel part specifying unit specifies, in line units, the used pixel part used to realize N double exposure. It is.

<52> The fact that the light spot position detector detects the column direction of the light spot on the surface to be exposed and the scanning direction of the exposure head when the exposure head is tilted based on the detected at least two light spot positions. The inclination angle θ ′ is specified, and the drawing element selection means selects the drawing element part so as to absorb the error between the actual inclination angle θ ′ and the set inclination angle θ. The permanent pattern forming method according to any one of the above.
<53> The average inclination angle θ ′ is an average value, a median value, and a plurality of actual inclination angles formed by the row direction of the light spots on the surface to be exposed and the scanning direction of the exposure head when the exposure head is inclined. The permanent pattern forming method according to <52>, wherein the permanent pattern forming method is one of a maximum value and a minimum value.
<54> The pixel part selection means derives a natural number T close to t that satisfies a relationship of ttan θ ′ = N (where N represents N of N double exposure numbers) based on the actual inclination angle θ ′, and m <50> to <53> for selecting the pixel part from the first line to the T-th line in a line element (where m represents a natural number of 2 or more) arranged as a used pixel part The permanent pattern forming method according to any one of the above.
<55> The pixel part selection means derives a natural number T close to t that satisfies a relationship of ttan θ ′ = N (where N represents N of N double exposure numbers) based on the actual inclination angle θ ′, and m In the picture element part arranged in a row (where m represents a natural number of 2 or more), the picture element part in the (T + 1) -th line to the m-th line is specified as an unused picture element part, and the unused picture element part is specified. The permanent pattern forming method according to any one of <50> to <53>, wherein the picture element part excluding the element part is selected as a use picture element part.

<56> In the region including at least the overlapping exposure region on the exposed surface formed by the plurality of pixel part columns, the pixel part selecting unit,
(1) Means for selecting a used pixel portion so that a total area of an overexposed region and an underexposed region is minimized with respect to an ideal N-fold exposure;
(2) Means for selecting a pixel part to be used so that the number of pixel units in an overexposed area and the number of pixel units in an underexposed area are equal to each other with respect to an ideal N double exposure;
(3) Means for selecting a pixel part to be used so that the area of an overexposed area is minimized and an underexposed area does not occur with respect to an ideal N double exposure, and (4) Ideal From <51>, which is one of means for selecting a used pixel portion so that the area of an underexposed region is minimized and an overexposed region does not occur with respect to typical N-exposure <55> The permanent pattern forming method according to any one of the above.
<57> In the connection region between the heads, which is an overlapping exposure region on the exposed surface formed by the plurality of exposure heads,
(1) With respect to the ideal N-multiple exposure, from the pixel part involved in the exposure of the inter-head connection region, the total area of the overexposed region and the underexposed region is minimized. Means for identifying a used pixel part and selecting the pixel part excluding the unused pixel part as a used pixel part;
(2) Involvement in the exposure of the head-to-head connecting region so that the number of pixel units in the overexposed region and the number of pixel units in the underexposed region are equal to the ideal N-double exposure. Means for identifying an unused pixel part from the pixel part to be selected, and selecting the pixel part excluding the unused pixel part as a used pixel part;
(3) For the ideal N-multiple exposure, from the pixel part involved in the exposure of the inter-head connecting region, the area of the overexposed region is minimized and the underexposed region is not generated. A means for identifying an unused pixel part and selecting the pixel part excluding the unused pixel part as a used pixel part; and
(4) For the ideal N-multiple exposure, from the pixel part involved in the exposure of the inter-head connecting region, the area of the underexposed region is minimized and the region that is overexposed is not generated. , Means for identifying an unused pixel part and selecting the pixel part excluding the unused pixel part as a used pixel part;
The method for forming a permanent pattern according to any one of <50> to <56>.
<58> The permanent pattern forming method according to <57>, wherein the unused pixel parts are specified in units of rows.

<59> In order to specify the used pixel part in the used pixel part specifying means, among the usable pixel parts, N (n−1) pixel part columns for N multiple exposures The permanent pattern forming method according to any one of <49> to <58>, wherein the reference exposure is performed using only the picture element portion that constitutes. In the permanent pattern forming method according to <59>, in order to specify the used pixel part in the used pixel part specifying unit, among the usable pixel parts, N-1) Reference exposure is performed using only the pixel part constituting the pixel part column for each column, and a simple pattern of substantially single drawing is obtained. As a result, the picture element portion in the head-to-head connection region is easily specified.
<60> In order to specify the used pixel part in the used pixel part specifying means, among the usable pixel elements, a N / N line pixel part row is configured for N of N multiple exposures. The permanent pattern forming method according to any one of <49> to <59>, wherein the reference exposure is performed using only the picture element portion. In the method for forming a permanent pattern according to <60>, in order to designate a used picture element part in the used picture element part specifying means, out of the usable picture element parts, N is one for N double exposure. / A reference exposure is performed using only the pixel part constituting the pixel part column for every N rows, and a simple pattern of substantially single drawing is obtained. As a result, the picture element portion in the head-to-head connection region is easily specified.

<61> The <40> to <60>, wherein the used pixel part designation means includes a slit and a photodetector as a light spot position detection means, and an arithmetic unit connected to the photodetector as a pixel part selection means. The permanent pattern forming method according to any one of the above.
<62> The method for forming a permanent pattern according to any one of <40> to <61>, wherein N in N-exposure exposure is a natural number of 3 or more and 7 or less.

<63> The light modulation means further includes a pattern signal generation means for generating a control signal based on the pattern information to be formed, and the control signal generated by the pattern signal generation means is emitted from the light irradiation means. The method for forming a permanent pattern according to any one of <40> to <62>, wherein the modulation is performed according to the method.
<64> From the above <40> to <40> having conversion means for converting the pattern information so that the dimension of the predetermined part of the pattern represented by the pattern information matches the dimension of the corresponding part that can be realized by the designated used pixel part 63>. The permanent pattern forming method according to any one of 63>.
<65> The permanent pattern forming method according to any one of <40> to <64>, wherein the light modulation unit is a spatial light modulation element.
<66> The method for forming a permanent pattern according to <65>, wherein the spatial light modulation element is a digital micromirror device (DMD).
<67> The permanent pattern forming method according to any one of <40> to <66>, wherein the pixel part is a micromirror.

<68> The permanent pattern forming method according to any one of <40> to <67>, wherein the light irradiation unit can synthesize and irradiate two or more lights. In the method for forming a permanent pattern described in <68>, since the light irradiation unit can synthesize and irradiate two or more lights, exposure is performed with exposure light having a deep focal depth. As a result, the photosensitive layer is exposed with extremely high definition, and then the photosensitive layer is developed to form an extremely high definition permanent pattern.
<69> The light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that collects and couples the laser beams irradiated from the plurality of lasers to the multimode optical fiber. The permanent pattern forming method according to any one of <40> to <68>. In the method for forming a permanent pattern according to <69>, the laser beam irradiated from each of the plurality of lasers is condensed by the collective optical system and can be coupled to the multimode optical fiber. Thus, exposure is performed with exposure light having a deep focal depth. As a result, the photosensitive layer is exposed with extremely high definition, and then the photosensitive layer is developed to form an extremely high definition permanent pattern.
<70> The method for forming a permanent pattern according to <69>, wherein the wavelength of the laser beam is 395 to 415 nm.

<71> The method for forming a permanent pattern according to any one of <38> to <70>, wherein the heating is performed at 120 to 250 ° C. In the method for forming a permanent pattern according to <71>, the film strength of the cured film is increased in the heat treatment performed under the temperature condition.
<72> The method for forming a permanent pattern according to the above <38> to <71>, wherein after the development, the entire surface of the photosensitive layer is exposed. In the permanent pattern forming method according to <72>, curing of the resin in the photosensitive composition is promoted in the entire surface exposure process.
<73> The method for forming a permanent pattern according to any one of <38> to <73>, wherein at least one of a protective film, an interlayer insulating film, and a solder resist pattern is formed.

<74> A pattern formed by the method for forming a permanent pattern according to any one of <38> to <73>.
Since the pattern according to <74> is formed by the permanent pattern forming method, it has high resolution, excellent chemical resistance, surface hardness, heat resistance, etc. This is useful for high-density mounting on multilayer wiring boards and build-up wiring boards.
<75> The pattern according to <74>, which is at least one of a protective film, an interlayer insulating film, and a solder resist pattern.
The pattern according to <75> is at least one of a protective film, an interlayer insulating film, and a solder resist pattern. Protected from.

  According to the present invention, conventional problems can be solved, no reaction occurs at low or normal temperature during storage, excellent storage stability, low surface tackiness, laminating properties when formed into a film, and Good handleability, excellent peelability from protective film and support, high sensitivity and excellent developability, excellent chemical resistance, surface hardness, heat resistance, dielectric properties, electrical insulation, etc. after development A photosensitive composition that expresses, a photosensitive film using the photosensitive composition, and a high-definition permanent pattern (such as a protective film, an interlayer insulating film, and a solder resist pattern) in the semiconductor field with high definition, and It is possible to provide a permanent pattern forming method that can be efficiently formed, and a pattern suitable for manufacturing a printed wiring board including a package substrate.

(Photosensitive composition)
The photosensitive composition of the present invention comprises at least (A) a binder, (B) a polymerizable compound, (C) a photopolymerization initiator, and (D) a thermal crosslinking agent. And a sensitizer and, if necessary, other components such as a color pigment, an extender pigment, a thermal polymerization inhibitor, and a surfactant.
In addition, at least one of the softening point and the melting point of the thermal crosslinking agent needs to be 50 to 250 ° C, and at least one of the softening point and the melting point of the thermal crosslinking agent is 70 to 150 ° C. Preferably there is. When the softening point or melting point is less than 50 ° C., a strong force is required for peeling, and the peelability of the protective film may be deteriorated. Moreover, when it exceeds 250 degreeC, crosslinkability deteriorates and sufficient cured film physical property may not be obtained in heat-hardening process.
The thermal crosslinking agent is soluble in a solvent. The thermal crosslinking agent is “soluble in a solvent” at 30 ° C., water, methanol, ethanol, propanol, 2-propanol, 1-methoxy-2-propanol, 2-methoxy-1-methylethyl. Of acetate, ethyl acetate, butyl acetate, acetonitrile, benzene, toluene, acetone, methyl ethyl ketone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane, diethyl ether, dioxane, pyridine, methylene chloride, chloroform, 1,2-dichloroethane, and chlorobenzene In any case, about 2% by mass is dissolved.

<(A) Binder>
The binder includes at least one (a ₁ ) epoxy acrylate compound, and (a ₂ ) at least one vinyl copolymer having a (meth) acryloyl group and an acidic group in the side chain, as necessary. And may contain other binders.
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.

- _{(a 1)} an epoxy acrylate compound -
The epoxy acrylate compound is a compound having a skeleton derived from an epoxy compound and containing an ethylenically unsaturated double bond and an acidic group such as 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 (“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 novolac type epoxy resin, glycidylamine type epoxy resin (for example, 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.); condensation of phenolic compounds such as phenol, o-cresol, naphthol and the like with aromatic aldehydes having a phenolic hydroxyl group (for example, p-hydroxybenzaldehyde) Anti Reaction product of polyphenol compound and epichlorohydrin obtained by the above; reaction product of polyphenol compound obtained by addition reaction of phenol compound and diolefin compound such as divinylbenzene and dicyclopentadiene and epichlorohydrin; 4-vinylcyclohexene-1- Epoxidized ring-opening polymer of oxide with peracetic acid or the like; epoxy resin having a heterocyclic ring such as triglycidyl isocyanurate; glycidyl methacrylate copolymer epoxy resin (“CP-50S, CP-50M; NOF Corporation) And the like, and a copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate. 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-cyano. Cinnamic acid, acrylic acid dimer; in addition, addition reaction of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate with a cyclic acid anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride A reaction product with a halogen-containing carboxylic acid compound, ω-carboxy-polycaprolactone mono (meth) acrylate, and the like. Furthermore, commercially available products include Aronix M-5300, M-5400, M-5500 and M-5600 manufactured by Toa Synthetic Chemical Industry Co., Ltd., NK Esters CB-1 and CBX- manufactured by Shin-Nakamura Chemical Co., Ltd. 1. Kyoeisha Yushi Chemical Co., Ltd. HOA-MP and HOA-MS, Osaka Organic Chemical Industry Co., Ltd. biscoat # 2100, etc. can be used. These may be used individually by 1 type and may use 2 or more types together.
Examples of the polybasic acid anhydride include succinic anhydride, methyl succinic anhydride, 2,3-dimethyl succinic anhydride, 2,2-dimethyl succinic anhydride, ethyl succinic anhydride, dodecenyl succinic anhydride, and 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 Acid, phthalic anhydride, tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylene Tetrahydro anhydride Dibasic acid anhydrides such as phosphoric acid, chlorendic anhydride and 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, anhydrous Polybasic acid anhydrides such as pyromellitic acid and 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.

Among the compounds obtained by introducing an ethylenically unsaturated double bond and an acidic group into the epoxy compound, epoxy acrylate compounds represented by the following structural formulas (III) and (IV) are preferable.
However, in the said general formula (III), X represents either a hydrogen atom and the substituent containing an acidic group at least, Y represents either a methylene group, an isopropylidene group, and a sulfonyl group, and n is The integer of 1-20 is represented.

However, in said general formula (IV), n represents the integer of 1-20.

The epoxy acrylate compound represented by the structural formula (III) is specifically represented by the bisphenol F type epoxy acrylate compound represented by the following structural formula (V) and the following structural formula (VI). Bisphenol A type epoxy acrylate compounds are more preferred.

  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₎ side chain (meth) acryloyl group, and a vinyl copolymer having an acid group -
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).

In the Structural Formula (1) ~ (9), R 1 represents a hydrogen atom or a methyl group, n, n1 and n2 represents an integer of 1 or more.

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

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

However, in the structural formulas (10) to (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. "," Lipoxy SPC-1X, Lipoxy SPC-2X, Lipoxy SPC-3X; 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.

  There is no restriction | limiting in particular as another copolymerizable monomer used as needed of said (3), According to the objective, it can select suitably, For example, (meth) acrylic acid esters, crotonic acid ester , Vinyl esters, maleic diesters, fumaric diesters, itaconic diesters, (meth) acrylamides, vinyl ethers, vinyl alcohol esters, styrenes (eg, styrene, styrene derivatives, etc.), (meta ) Acrylonitrile, heterocyclic group substituted with vinyl group (for example, vinylpyridine, vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinylcaprolactone, 2-acrylamide-2- Methylpropanesulfonic acid, phosphorus Vinyl monomers having mono (2-acryloyloxyethyl ester), mono (1-methyl-2-acryloyloxyethyl ester) phosphate, functional groups (for example, urethane group, urea group, sulfonamide group, imide group), etc. Can be mentioned.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

As the compound having a (meth) acryloyl group and a functional group reactive to at least one of the acidic group in the (co) polymer of (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-
Examples of the other binders include maleamic acid copolymers and other binders.
[Maleamic acid copolymer]
The maleamic acid-based copolymer is a copolymer obtained by reacting one or more primary amine compounds with an anhydride group of a maleic anhydride copolymer. The copolymer is a maleamic acid-based copolymer having at least a maleamic acid unit B having a maleic acid half amide structure and a unit A not having the maleic acid half amide structure, represented by the following structural formula (14). It is preferably a coalescence.
The unit A may be one type or two or more types. For example, assuming that the unit B is one type, when the unit A is one type, the maleamic acid-based copolymer means a binary copolymer, and the unit A is 2 When it is a seed, the maleamic acid-based copolymer means a terpolymer.
The unit A is an aryl group which may have a substituent and a vinyl monomer described later, and the glass transition temperature (Tg) of the homopolymer of the vinyl monomer is less than 80 ° C. A combination with the vinyl monomer (c) is preferred.

In the Structural Formula (14), R ³ and R ⁴ represents a hydrogen atom or a lower alkyl group. x and y represent the mole fraction of the repeating unit. For example, when the unit A is one, x is 85 to 50 mol%, and y is 15 to 50 mol%.

In the structural formula (14), as R ¹ , for example, (—COOR ¹⁰ ), (—CONR ¹¹ R ¹² ), an aryl group which may have a substituent, (—OCOR ¹³ ), (—OR ¹⁴ ), substituents such as (—COR ¹⁵ ). Here, said R < ¹⁰ > -R < ¹⁵ > represents either a hydrogen atom (-H), the alkyl group which may have a substituent, an aryl group, and an aralkyl group. The alkyl group, aryl group and aralkyl group may have a cyclic structure or a branched structure.
Examples of R ^{10 to} R ¹⁵ include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, pentyl, allyl, n-hexyl, and cyclohexyl. 2-ethylhexyl, dodecyl, methoxyethyl, phenyl, methylphenyl, methoxyphenyl, benzyl, phenethyl, naphthyl, chlorophenyl and the like.
Specific examples of R ¹ include, for example, benzene derivatives such as phenyl, α-methylphenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl; n-propyloxycarbonyl, Examples include n-butyloxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, n-butyloxycarbonyl, n-hexyloxycarbonyl, 2-ethylhexyloxycarbonyl, methyloxycarbonyl and the like.

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

The binder made of the maleamic acid copolymer is, in particular, (a ₃ ) maleic anhydride, (a ₄ ) an aromatic vinyl monomer, and (a ₅ ) a vinyl monomer, A copolymer obtained by reacting a primary amine compound with an anhydride group of a copolymer comprising a vinyl monomer having a glass transition temperature (Tg) of a monomer homopolymer of less than 80 ° C. Preferably there is. A copolymer comprising the component (a ₃ ) and the component (a ₄ ) can obtain a high surface hardness of the photosensitive layer described later, but it may be difficult to ensure laminating properties. Further, the said (a ₃₎ component, and the (a ₅₎ component, a copolymer consisting of, although laminating property can be secured, ensuring the surface hardness may become difficult.

- _{(a 4)} the aromatic vinyl monomer -
There is no restriction | limiting in particular as said aromatic vinyl monomer, According to the objective, it can select suitably, The surface hardness of the photosensitive layer formed using the photosensitive composition of this invention can be made high. In this respect, a compound having a glass transition temperature (Tg) of the homopolymer of 80 ° C. or higher is preferable, and a compound of 100 ° C. or higher is more preferable.
Specific examples of the aromatic vinyl monomer include, for example, styrene (homopolymer Tg = 100 ° C.), α-methylstyrene (homopolymer Tg = 168 ° C.), 2-methylstyrene (homopolymer Tg = 136 ° C.), 3-methylstyrene (homopolymer Tg = 97 ° C.), 4-methylstyrene (homopolymer Tg = 93 ° C.), 2,4-dimethylstyrene (homopolymer Tg = 112 ° C.) Preferred examples include derivatives. These may be used individually by 1 type and may use 2 or more types together.

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

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

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

The content of the (a ₃ ) maleic anhydride in the binder is preferably 15 to 50 mol%, more preferably 20 to 45 mol%, particularly preferably 20 to 40 mol%. When the content is less than 15 mol%, alkali developability cannot be imparted, and when it exceeds 50 mol%, alkali resistance deteriorates and synthesis of the copolymer becomes difficult, resulting in a normal permanent pattern. Formation may not be possible. In this case, the content of the vinyl monomer having a glass transition temperature (Tg) of the (a ₄ ) aromatic vinyl monomer and (a ₅ ) homopolymer of less than 80 ° C. in the binder is: 20-60 mol% and 15-40 mol% are respectively preferable. When the content satisfies the numerical range, both surface hardness and laminating properties can be achieved.

  The molecular weight of the maleamic acid copolymer is preferably 3,000 to 500,000, more preferably 8,000 to 150,000. When the molecular weight is less than 3,000, the film quality becomes brittle and the surface hardness may deteriorate after curing of the photosensitive layer described later. When the molecular weight exceeds 500,000, the photosensitive composition is heated and laminated. The fluidity of the resin tends to be low, and it may be difficult to ensure proper laminating properties, and the developability may deteriorate.

[Other binders]
As the other binder, a polyamide (imide) resin described in JP-A-11-288087, a polyimide precursor described in JP-A-11-282155, or 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 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, 5-70 mass% is preferable, and 10-50 mass% is 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 is not particularly limited and may be appropriately selected depending on the purpose. The compound has at least one addition-polymerizable group in the molecule and has a boiling point of 100 ° C. or higher at normal pressure. For example, at least one selected from monomers having a (meth) acryl group is preferable.

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

  As solid content in the said photosensitive composition solid content of the said polymeric compound, 5-50 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.

<(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 (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, ⁵ -cyclopentadienyl-η ⁶ -cumenyl-iron (1 +)-hexafluorophosphate (1-), and the like.

  Further, as photopolymerization initiators other than the above, N-phenylglycine and other polyhalogen compounds (for example, carbon tetrabromide, phenyltribromomethylsulfone, phenyltrichloromethyl ketone, etc.), amines (for example, 4-dimethylamino) Ethyl benzoate, n-butyl 4-dimethylaminobenzoate, phenethyl 4-dimethylaminobenzoate, 2-phthalimidoethyl 4-dimethylaminobenzoate, 2-methacryloyloxyethyl 4-dimethylaminobenzoate, pentamethylenebis (4 -Dimethylaminobenzoate), phenethyl of 3-dimethylaminobenzoic acid, pentamethylene ester, 4-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylaminobenzyl alcohol, ethyl (4-di- Tilaminobenzoyl) acetate, 4-piperidinoacetophenone, 4-dimethylaminobenzoin, N, N-dimethyl-4-toluidine, N, N-diethyl-3-phenetidine, tribenzylamine, dibenzylphenylamine, N- Methyl-N-phenylbenzylamine, 4-bromo-N, N-dimethylaniline, tridodecylamine, crystal violet lactone, leuco crystal violet, etc.), 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.

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 film 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 as long as at least one of the softening point and the melting point of the thermal crosslinking agent is 50 to 250 ° C. and soluble in a solvent, and may be appropriately selected according to the purpose. In order to improve the film strength after curing of the photosensitive layer formed using the photosensitive composition, it can be used within a range that does not adversely affect the developability.
A thermal cross-linking agent having at least one of the softening point and melting point of 50 to 250 ° C. and soluble in a solvent does not cause a reaction at a low temperature or normal temperature during storage, and initiates a cross-linking reaction by heating. And has a function of curing the resin in the photosensitive composition. By containing the thermal crosslinking agent in the photosensitive composition of the present invention, the photosensitive composition does not react at a low temperature or normal temperature, and excellent storage stability can be achieved. It cures with a rapid reaction, and a cured product having excellent surface hardness and alkali resistance is obtained.
The thermal crosslinking agent is preferably selected from an epoxy compound, an oxetane compound, an isocyanate compound, a cyanate compound, a methylolated melamine compound, a bismaleimide compound, and an oxazoline compound, and an epoxy having at least two oxirane rings in one molecule. Particularly preferred are compounds, oxetane compounds having at least two oxetanyl groups in one molecule, and epoxy compounds having at least two epoxy groups having an alkyl group at the β-position in one molecule.
Examples of the epoxy compound having at least two oxirane rings in one molecule include, for example, a bixylenol type or biphenol type epoxy resin (“YX4000 Japan Epoxy Resin” etc.) or a mixture thereof, a complex having an isocyanurate skeleton, etc. Cyclic epoxy resins ("TEPIC; manufactured by Nissan Chemical Industries", "Araldite PT810; manufactured by Ciba Specialty Chemicals"), bisphenol A type epoxy resin, novolac type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, halogenated epoxy resin (for example, low brominated epoxy resin, high halogenated epoxy resin, odor Phenol novolac type epoxy resin), allyl group-containing bisphenol A type epoxy resin, trisphenol methane type epoxy resin, diphenyldimethanol type epoxy resin, phenol biphenylene type epoxy resin, dicyclopentadiene type epoxy resin ("HP-7200, HP-7200H; manufactured by Dainippon Ink & Chemicals, Inc.), glycidylamine type epoxy resin (diaminodiphenylmethane type epoxy resin, diglycidylaniline, triglycidylaminophenol, etc.), glycidyl ester type epoxy resin (phthalic acid diglycidyl ester) Adipic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer acid diglycidyl ester, etc.) hydantoin type epoxy resin, alicyclic epoxy resin (3,4 Poxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, dicyclopentadiene diepoxide, “GT-300, GT-400, ZEHPE3150; manufactured by Daicel Chemical Industries”, etc. )), Imide type alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A novolak type epoxy resin, tetraphenylolethane type epoxy resin, glycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group-containing epoxy Resin (naphthol aralkyl type epoxy resin, naphthol novolac type epoxy resin, tetrafunctional naphthalene type epoxy resin, commercially available products such as “ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.” HP-4032, EXA-4750, EXA-4700; manufactured by Dainippon Ink & Chemicals, Inc.), polyphenol compounds obtained by addition reaction of phenol compounds with diolefin compounds such as divinylbenzene and dicyclopentadiene, and epichlorohydrin A reaction product of 4-vinylcyclohexene-1-oxide obtained by epoxidation with peracetic acid, an epoxy resin having a linear phosphorus-containing structure, an epoxy resin having a cyclic phosphorus-containing structure, α-methylstilbene Type liquid crystal epoxy resin, dibenzoyloxybenzene type liquid crystal epoxy resin, azophenyl type liquid crystal epoxy resin, azomethine phenyl type liquid crystal epoxy resin, binaphthyl type liquid crystal epoxy resin, azine type epoxy resin, glycidyl methacrylate copolymer epoxy resin ("CP- 5 0S, CP-50M; manufactured by NOF Corporation, etc.), copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, bis (glycidyloxyphenyl) fluorene type epoxy resin, bis (glycidyloxyphenyl) adamantane type epoxy resin, etc. Although it is mentioned, it is not restricted to these. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.

As an epoxy compound containing at least two epoxy groups having an alkyl group at the β-position in one molecule, an epoxy group in which the β-position is substituted with an alkyl group (more specifically, a β-alkyl-substituted glycidyl group, etc.) Particularly preferred are compounds comprising
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
These epoxy compounds containing an epoxy group having an alkyl group at the β-position may be used alone or in combination of two or more. It is also possible to use together an epoxy compound having at least two oxirane rings in one molecule and an epoxy compound containing an epoxy group having an alkyl group at the β-position.

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

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, bifunctional isocyanate (for example, a mixture of 1,3-phenylene diisocyanate and 1,4-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate, 1,3- and 1,4-xylylene). Diisocyanate, bis (4-isocyanate-phenyl) methane, bis (4-isocyanatocyclohexyl) methane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, etc.), the bifunctional isocyanate, trimethylolpropane, pentalithol tol Polyfunctional alcohols such as glycerin; alkylene oxide adducts of the polyfunctional alcohols and adducts of the bifunctional isocyanates; hexamethylene diisocyanate, hexamethylene-1,6-di Isocyanate and cyclic trimers and biurets of derivatives thereof; norbornane diisocyanate; and the like.

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

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

  As other thermal crosslinking agents, aldehyde condensation products other than melamine, resin precursors, and the like can be used. Specifically, N, N′-dimethylolurea, N, N′-dimethylolmalonamide, N, N′-dimethylolsuccinimide, 1,3-N, N′-dimethylolterephthalamide, 2,4,4 Examples thereof include 6-trimethylolphenol, 2,6-dimethylol-4-methyloanisole, 1,3-dimethylol-4,6-diisopropylbenzene, and the like. Instead of these methylol compounds, the corresponding ethyl or butyl ether, or acetic acid or propionic acid ester may be used.

Moreover, at least any one of the said softening point and melting | fusing point is 50-250 degreeC, As a specific example of the thermal crosslinking agent soluble in a solvent, following structural formula (a-1)-(a-2) And the like.
In the structural formulas (a-1) to (a-2), n represents an integer of 1 or more.

As the thermal crosslinking agent, those having two or more oxirane rings having a substituent at the oxirane ring portion in one molecule and represented by any of the following general formulas (1) and (2) are preferable.
However, in said general formula (1) and (2), P represents either a single bond, an oxygen atom, a carbonyl group, alkylene, and arylene. Q represents any of alkylene having 2 or more carbon atoms and arylene. A ^{1 to} A ^{5 each} represents a single bond, alkylene, or arylene, and X ^{1 to} X ⁵ each represents a single bond, an oxygen atom, a sulfur atom, an amino group, a carbonyl group, —COO—, —OCO—, It represents either alkylene or arylene. R ^{1 to} R ^{5 each} represents a halogen atom, an alkyl group, or an aryl group.

In the general formulas (1) and (2), the alkylene of P is an unsubstituted alkylene and a substituent-containing alkylene substituted with an aryl group, an alkenyl group, a hydroxyl group, an alkoxy group, a cyano group, or a halogen atom. Show.
The unsubstituted alkylene may have a branch, may have a double bond or a triple bond, and preferably has a total carbon number of 1 to 20, more preferably 1 to 8. Examples of such alkylene include ethylene, propylene, i-propylene, butylene, i-butylene, cyclohexylene, and the like.
The aryl substituent in the substituent-containing alkylene preferably has a total carbon number of 6 to 30, particularly preferably 6 to 15, and examples of the substituent include a phenyl group, a naphthyl group, an anthracenyl group, a methoxyphenyl group, And a chlorophenyl group.
The alkenyl substituent in the substituent-containing alkylene preferably has a total carbon number of 2 to 10, more preferably 2 to 6, and examples of the substituent include an ethynyl group, a propenyl group, and a butyryl group.
The alkoxy substituent in the substituent-containing alkylene may have a branch, preferably has a total carbon number of 1 to 10, more preferably 1 to 5, and examples of the substituent include a methoxy group, an ethoxy group, Examples thereof include a propyloxy group, a 2-methylpropyloxy group, and a butoxy group.
Such a substituent-containing alkylene may have a branch, may have a double bond or a triple bond, preferably has 2 to 40 carbon atoms, and particularly preferably has 2 to 25 carbon atoms. Examples of such a substitution-containing alkylene include 2-ethylhexyl group, chlorobutyl group, benzyl group, 2-ethynylpropyl group, phenylethyl group, cyanopropyl group, methoxyethyl group, and the like.
The arylene of P has the same meaning as the arylene of A ^{1 to} A ⁵ described later.

In the general formulas (1) and (2), the alkylene of Q includes the unsubstituted alkylene, and the unsubstituted alkylene may have a branch, a double bond, a triple bond. The total number of carbon atoms is preferably 2-30. Examples of such alkylene include ethylene, propylene, i-propylene, butylene, i-butylene, cyclohexylene, and the like.
As the arylene of Q, A ^{1 to} A ⁵ described later have the same meaning as the arylene.

In the general formulas (1) and (2)), the arylene of A ^{1 to} A ⁵ is substituted with a benzene ring and an alkyl group, aryl group, alkenyl group, alkoxy group, cyano group, or halogen atom. And a substituent-containing arylene.
The alkyl group in the substituent-containing arylene may have a branch, may have a double bond or a triple bond, and preferably has 1 to 20 carbon atoms in total. Is particularly preferred. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an s-butyl group, a t-butyl group, a butyryl group, a cyclohexyl group, and a cyclohexenyl group.
The aryl substituent in the substituent-containing arylene preferably has a total carbon number of 6-30, particularly preferably 6-15, and examples of the substituent include a phenyl group, a naphthyl group, an anthracenyl group, and a methoxyphenyl group. , A chlorophenyl group, and the like.
The alkyl group in the substituent-containing arylene may have a branch, may have a double bond or a triple bond, and preferably has 1 to 20 carbon atoms in total. Is particularly preferred. Examples of such an alkyl group include a methyl group, an ethyl group, an ethynyl group, a propyl group, an isopropyl group, a butyl group, a s-butyl group, a t-butyl group, a butyryl group, a cyclohexyl group, and a cyclohexenyl group.
The alkenyl substituent in the substituent-containing arylene preferably has a total carbon number of 2 to 10, particularly preferably 2 to 6, and examples of the substituent include an ethynyl group, a propenyl group, and a butyryl group.
The alkoxy substituent in the substituent-containing arylene may have a branch, preferably has a total carbon number of 1 to 10, more preferably 1 to 5, and examples of the substituent include a methoxy group, an ethoxy group, Examples thereof include a propyloxy group, a 2-methylpropyloxy group, and a butoxy group.
Such a substituent-containing arylene may have a branch, may have a double bond or a triple bond, preferably has 2 to 40 carbon atoms, and particularly preferably has 2 to 25 carbon atoms.
Examples of such a substitution-containing arylene include a methylphenyl ring, a dimethylphenyl ring, a dibutylphenyl ring, a methoxyphenyl ring, a cyclohexylphenyl ring, a biphenyl structure, a dichlorophenyl ring, a tribromophenyl ring, and a chlorocyanophenyl ring. It is done.
The alkylene of A ^{1 to} A ^{5 has} the same meaning as the alkylene of P.

In the general formulas (1) and (2), X ^{1 to} X ⁵ are each a single bond, an oxygen atom, a sulfur atom, an amino group, a carbonyl group, —COO—, —OCO—, alkylene, as described above. And arylene.
The alkylene may form a branched structure, may have a substituent, may have a double bond or a triple bond, and may form a ring.
The arylene may have a substituent.

In the general formulas (1) and (2), the alkyl group represented by R ^{1 to} R ⁵ is substituted with an unsubstituted alkyl group, an aryl group, an alkenyl group, a hydroxyl group, an alkoxy group, a cyano group, or a halogen atom. And a substituent-containing alkyl group which may have a divalent group of an oxygen atom, a sulfur atom, a carbonyl group, an amide group, a urethane group, a urea group, or an ester group.
The unsubstituted alkyl group may have a branch, may have a double bond or a triple bond, and preferably has a total carbon number of 1 to 20, more preferably 1 to 10. Examples of such an alkyl group include a methyl group, an ethyl group, an ethynyl group, a propyl group, an isopropyl group, a butyl group, a s-butyl group, a t-butyl group, a butyryl group, a cyclohexyl group, and a cyclohexenyl group. .
The aryl substituent in the substituent-containing alkyl group preferably has a total carbon number of 6 to 30, more preferably 6 to 15, and examples of the substituent include a phenyl group, a naphthyl group, an anthracenyl group, and methoxyphenyl. Group, chlorophenyl group, and the like.
The alkenyl substituent in the substituent-containing alkyl group preferably has a total carbon number of 2 to 10, more preferably 2 to 6, and examples of the substituent include an ethynyl group, a propenyl group, and a butyryl group. .
The alkoxy substituent in the substituent-containing alkyl group may have a branch, preferably has a total carbon number of 1 to 10, more preferably 1 to 5, and examples of the substituent include a methoxy group and an ethoxy group. Group, propyloxy group, 2-methylpropyloxy group, butoxy group, and the like.
Such a substituent-containing alkyl group may have a branch, may have a double bond or a triple bond, preferably has 2 to 40 carbon atoms, and particularly preferably has 2 to 25 carbon atoms. Examples of such substitution-containing alkyl groups include 2-ethylhexyl group, chlorobutyl group, benzyl group, 2-ethynylpropyl group, phenylethyl group, cyanopropyl group, methoxyethyl group, and the like.

Specific examples of the thermal crosslinking agent include compounds represented by the following structural formulas (i) to (ix), but are not limited to these compounds.

The compounds represented by the structural formulas (i) to (ix) are compounds having two or more oxirane rings having a substituent at the oxirane ring portion in one molecule, and these compounds are contained in the photosensitive composition. Inclusion can be identified by measuring the ¹ H-NMR spectrum.

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

<Other ingredients>
Examples of the other components include sensitizers, thermal polymerization inhibitors, plasticizers, colorants (coloring pigments or dyes), extender pigments, and the like, and further adhesion promoters to the substrate surface and other components. Auxiliaries (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, perfumes, surface tension modifiers, chain transfer agents, etc.) may be used in combination. By appropriately containing these components, properties such as stability, photographic properties, film physical properties, etc. of the intended photosensitive composition or the photosensitive film described later can be adjusted.
Among these, in the case of exposing and developing the photosensitive layer, from the viewpoint of improving the minimum energy (sensitivity) of the light that does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development, for example, It is particularly preferred to use a sensitizer together.
In addition, by appropriately containing these components, properties such as stability, photographic properties, print-out properties, and film properties of the target photosensitive layer (the pattern forming material) can be adjusted.

-Sensitizer-
There is no restriction | limiting in particular as said sensitizer, According to the said light irradiation means (For example, visible light, an ultraviolet light, visible light laser etc.), it can select suitably. When the light irradiation means is combined with a laser of 380 to 420 nm, a sensitizer having a maximum absorption wavelength of 380 to 450 nm is preferable.
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
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 not only improves the sensitivity of the photosensitive layer, but also has a function as a photopolymerization initiator that initiates polymerization of the monomer by photoexcitation.

The sensitizer is not particularly limited and may be appropriately selected from known sensitizers. For example, a compound in which an aromatic ring or a heterocycle is condensed (condensed ring compound), at least two An amine compound substituted with either an aromatic hydrocarbon ring or an aromatic heterocyclic ring is preferred.
Among the condensed ring compounds, hetero condensed ring compounds are 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.

  Among the amine compounds substituted with any of the at least two aromatic hydrocarbon rings and aromatic heterocyclic rings, at least two aromatic rings represented by the following general formulas (V) to (VII): Are more preferred, and triarylamine compounds are particularly preferred.

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

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

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

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

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

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

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

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

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

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

Examples of the optional substituent that the rings A to G and the linking group L may have include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxyl group; nitro group; cyano group; monovalent organic group and the like Examples of the monovalent organic group include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a tert-butyl group, an amyl group, and a tert-amyl group. , N-hexyl group, n-heptyl group, n-octyl group, tert-octyl group, etc., linear or branched alkyl group having 1 to 18 carbon atoms; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl A cycloalkyl group having 3 to 18 carbon atoms such as a group; a linear or branched alkenyl group having 2 to 18 carbon atoms such as a vinyl group, a propenyl group, and a hexenyl group; C3-C18 cycloalkenyl groups such as tenenyl group, cyclohexenyl group; methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, amyloxy A straight chain or branched alkoxy group having 1 to 18 carbon atoms such as a group, tert-amyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, tert-octyloxy group; methylthio group, ethylthio group Group, n-propylthio group, iso-propylthio group, n-butylthio group, sec-butylthio group, tert-butylthio group, amylthio group, tert-amylthio group, n-hexylthio group, n-heptylthio group, n-octylthio group, C1-C18 linear or branched such as tert-octylthio group Aryl group having 6 to 18 carbon atoms such as phenyl group, tolyl group, xylyl group and mesityl group; aralkyl group having 7 to 18 carbon atoms such as benzyl group and phenethyl group; vinyloxy group, propenyloxy group and hexenyloxy Table with -COR ^21; alkenylthio group linear or branched containing from 2 to 18 carbon atoms such as vinylthio group, propenylthio group, hexenyl thio group; a straight-chain or branched alkenyloxy group having 2 to 18 carbon atoms group Carboxyl group; acyloxy group represented by —OCOR ²² ; amino group represented by —NR ²³ R ²⁴ ; acylamino group represented by —NHCOR ²⁵ ; carbamate group represented by —NHCOOR ²⁶ ; a carboxylate group represented by -COOR ^29; carbamoyl groups represented by -CONR ²⁷ R ^28; Represented by ^{-C = N-NR 34 R 35} ; -SO 3 sulfonic acid represented by ^{R 32} ester _group;; -C = group represented by ^{NR 33} SO ₃ ^{NR 30} sulfamoyl group represented by R ³¹ 2-thienyl group, 2-pyridyl group, furyl group, oxazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl group, morpholino group, pyrrolidinyl group, tetrahydrothiophene dioxide group, etc. Is mentioned.

R ^{21 to} R ³⁵ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, or an optionally substituted aralkyl. Represents a group. In these substituent groups, the alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkoxy group, alkylthio group, aryl group, aralkyl group, alkenyloxy group, and alkenylthio group are further substituted with a substituent. May be.

There is no restriction | limiting in particular as a substitution position in the rings A-G and the coupling group L of these substituents. Moreover, when it has several substituents, these may be the same kind and are different. May be.
Rings A to G and linking group L are unsubstituted or substituted as a halogen atom, a cyano group, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, or a substituted group. An optionally substituted alkenyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted alkenyloxy group, an optionally substituted alkenylthio Group, optionally substituted amino group, optionally substituted acyl group, carboxyl group, group represented by —C═NR ³³ , group represented by —C═N—NR ³⁴ R ³⁵ , saturated Alternatively, it is preferably substituted with an unsaturated heterocyclic group. In the case of having a substituent, examples of the substituent include a halogen atom, a cyano group, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkenyl group, and an optionally substituted group. A good alkoxy group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted amino group, a group represented by —C═NR ³³ , —C═N—NR ³⁴ R ^The group represented by ³⁵ and a saturated or unsaturated heterocyclic group are preferred.

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

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

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

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

  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 film, 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.

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

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

-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 (CI. 26150), Monolite Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow HR). Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Hoster Balm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11) Fastel Pink B Supra (CI Pigment Red 81) Monastral Fa Strike Blue (C.I. Pigment Blue 15), mono Light Fast Black B (C.I. Pigment Black 1), carbon, C. I. Pigment red 97, C.I. I. Pigment red 122, C.I. I. Pigment red 149, C.I. I. Pigment red 168, C.I. I. Pigment red 177, C.I. I. Pigment red 180, C.I. I. Pigment red 192, C.I. I. Pigment red 215, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 22, C.I. I. Pigment blue 60, C.I. I. Pigment blue 64 and the like. These may be used alone or in combination of two or more. Moreover, the dye suitably selected from well-known dye can be used as needed.

  The solid content in the photosensitive composition solid content of the color pigment can be determined in consideration of the exposure sensitivity, resolution, etc. of the photosensitive layer at the time of permanent pattern formation, depending on the type of the color pigment. Generally, 0.01 to 10% by mass is preferable, and 0.05 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.

  Suitable examples of the adhesion promoter include adhesion promoters described in JP-A-5-11439, JP-A-5-341532, and JP-A-6-43638. 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, 0.001-20 mass% is preferable with respect to all the components in the said photosensitive composition, 0.01-10 mass% is more preferable, 0.1-5 mass% Is particularly preferred.

  The photosensitive composition of the present invention does not react at low temperature or normal temperature during storage, is excellent in storage stability, has low surface tackiness, and has good laminating properties and handling properties when formed into a film. Excellent peelability from protective film and support, high sensitivity and excellent developability, and excellent chemical resistance, surface hardness, heat resistance, dielectric properties, and electrical insulation after development. For this reason, protective films for printed wiring boards (multilayer wiring boards, build-up wiring boards, etc.), interlayer insulating films, and solder resist patterns, color filters, pillar materials, rib materials, spacers, display members such as spacers, holograms, It can be widely used for forming permanent patterns such as micromachines and proofs, and can be particularly suitably used for the photosensitive film of the present invention, permanent patterns and methods for forming the same.

(Photosensitive film)
The photosensitive film of the present invention comprises a support, and on the support, (A) a binder, (B) a polymerizable compound, (C) a photopolymerization initiator, and (D) at least a softening point and a melting point. A photosensitive layer obtained by using the photosensitive composition of the present invention, which includes at least a thermal crosslinking agent that is 50 to 250 ° C. and soluble in a solvent, and is protected on the photosensitive layer And, if necessary, other layers such as a cushion layer and an oxygen barrier layer (PC layer).
In addition, the said photosensitive film is used for the permanent pattern formation method mentioned later, This permanent pattern formation method is performed by laminating | stacking the photosensitive layer of the said photosensitive film on a base material.
Further, in the case where 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 preferably 100 mJ / cm ² or less. .
In the case of exposing and developing the photosensitive layer, the minimum energy of light that does not change the thickness of the exposed portion of the photosensitive layer before and after the exposure and development is particularly limited as long as it is 100 mJ / cm ² or less. rather, may be appropriately selected depending on the intended purpose, for example, preferably 0.1~80mJ / cm ^2, more preferably 0.5~70mJ / cm ^2, more preferably 1~50mJ / cm ^2, 1 5-30 mJ / cm ² is particularly preferable.
The minimum energy is less than 0.1 mJ / cm ^2, may fogging in process step occurs, it exceeds 100 mJ / cm ^2, increases the time necessary for exposure, processing speed is slow Sometimes.

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

In the photosensitive film of the present invention, a sample cut into a width of 4.5 cm and a length of 8 cm is fixed on a pedestal so that the support is on the surface side, and the support is pulled from the sample at a speed of 160 cm / min. The peeling force between the photosensitive layer and the support when peeled in the length direction is preferably 1 to 40 g, more preferably 1 to 30 g, per 4.5 cm length of the sample. Particularly preferred is 20 g.
When the peeling force between the photosensitive layer and the support is more than 500 g, the peelability between the photosensitive layer and the support is inferior, and the tackiness of the surface of the photosensitive layer may increase, and is less than 1 g. The protective film and the support may be peeled off during storage of the photosensitive film.

[Method for producing photosensitive film]
There is no restriction | limiting in particular as a manufacturing method of the said photosensitive film, According to the objective, it can select suitably, Said (A) binder, (B) polymeric compound, (C) photoinitiator, and (D) A photosensitive composition containing a thermal crosslinking agent having at least one of a softening point and a melting point of 50 to 250 ° C. and soluble in a solvent, the sensitizer appropriately selected as necessary, and other components The photosensitive layer obtained by using the product, and at least a protective film on the photosensitive layer, and further include other layers such as a cushion layer and an oxygen barrier layer (PC layer) as necessary.
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.

<Photosensitive layer>
The photosensitive layer in the photosensitive film is formed of 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, According to the objective, it can select suitably, Usually, it laminates | stacks on the said support body.
The photosensitive layer can be formed by applying the photosensitive composition of the present invention on a support described later and drying it.

  The method for applying and drying the photosensitive composition on the support is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the photosensitive composition is applied to the surface of the support. And a method of laminating by dissolving, emulsifying or dispersing in water or a solvent to prepare a photosensitive composition solution, directly applying the solution and drying.

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

The coating method is not particularly limited and can be appropriately selected depending on the purpose. For example, using a spin coater, a slit spin coater, a roll coater, a die coater, a curtain coater, 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.

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

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

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

  There is no restriction | limiting in particular as thickness of the said support body, According to the objective, it can select suitably, 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, According to the objective, it can select suitably, 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 10-20,000 m is mentioned.

<Protective film>
The photosensitive film has a protective film on the photosensitive layer.
Examples of the protective film include those used for the support, silicone paper, polyethylene, paper laminated with polypropylene, polyolefin or polytetrafluoroethylene sheet, etc. Among these, polyethylene film, Polypropylene film is preferred.
There is no restriction | limiting in particular as thickness of the said protective film, According to the objective, it can select suitably, 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 discharge irradiation treatment, active plasma irradiation treatment, and laser beam irradiation treatment.

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 10-20,000m. Further, slitting may be performed so that the user can easily use, and a long body in the range of 100 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 has at least one of a softening point and a melting point of 50 to 250 ° C., and includes a thermal crosslinking agent that is soluble in a solvent. No reaction at low or normal temperatures, excellent storage stability, low surface tack, good laminating and handling properties when formed into a film, and excellent peelability from protective film and support High sensitivity, good developability, excellent chemical resistance, surface hardness, heat resistance, dielectric properties, electrical insulation after development, printed wiring boards, color filters and pillar materials, rib materials, spacers, partition walls It can be widely used for pattern formation of display members such as holograms, micromachines, and proofs, and can be suitably used for the permanent pattern formation method of the present invention.
In particular, since the thickness of the photosensitive film is uniform, the lamination to the base material is performed more finely when forming the laminated body described later.

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

<Formation of laminate>
When pattern formation is performed using the photosensitive composition of the present invention, a laminate is formed by laminating a photosensitive layer comprising the photosensitive composition on a substrate.
When pattern formation is performed using the photosensitive film of the present invention, at least a photosensitive layer of the photosensitive film is laminated on a substrate to form a laminate.

-Base material-
The substrate is not particularly limited and can be appropriately selected from known materials having high surface smoothness to those having an uneven surface. A plate-like substrate (substrate) is preferred. Specifically, known printed wiring board forming substrates (for example, copper-clad laminates), glass plates (for example, soda glass plates, etc.), synthetic resin films, paper, metal plates and the like can be mentioned. Among these, a printed wiring board forming substrate is preferable, and the printed wiring board forming substrate has already been formed with a wiring pattern in that high-density mounting of a semiconductor or the like on a multilayer wiring board or a build-up wiring board is possible. It is particularly preferred that

-Laminate-
There is no restriction | limiting in particular as a formation method of the laminated body of the said 1st aspect, Although it can select suitably according to the objective, It formed by apply | coating and drying the said photosensitive composition on the said base material. It is preferable to laminate a photosensitive layer.
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.

  The method for forming the laminate of the second aspect is not particularly limited and can be appropriately selected according to the purpose. However, the layer structure in the laminate is not particularly limited and is appropriately selected according to the purpose. For example, a layer structure having the base, the photosensitive layer, and the support in this order is preferable. Since the photosensitive film has a protective film on the photosensitive layer, when the photosensitive film is laminated on a substrate, the protective film is peeled off from the photosensitive layer so that the photosensitive layer and the substrate are in contact with each other. It is preferable to laminate on the substrate so as to be in contact with each other.

There is no restriction | limiting in particular as a formation method of this laminated body, Although it can select suitably, It is preferable to laminate | stack the said photosensitive film on the said base material, performing at least any one of a heating and pressurization.
There is no restriction | limiting in particular as said heating temperature, According to the objective, it can select suitably, 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, According to the objective, it can select suitably, 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, VP130 manufactured by Nichigo Morton Co., Ltd.) and the like.

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

<Exposure process>
The said exposure process is a process of exposing with respect to the said photosensitive layer in the said photosensitive laminated body. Examples of the photosensitive layer in the photosensitive laminate of the present invention include a photosensitive layer formed of the photosensitive composition in the photosensitive composition or the photosensitive film of the present invention.

  In addition, there is no restriction | limiting in particular as exposure to the laminated body which has the photosensitive layer formed by the formation method of the said photosensitive layer, According to the objective, it can select suitably, For example, the said support body, cushion layer, and PC The photosensitive layer may be exposed through a layer, and after the support is peeled off, the photosensitive layer may be exposed through the cushion layer and a PC layer, and the support and the cushion layer are peeled off. Then, the photosensitive layer may be exposed through the PC layer, or 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 means is not particularly limited and may be appropriately selected depending on the purpose. For example, the light irradiation means for irradiating light, and the light irradiation means for irradiating based on the pattern information to be formed. Examples thereof include light modulation means for modulating light.

  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. For example, the photosensitive layer is arranged in a two-dimensional array of light irradiation means and n pieces (where n is a natural number of 2 or more) that receives and emits light from the light irradiation means. An exposure head comprising a light modulation means capable of controlling the drawing portion in accordance with pattern information, the column direction of the drawing portion relative to the scanning direction of the exposure head Using an exposure head arranged so as to form a predetermined set inclination angle θ, the exposure head is subjected to N-fold exposure (where N is (Natural number of 2 or more) Designation of a grapheme part and control of the pixel part for the exposure head so that only the picturee part designated by the use picture element part designation means is involved in exposure by the picture element part control means It is preferable that the exposure head is moved relative to the photosensitive layer in the scanning direction.

In the present invention, “N double exposure” means that the exposed surface is irradiated with a straight line parallel to the scanning direction of the exposure head in almost all of the exposed region on the exposed surface of the photosensitive layer. This means exposure by setting that intersects N light spot rows (pixel rows). Here, the “light spot array (pixel array)” is a direction in which the angle formed with the scanning direction of the exposure head is smaller in the array of light spots (pixels) as pixel units generated by the pixel unit. Refers to a sequence of Note that the arrangement of the picture element portions is not necessarily a rectangular lattice shape, and may be, for example, an arrangement of parallelograms.
Here, “substantially all areas” of the exposure area is described as a straight line parallel to the scanning direction of the exposure head by tilting the pixel part rows at both side edges of each picture element part. Since the number of drawing element rows of the used drawing element parts to be crossed decreases, even if it is used to connect a plurality of exposure heads in such a case, it is parallel to the scanning direction due to errors in the mounting angle and arrangement of the exposure heads. The number of pixel parts in the used pixel part that intersect with a straight line may slightly increase or decrease, and the connection between the pixel parts in each used pixel part is only a fraction of the resolution. However, due to errors such as the mounting angle and the arrangement of the picture element parts, the pitch of the picture element parts along the direction orthogonal to the scanning direction does not exactly match the pitch of the picture element parts of other parts, and is parallel to the scanning direction. The number of used pixel parts that intersect with the straight line may increase or decrease within a range of ± 1. It is an order. In the following description, N multiple exposures where N is a natural number of 2 or more are collectively referred to as “multiple exposure”. Further, in the following description, “N multiple drawing” and “multiple exposure” are used as terms corresponding to “N double exposure” and “multiple exposure” for an embodiment in which the exposure apparatus or exposure method of the present invention is implemented as a drawing apparatus or drawing method. The term “multiple drawing” shall be used.
N in the N-fold exposure is not particularly limited as long as it is a natural number of 2 or more, and can be appropriately selected according to the purpose. However, a natural number of 3 or more is preferable, and a natural number of 3 or more and 7 or less is more preferable. .

-Pattern forming device-
An example of a pattern forming apparatus according to the permanent pattern forming method of the present invention will be described with reference to the drawings.
The pattern forming apparatus is a so-called flatbed type exposure apparatus, and as shown in FIG. 1, a sheet-like photosensitive laminate 12 (hereinafter, referred to as a laminate) in which at least the photosensitive layer in the pattern forming material is laminated. , “Photosensitive material 12” or “photosensitive layer 12”) is provided. Two guides 20 extending along the stage moving direction are installed on the upper surface of the thick plate-shaped installation table 18 supported by the four legs 16. The stage 14 is arranged so that the longitudinal direction thereof faces the stage moving direction, and is supported by the guide 20 so as to be reciprocally movable. The pattern forming apparatus 10 is provided with a stage driving device (not shown) that drives the stage 14 along the guide 20.

  A U-shaped gate 22 is provided at the center of the installation base 18 so as to straddle the movement path of the stage 14. Each end of the U-shaped gate 22 is fixed to both side surfaces of the installation base 18. A scanner 24 is provided on one side across the gate 22, and a plurality of (for example, two) sensors 26 that detect the front and rear ends of the photosensitive material 12 are provided on the other side. The scanner 24 and the sensor 26 are respectively attached to the gate 22 and fixedly arranged above the moving path of the stage 14. The scanner 24 and the sensor 26 are connected to a controller (not shown) that controls them.

  Here, for explanation, an X axis and a Y axis orthogonal to each other are defined in a plane parallel to the surface of the stage 14 as shown in FIG.

  A slit formed in a “<” shape that opens in the direction of the X-axis at the upstream edge (hereinafter sometimes simply referred to as “upstream”) along the scanning direction of the stage 14. 10 are formed at equal intervals. Each slit 28 includes a slit 28 a located on the upstream side and a slit 28 b located on the downstream side. The slit 28a and the slit 28b are orthogonal to each other, and the slit 28a has an angle of −45 degrees and the slit 28b has an angle of +45 degrees with respect to the X axis.

  The position of the slit 28 is substantially coincident with the center of the exposure head 30. Further, the size of each slit 28 is set to sufficiently cover the width of the exposure area 32 by the corresponding exposure head 30. Further, the position of the slit 28 may be substantially coincident with the center position of the overlapping portion between the adjacent exposed regions 34. In this case, the size of each slit 28 is set so as to sufficiently cover the width of the overlapping portion between the exposed regions 34.

  In the position below each slit 28 inside the stage 14, single cell type light detection as a light spot position detecting means for detecting a light spot as a pixel unit in a used pixel part designation process described later. A vessel (not shown) is incorporated. In addition, each photodetector is connected to an arithmetic unit (not shown) as a pixel part selection means for selecting the pixel part in the used pixel part specifying process described later.

  The operation form of the pattern forming apparatus at the time of exposure may be a form in which exposure is continuously performed while constantly moving the exposure head, or each movement destination position while the exposure head is moved stepwise. The exposure head may be stationary to perform the exposure operation.

<< Exposure head >>
Each exposure head 30 is connected to the scanner 24 so that each pixel portion (micromirror) row direction of an internal digital micromirror device (DMD) 36 described later forms a predetermined set inclination angle θ with the scanning direction. It is attached. For this reason, the exposure area 32 by each exposure head 30 is a rectangular area inclined with respect to the scanning direction. As the stage 14 moves, a strip-shaped exposed region 34 is formed in the photosensitive layer 12 for each exposure head 30. In the example shown in FIGS. 2 and 3B, the scanner 24 includes ten exposure heads arranged in a substantially matrix of 2 rows and 5 columns.
In the following description, when the individual exposure heads arranged in the mth row and the nth column are indicated, the exposure head 30 _mn is indicated, and exposure by the individual exposure heads arranged in the mth row and the nth column is performed. When an area is indicated, it is expressed as an exposure area 32 _mn .

Further, as shown in FIGS. 3A and 3B, each of the exposure heads 30 in each row arranged in a line so that each of the strip-shaped exposed regions 34 partially overlaps the adjacent exposed region 34 is In the arrangement direction, they are shifted by a predetermined interval (a natural number times the long side of the exposure area, twice in this embodiment). Therefore, can not be exposed portion between the exposure area _{32 11} in the first row and the exposure area _{32 12,} it can be exposed by the second row of the exposure area _{32 21.}

  As shown in FIGS. 4 and 5, each of the exposure heads 30 includes a light modulation unit (spatial light modulation element that modulates each pixel unit) that modulates incident light for each pixel unit according to image data. As a DMD 36 (manufactured by Texas Instruments, USA). The DMD 36 is connected to a controller serving as a pixel part control unit including a data processing unit and a mirror drive control unit. The data processing unit of this controller generates a control signal for driving and controlling each micromirror in the use area on the DMD 36 for each exposure head 30 based on the input image data. The mirror drive control unit controls the angle of the reflection surface of each micromirror of the DMD 36 for each exposure head 30 based on the control signal generated by the image data processing unit.

  As shown in FIG. 4, on the light incident side of the DMD 36, there is provided a laser emission portion in which the emission end portion (light emission point) of the optical fiber is arranged in a line along the direction that coincides with the long side direction of the exposure area 32. The fiber array light source 38, the lens system 40 for correcting the laser light emitted from the fiber array light source 38 and condensing it on the DMD, and the mirror 42 for reflecting the laser light transmitted through the lens system 40 toward the DMD 36 Arranged in order. In FIG. 4, the lens system 40 is schematically shown.

  As shown in detail in FIG. 5, the lens system 40 has a pair of combination lenses 44 that collimate the laser light emitted from the fiber array light source 38, and the light quantity distribution of the collimated laser light becomes uniform. A pair of combination lenses 46 to be corrected in this way, and a condensing lens 48 that condenses the laser light whose light quantity distribution has been corrected on the DMD 36.

  Further, on the light reflection side of the DMD 36, a lens system 50 that images the laser light reflected by the DMD 36 on the exposed surface of the photosensitive layer 12 is disposed. The lens system 50 includes two lenses 52 and 54 arranged so that the DMD 36 and the exposed surface of the photosensitive layer 12 have a conjugate relationship.

  In the present embodiment, the laser light emitted from the fiber array light source 38 is substantially magnified five times, and then the light from each micromirror on the DMD 36 is reduced to about 5 μm by the lens system 50. Is set to

-Light modulation means-
The light modulating means has n (where n is a natural number of 2 or more) two-dimensionally arranged image elements, and can control the image elements according to the pattern information. If it is, there will be no restriction | limiting in particular, According to the objective, it can select suitably, For example, a spatial light modulation element is preferable.

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

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

Hereinafter, an example of the light modulation means will be described with reference to the drawings.
As shown in FIG. 6, the DMD 36 is a mirror device in which a large number of micromirrors 58 are arranged in a lattice pattern on a SRAM cell (memory cell) 56 as a pixel portion constituting each pixel (pixel). . In this embodiment, the DMD 36 in which the micromirrors 58 of 1,024 columns × 768 rows are arranged is used. Of these, the micromirrors 58 that can be driven by the controller connected to the DMD 36, that is, usable, are 1,024. It is assumed that there are only columns × 256 rows. The data processing speed of the DMD 36 is limited, and the modulation speed per line is determined in proportion to the number of micromirrors to be used. Thus, by using only some of the micromirrors in this way, Modulation speed increases. Each micromirror 58 is supported by a support column, and a material having high reflectivity such as aluminum is deposited on the surface thereof. In the present embodiment, the reflectance of each micromirror 58 is 90% or more, and the arrangement pitch thereof is 13.7 μm in both the vertical direction and the horizontal direction. The SRAM cell 56 is of a silicon gate CMOS manufactured in a normal semiconductor memory manufacturing line via a support including a hinge and a yoke, and the whole is configured monolithically (integrated).

  When an image signal representing the density of each point constituting a desired two-dimensional pattern in binary is written in the SRAM cell (memory cell) 56 of the DMD 36, each micromirror 58 supported by the column is centered on the diagonal line. As shown in FIG. 1, the inclination is inclined to ± α degrees (for example, ± 10 degrees) with respect to the substrate side on which the DMD 36 is disposed. FIG. 7A shows a state in which the micromirror 58 is tilted to + α degrees in the on state, and FIG. 7B shows a state in which the micromirror 58 is tilted to −α degrees in the off state. In this way, by controlling the inclination of the micromirror 58 in each pixel of the DMD 36 as shown in FIG. 6 in accordance with the image signal, the laser light B incident on the DMD 36 moves in the inclination direction of each micromirror 58. Reflected.

  FIG. 6 shows an example in which a part of the DMD 36 is enlarged and each micromirror 58 is controlled to + α degrees or α degrees. The on / off control of each micromirror 58 is performed by the controller connected to the DMD 36. Further, a light absorber (not shown) is arranged in the direction in which the laser beam B reflected by the off-state micromirror 58 travels.

-Light irradiation means-
The light irradiation means is not particularly limited and may be appropriately selected depending on the purpose. For example, (ultra) high pressure mercury lamp, xenon lamp, carbon arc lamp, halogen lamp, copier, fluorescent tube, LED, etc. , A known light source such as a semiconductor laser, or a means capable of synthesizing and irradiating two or more lights. Among these, a means capable of synthesizing and irradiating two or more lights is preferable.
The light irradiated from the light irradiation means, for example, when light irradiation is performed through a support, transmits the support and activates the used photopolymerization initiating compound or sensitizer. Examples include electromagnetic waves, ultraviolet to visible light, electron beams, X-rays, and laser beams. Among these, laser beams are preferable, and a laser that combines two or more lights (hereinafter sometimes referred to as a “combined laser”). Is more preferable. Even when light irradiation is performed after the support is peeled off, the same light can be used.

The wavelength of ultraviolet to visible light is preferably, for example, 300 to 1,500 nm, more preferably 320 to 800 nm, and particularly preferably 330 to 650 nm.
As a wavelength of the said laser beam, 200-1500 nm is preferable, for example, 300-800 nm is more preferable, 330-500 nm is still more preferable, 400-450 nm is especially preferable.

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

Hereinafter, means (fiber array light source) capable of irradiating the combined laser will be described with reference to the drawings.
As shown in FIG. 8, the fiber array light source 38 includes a plurality of (for example, 14) laser modules 60, and one end of a multimode optical fiber 62 is coupled to each laser module 60. An optical fiber 64 having a cladding diameter smaller than that of the multimode optical fiber 62 is coupled to the other end of the multimode optical fiber 62. As shown in detail in FIG. 9, seven ends of the optical fiber 64 opposite to the multimode optical fiber 62 are arranged along the direction orthogonal to the scanning direction, and these are arranged in two rows to form the laser emitting unit 66. Is configured.

  As shown in FIG. 9, the laser emitting portion 66 constituted by the end portion of the optical fiber 64 is sandwiched and fixed between two support plates 68 having a flat surface. Moreover, it is desirable that a transparent protective plate such as glass is disposed on the light emitting end face of the optical fiber 64 for protection. The light exit end face of the optical fiber 64 has a high light density and is likely to collect dust and easily deteriorate. However, by arranging the protective plate as described above, it is possible to prevent the dust from adhering to the end face and to delay the deterioration. Can do.

  For example, as shown in FIG. 25, such an optical fiber is formed by coaxially connecting an optical fiber 64 having a length of 1 to 30 cm with a small cladding diameter at the tip portion on the laser light emission side of a multimode optical fiber 62 having a large cladding diameter. Can be obtained by linking them together. In the two optical fibers, the incident end face of the optical fiber 64 is fused and joined to the outgoing end face of the multimode optical fiber 62 so that the central axes of both optical fibers coincide. As described above, the diameter of the core 64 a of the optical fiber 64 is the same as the diameter of the core 62 a of the multimode optical fiber 62.

  In addition, a short optical fiber in which an optical fiber having a short cladding diameter and a large cladding diameter is fused with an optical fiber having a small cladding diameter may be coupled to the output end of the multimode optical fiber 62 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 64 may be referred to as an emission end portion of the multimode optical fiber 62.

  The multimode optical fiber 62 and the optical fiber 64 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 62 and the optical fiber 64 are step index type optical fibers, and the multimode optical fiber 62 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 64 has a clad 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 is not limited to 60 μm. The clad diameter of the optical fiber used in the conventional fiber array light source is 125 μm. However, the smaller the clad diameter, the deeper the focal depth, so the clad diameter of the optical fiber is preferably 80 μm or less, more preferably 60 μm or less. 40 μm or less is more preferable. On the other hand, since the core diameter needs to be at least 3 to 4 μm, the cladding diameter of the optical fiber 64 is preferably 10 μm or more.

  The laser module 60 is composed of 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 arranged on the heat block 110, And LD7, collimator lenses L1, L2, L3, L4, L5, L6, and L7 provided corresponding to each of the GaN-based semiconductor lasers LD1 to LD7, one condenser lens 200, and one multimode. And an optical fiber 62. 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 semiconductor lasers LD1 to LD7, lasers having an oscillation wavelength other than the above-described 405 nm in a wavelength range of 350 to 450 nm may be used.

  As shown in FIGS. 27 and 28, the combined laser light source is housed in a box-shaped package 400 having an upper opening together with other optical elements. The package 400 includes a package lid 410 created so as to close the opening. After the degassing process, a sealing gas is introduced, and the package 400 and the package lid are closed by closing the opening of the package 400 with the package lid 410. The combined laser light source is hermetically sealed in a closed space (sealed space) formed by the reference numeral 410.

  A base plate 420 is fixed to the bottom surface of the package 400, and the heat block 110, a condensing lens holder 450 that holds the condensing lens 200, and the multimode optical fiber 62 are disposed on the top surface of the base plate 420. A fiber holder 460 that holds the incident end is attached. The exit end of the multimode optical fiber 62 is drawn out of the package from an opening formed in the wall surface of the package 400.

  A collimator lens holder 440 is attached to the side surface of the heat block 110, and the collimator lenses L1 to L7 are held. An opening is formed in the lateral wall surface of the package 400, and a wiring 470 for supplying a driving current to the GaN semiconductor lasers LD1 to LD7 is drawn out of the package through the opening.

  In FIG. 28, in order to avoid complication of the drawing, only the GaN semiconductor laser LD7 is numbered among the plurality of GaN semiconductor lasers, and only the collimator lens L7 is numbered among the plurality of collimator lenses. is doing.

  FIG. 29 shows a front shape of a mounting portion of the collimator lenses L1 to L7. Each of the collimator lenses L <b> 1 to L <b> 7 is formed in a shape in which a region including the optical axis of a circular lens having an aspherical surface is cut out in a parallel plane. This elongated collimator lens can be formed, for example, by molding resin or optical glass. The collimator lenses L1 to L7 are closely arranged in the light emitting point arrangement direction so that the length direction is orthogonal to the light emitting point arrangement direction of the GaN-based semiconductor lasers LD1 to LD7 (left-right direction in FIG. 29).

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

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 L1 to L7 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 L1 to L7 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. In addition, each of the collimator lenses L1 to L7 has a focal length f ₁ = 3 mm, NA = 0.6, and a lens arrangement pitch = 1.25 mm.

The condensing lens 200 is formed by cutting a region including the optical axis of a circular lens having an aspherical surface into a long and narrow plane in parallel planes, and is long in the arrangement direction of the collimator lenses L1 to L7, that is, in the horizontal direction and short in the direction perpendicular thereto. Is formed. The condenser lens 200 has a focal length f ₂ = 23 mm and NA = 0.2. This condensing lens 200 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.

  Moreover, as a light irradiation means provided with a plurality of light emitting points, for example, as shown in FIG. 30, a laser in which a plurality of (for example, seven) chip-shaped semiconductor lasers LD1 to LD7 are arranged on a heat block 110. An array can be used. Further, a chip-shaped multi-cavity laser 110 shown in FIG. 31A in which a plurality of (for example, five) light emitting points 111a are arranged in a predetermined direction is known. Since the multicavity laser 111 can arrange the light emitting points with higher positional accuracy than 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 multi-cavity laser 111 is likely to be bent at the time of laser manufacture. Therefore, the number of light emitting points 111a is preferably 5 or less.

  As the light irradiation means, as shown in FIG. 31B, a plurality of multi-cavity lasers 111 are arranged on the heat block 110 in the same direction as the arrangement direction of the light emitting points 111a of each chip. A 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. 32, a combined laser light source including a chip-shaped multicavity laser 111 having a plurality of (for example, three) emission points 111a can be used. The combined laser light source includes a multi-cavity laser 111, a single multi-mode optical fiber 62, and a condenser lens 200. The multicavity laser 111 can be composed of, for example, a GaN laser diode having an oscillation wavelength of 405 nm.

  In the above-described configuration, each of the laser beams B emitted from each of the plurality of light emitting points 111 a of the multicavity laser 111 is collected by the condenser lens 200 and enters the core 62 a of the multimode optical fiber 62. The laser light incident on the core 62a propagates in the optical fiber, is combined into one, and is emitted.

  A plurality of light emitting points 111 a of the multicavity laser 111 are arranged in parallel within a width substantially equal to the core diameter of the multimode optical fiber 62, and a focal point substantially equal to the core diameter of the multimode optical fiber 62 is formed as the condenser lens 200. By using a convex lens of a distance or a rod lens that collimates the outgoing beam from the multicavity laser 111 only in a plane perpendicular to the active layer, the coupling efficiency of the laser beam B to the multimode optical fiber 62 can be increased. it can.

  As shown in FIG. 33, a multi-cavity laser 111 having a plurality of (for example, three) emission points is used, and a plurality of (for example, nine) multi-cavity lasers 111 are equidistant from each other on the heat block 110. A combined laser light source including the laser array 140 arranged in (1) can be used. The plurality of multi-cavity lasers 111 are arranged and fixed in the same direction as the arrangement direction of the light emitting points 111a 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 111, 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 111 a of the plurality of multi-cavity lasers 111 is condensed 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 collected by the condenser lens 200 and enters the core 62 a of the multimode optical fiber 62. The laser light incident on the core 62a propagates in the optical fiber, is combined into one, and is emitted.

  Still another example of the combined laser light source will be described. As shown in FIGS. 34A and 34B, this combined laser light source has a heat block 182 having an L-shaped cross section in the optical axis direction mounted on a substantially rectangular heat block 180 and is housed between two heat blocks. A space is formed. On the upper surface of the L-shaped heat block 182, a plurality of (for example, two) multi-cavity lasers 111 in which a plurality of light emitting points (for example, five) are arranged in an array form the light emitting points 111a 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 111, a collimator lens array 184 in which collimator lenses are arranged corresponding to the light emission points 111a 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 divergence angle of the laser beam is large (the fast axis direction), and the width direction of each collimating lens is 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 beam emitting side of the collimating lens array 184, there is one multimode optical fiber 62 and a condensing lens 200 that condenses and couples the laser beam to the incident end of the multimode optical fiber 62. Is arranged.

  In the above configuration, each of the laser beams B emitted from each of the plurality of light emitting points 111a of the plurality of multi-cavity lasers 111 arranged on the laser blocks 180 and 182 is collimated by the collimating lens array 184 and collected. The light is collected by the optical lens 200 and is incident on the core 62 a of the multimode optical fiber 62. The laser light incident on the core 62a 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.

  A laser module in which each of the combined laser light sources is housed in a casing and the emission end portion of the multimode optical fiber 62 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.

<< Used pixel part designation means >>
The used pixel part specifying means includes a light spot position detecting means for detecting the position of a light spot on a surface to be exposed as a pixel unit, and N-fold exposure based on a detection result by the light spot position detecting means. It is preferable to include at least a pixel part selection unit that selects a pixel part to be used for the realization.
Hereinafter, an example of a method for designating a pixel part used for N-exposure by the used pixel part designation unit will be described.

(1) Method for Specifying Picture Element Portions Used in Single Exposure Head In the present embodiment (1), the pattern forming apparatus 10 performs double exposure on the photosensitive material 12, and each exposure head 30. A description will be given of a method for designating a used pixel part for reducing the variation in resolution and density unevenness caused by the mounting angle error and realizing ideal double exposure.

The set inclination angle θ in the column direction of the image element (micromirror 58) with respect to the scanning direction of the exposure head 30 can be used in an ideal state where there is no mounting angle error of the exposure head 30 or the like. It is assumed that an angle slightly larger than the angle θ _ideal, which is exactly double exposure using a column × 256 rows of pixel parts, is adopted.
This angle θ _ideal is equal to the number N of N double exposures, the number s of usable micromirrors 58 in the column direction, the interval p of usable micromirrors 58 in the column direction, and the microscopic exposure head 30 in a tilted state. For the pitch δ of the scanning line formed by the mirror,
spsinθ _ideal ≧ Nδ (Formula 1)
Given by. As described above, the DMD 36 according to the present embodiment includes a large number of micromirrors 58 having equal vertical and horizontal arrangement intervals arranged in a rectangular lattice shape.
pcosθ _ideal = δ (Formula 2)
And the above equation 1 is
stanθ _ideal = N (Formula 3)
It becomes. In the present embodiment (1), since s = 256 and N = 2 as described above, the angle θ _ideal is about 0.45 degrees according to Equation 3. Therefore, for example, an angle of about 0.50 degrees may be employed as the set inclination angle θ. It is assumed that the pattern forming apparatus 10 is initially adjusted so that the mounting angle of each exposure head 30, that is, each DMD 36 is close to the set inclination angle θ within an adjustable range.

  FIG. 10 illustrates an example of unevenness in a pattern on an exposed surface due to the influence of an attachment angle error of one exposure head 30 and pattern distortion in the pattern forming apparatus 10 that is initially adjusted as described above. FIG. In the following drawings and description, the light spot in the m-th row is represented by r (m) with respect to the light spot generated by each pixel part (micromirror) and constituting the exposure area on the exposed surface. ), The light spot in the nth column is denoted as c (n), and the light spot in the mth row and the nth column is denoted as P (m, n).

The upper part of FIG. 10 shows a pattern of light spot groups from the usable micromirrors 58 projected onto the exposed surface of the photosensitive material 12 with the stage 14 being stationary, and the lower part is the upper part. 2 shows the state of the exposure pattern formed on the surface to be exposed when the stage 14 is moved and continuous exposure is performed in the state where the pattern of light spots as shown in FIG.
In FIG. 10, for convenience of explanation, the exposure pattern of the odd-numbered columns of the usable micromirrors 58 and the exposure pattern of the even-numbered columns are shown separately. However, the actual exposure patterns on the exposed surface are shown in FIG. Two exposure patterns are superimposed.

In the example of FIG. 10, as a result of adopting the set inclination angle θ slightly larger than the angle θ _ideal , and because it is difficult to finely adjust the mounting angle of the exposure head 30, the actual mounting angle and the above As a result of the error in the set inclination angle θ, density unevenness occurs in any region on the exposed surface. Specifically, in both the exposure pattern by the odd-numbered micromirrors and the exposure pattern by the even-numbered micromirrors, it is ideal in the overlapped exposure region on the exposed surface formed by a plurality of pixel part rows. Overexposure occurs with respect to double exposure, resulting in a redundant drawing area and uneven density.

Furthermore, the example of FIG. 10 is an example of pattern distortion appearing on the surface to be exposed, and “angular distortion” occurs in which the inclination angle of each pixel row projected on the surface to be exposed is not uniform. Causes of such angular distortion include various aberrations and alignment deviations of the optical system between the DMD 36 and the exposed surface, distortion of the DMD 36 itself, micromirror placement errors, and the like.
The angular distortion appearing in the example of FIG. 10 is a distortion in which the tilt angle with respect to the scanning direction is smaller in the left column of the figure and larger in the right column of the figure. As a result of this angular distortion, the overexposed area is smaller on the exposed surface shown on the left side of the figure and larger on the exposed surface shown on the right side of the figure.

In order to reduce the density unevenness in the overlapped exposure region on the exposed surface formed by a plurality of pixel part rows as described above, a set of the slit 28 and the photodetector is used as the light spot position detecting means. The actual inclination angle θ ′ is specified for each exposure head 30, and based on the actual inclination angle θ ′, the arithmetic unit connected to the photodetector as the pixel portion selection unit is used for actual exposure. A process of selecting a micromirror to be used is performed.
The actual inclination angle θ ′ is based on at least two light spot positions detected by the light spot position detection means, and the light spot column direction on the surface to be exposed and the scanning direction of the exposure head when the exposure head is tilted. It is specified by the angle formed by.
Hereinafter, the specification of the actual inclination angle θ ′ and the used pixel selection process will be described with reference to FIGS.

-Specification of actual inclination angle θ'-
FIG. 11 is a top view showing the positional relationship between the exposure area 32 by one DMD 36 and the corresponding slit 28. The size of the slit 28 is set to sufficiently cover the width of the exposure area 32.
In the example of the present embodiment (1), the angle formed by the 512th light spot row positioned substantially at the center of the exposure area 32 and the scanning direction of the exposure head 30 is measured as the actual inclination angle θ ′. . Specifically, the micromirror 58 in the first row and the 512th column and the micromirror 58 in the 256th row and the 512th column on the DMD 36 are turned on, and the light spots on the exposure surface corresponding to each of the micromirrors 58 are turned on. The positions of P (1,512) and P (256,512) are detected, and the angle formed by the straight line connecting them and the scanning direction of the exposure head is specified as the actual inclination angle θ ′.

FIG. 12 is a top view illustrating a method for detecting the position of the light spot P (256, 512).
First, in a state where the micromirror 58 in the 256th row and the 512th column is turned on, the stage 14 is slowly moved to relatively move the slit 28 along the Y-axis direction, and the light spot P (256, 512) is changed. The slit 28 is positioned at an arbitrary position so as to be between the upstream slit 28a and the downstream slit 28b. At this time, the coordinates of the intersection of the slit 28a and the slit 28b are (X0, Y0). The value of this coordinate (X0, Y0) is determined and recorded from the movement distance of the stage 14 to the position indicated by the drive signal given to the stage 14 and the known X-direction position of the slit 28. .

  Next, the stage 14 is moved, and the slit 28 is relatively moved to the right in FIG. 12 along the Y axis. Then, as indicated by a two-dot chain line in FIG. 12, the stage 14 is stopped when the light at the light spot P (256, 512) passes through the left slit 28b and is detected by the photodetector. The coordinates (X0, Y1) of the intersection of the slit 28a and the slit 28b at this time are recorded as the position of the light spot P (256, 512).

  Next, the stage 14 is moved in the opposite direction, and the slit 28 is relatively moved to the left in FIG. 12 along the Y axis. Then, as indicated by a two-dot chain line in FIG. 12, the stage 14 is stopped when the light at the light spot P (256, 512) passes through the right slit 28a and is detected by the photodetector. The coordinates (X0, Y2) of the intersection of the slit 28a and the slit 28b at this time are recorded as the position of the light spot P (256, 512).

  From the above measurement results, the coordinates (X, Y) indicating the position of the light spot P (256, 512) on the surface to be exposed are X = X0 + (Y1-Y2) / 2, Y = (Y1 + Y2) / 2. Determine by calculation. By the same measurement, coordinates indicating the position of P (1,512) are also determined, an inclination angle formed by a straight line connecting the respective coordinates and the scanning direction of the exposure head 30 is derived, and this is obtained as an actual inclination angle θ ′. As specified.

-Selection of used pixel part-
Using the actual inclination angle θ ′ thus specified, the arithmetic unit connected to the photodetector is expressed by the following equation 4
ttanθ ′ = N (Formula 4)
The natural number T closest to the value t satisfying the above relationship is derived, and the first to T-th row micromirrors on the DMD 36 are selected as micromirrors that are actually used during the main exposure. In this way, in the exposure region near the 512th column, a micromirror that minimizes the total area of the overexposed region and the underexposed region with respect to the ideal double exposure is actually obtained. It can be selected as a micromirror to be used for.

Here, instead of deriving the natural number closest to the above value t, the minimum natural number greater than or equal to the value t may be derived. In that case, in the exposure region near the 512th column, a micromirror that minimizes the area of the overexposed region and does not produce an underexposed region with respect to ideal double exposure. It can be selected as a micromirror to be actually used.
It is also possible to derive the maximum natural number equal to or less than the value t. In that case, in the exposure region near the 512th column, a micromirror that minimizes the area of the underexposed region and does not produce an overexposed region with respect to ideal double exposure. It can be selected as a micromirror to be actually used.

FIG. 13 shows how the unevenness on the exposed surface shown in FIG. 10 is improved in the exposure performed using only the light spot generated by the micromirror selected as the micromirror to be actually used as described above. It is explanatory drawing which showed what was done.
In this example, it is assumed that T = 253 is derived as the natural number T and the micromirrors in the first row to the 253rd row are selected. For the micromirrors in the 254th to 256th rows that are not selected, the pixel part control means sends a signal to set the angle of the always-off state, and these micromirrors are substantially Not involved in exposure. As shown in FIG. 13, in the exposure region near the 512th column, overexposure and underexposure are almost completely eliminated, and uniform exposure very close to ideal double exposure is realized.

On the other hand, in the left region of FIG. 13 (near c (1) in the figure), the inclination angle of the light spot sequence on the exposed surface is near the center (near c (512) in the figure) due to the angular distortion. This is smaller than the inclination angle of the light beam row in the region. Therefore, in the exposure using only the micromirror selected based on the actual inclination angle θ ′ measured with c (512) as a reference, the ideal double pattern is used for each of the even-numbered exposure pattern and the odd-numbered exposure pattern. An area that is underexposed with respect to the exposure is slightly generated.
However, in the actual exposure pattern formed by overlaying the exposure pattern of the odd-numbered columns and the exposure pattern of the even-numbered columns shown in the figure, the regions where the exposure amount is insufficient are complemented with each other, and the exposure unevenness due to the angular distortion is double-exposed. The effect of offsetting can be minimized.

Further, in the region on the right side of FIG. 13 (near c (1024) in the figure), the inclination angle of the light beam on the exposed surface is near the center (near c (512) in the figure) due to the angular distortion. It is larger than the inclination angle of the light beam row in the region. Therefore, in the exposure with the micromirror selected based on the actual inclination angle θ ′ measured with c (512) as a reference, as shown in the figure, there is an overexposed region with respect to the ideal double exposure. It will occur slightly.
However, in the actual exposure pattern formed by superimposing the exposure pattern of the odd-numbered columns and the exposure pattern of the even-numbered columns shown in the figure, the overexposed regions are complemented with each other, and the density unevenness due to the angular distortion is caused by the double exposure. The effect of offsetting can be minimized.

In the present embodiment (1), as described above, the actual inclination angle θ ′ of the 512th ray array is measured, and based on the T derived from the equation (4) using the actual inclination angle θ ′. The micro-mirror 58 to be used is selected. However, as a method of specifying the actual inclination angle θ ′, a plurality of actual directions formed by the column direction (light spot column) of the plurality of image elements and the scanning direction of the exposure head are used. Each of the tilt angles is measured, and any one of the average value, median value, maximum value, and minimum value is specified as an actual tilt angle θ ′. It is good also as a form to select.
When the average value or the median value is set to the actual inclination angle θ ′, it is possible to realize exposure with a good balance between an overexposed area and an underexposed area with respect to an ideal N-fold exposure. For example, the total area of the overexposed region and the underexposed region is minimized, and the number of pixel units (number of light spots) in the overexposed region and the underexposed region are drawn. It is possible to realize exposure such that the number of prime units (number of light spots) is equal.
Further, if the maximum value is set to the actual inclination angle θ ′, it is possible to realize an exposure that places more importance on eliminating an overexposed region with respect to an ideal N double exposure, for example, an underexposure. It is possible to realize exposure that minimizes the area of the region and does not generate an overexposed region.
Further, if the minimum value is set to the actual inclination angle θ ′, it is possible to realize exposure that places more importance on eliminating underexposed areas with respect to ideal N-fold exposure, for example, overexposure. It is possible to realize exposure that minimizes the area of the region and does not cause a region that is underexposed.

On the other hand, the specification of the actual inclination angle θ ′ is not limited to the method based on the positions of at least two light spots in the same pixel part row (light spot row). For example, the angle obtained from the position of one or more light spots in the same pixel part sequence c (n) and the position of one or more light spots in the row near the c (n), The actual inclination angle θ ′ may be specified.
Specifically, one light spot position in c (n) and one or a plurality of light spot positions included in a light spot row on a straight line and in the vicinity along the scanning direction of the exposure head are detected. The actual inclination angle θ ′ can be obtained from the position information. Further, the angle obtained based on the positions of at least two light spots (for example, two light spots arranged so as to straddle c (n)) in the light spot array in the vicinity of the c (n) line is an actual inclination. The angle θ ′ may be specified.

  As described above, according to the specification method of the used picture element portion of the present embodiment (1) using the pattern forming apparatus 10, resolution variation and density unevenness due to the influence of the mounting angle error of each exposure head and pattern distortion are eliminated. It is possible to reduce and realize an ideal N double exposure.

(2) Method for designating used pixel parts between a plurality of exposure heads <1>
In the present embodiment (2), the pattern forming apparatus 10 performs double exposure on the photosensitive material 12 and is a head that is an overlapped exposure region on the exposed surface formed by the plurality of exposure heads 30. In the intermittent region, the variation in resolution and density unevenness due to the deviation from the ideal state of the relative position of the two exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) in the X-axis direction are reduced; A description will be given of a method for designating a used pixel portion for realizing ideal double exposure.

The set tilt angle θ of each exposure head 30, that is, each DMD 36, can be used in an ideal state where there is no mounting angle error of the exposure head 30. And the angle θ _ideal, which is exactly double exposure, is adopted.
This angle θ _ideal is obtained from the above equations 1 to 3 in the same manner as in the above embodiment (1). In the present embodiment (2), it is assumed that the pattern forming apparatus 10 is initially adjusted so that the mounting angle of each exposure head 30, that is, each DMD 36 becomes this angle θ _ideal .

FIG. 14 shows the deviation of the relative positions of the two exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) in the X-axis direction from the ideal state in the pattern forming apparatus 10 initially adjusted as described above. It is explanatory drawing which showed the example of the density nonuniformity which arises in the pattern on a to-be-exposed surface by the influence. The displacement of the relative position of each exposure head in the X-axis direction can occur because it is difficult to finely adjust the relative position between the exposure heads.

14 is projected onto the exposed surface of the photosensitive material 12 in a state where the stage 14 is stationary, the light spot group from the usable micromirror 58 of the DMD 36 of the exposure heads 30 ₁₂ and 30 _21. It is the figure which showed these patterns. The lower part of FIG. 14 shows the exposure pattern formed on the exposed surface when the stage 14 is moved and the continuous exposure is performed with the light spot group pattern as shown in the upper part appearing. The state is shown for exposure areas 32 ₁₂ and 32 ₂₁ .
In FIG. 14, for convenience of explanation, every other exposure pattern of the micromirrors 58 that can be used is divided into an exposure pattern based on the pixel column group A and an exposure pattern based on the pixel column group B. The actual exposure pattern on the exposed surface is a superposition of these two exposure patterns.

In the example of FIG. 14, the exposure pattern by the pixel column group A and the pixel column group B as a result of the deviation of the relative position between the exposure heads 30 ₁₂ and 30 ₂₁ in the X-axis direction from the ideal state. In both of the above exposure patterns, a portion where the exposure amount is larger than the ideal double exposure state occurs in the connection area between the heads in the exposure areas 32 ₁₂ and 32 ₂₁ .

In order to reduce density unevenness appearing in the inter-head connecting region formed on the exposed surface by the plurality of exposure heads as described above, in this embodiment (2), a slit is used as the light spot position detecting means. 28 and a set of photodetectors, the positions of some of the light spots constituting the connecting area between the heads formed on the exposed surface among the light spot groups from the exposure heads 30 ₁₂ and 30 _21. Detect (coordinates). Based on the position (coordinates), processing for selecting a micromirror to be used for actual exposure is performed using an arithmetic unit connected to the photodetector as the pixel portion selection means.

-Detection of position (coordinates)-
FIG. 15 is a top view showing the positional relationship between the exposure areas 32 ₁₂ and 32 ₂₁ similar to those in FIG. 14 and the corresponding slits 28. The size of the slit 28 is large enough to cover the width of the overlapping portion between the exposed areas 34 by the exposure heads 30 ₁₂ and 30 ₂₁ , that is, the slit 28 is formed on the exposed surface by the exposure heads 30 ₁₂ and 30 _21. The size is sufficient to cover the connection area between the heads.

Figure 16 is a top view for explaining a detection method of detecting the position of a point P of the exposure area _{32 21} as an example (256, 1024).
First, in a state where the micromirrors in the 256th row and the 1,024th column are turned on, the stage 14 is slowly moved to relatively move the slit 28 along the Y-axis direction, and the light spot P (256, 1024). The slit 28 is positioned at an arbitrary position such that is between the upstream slit 28a and the downstream slit 28b. At this time, the coordinates of the intersection of the slit 28a and the slit 28b are (X0, Y0). The value of this coordinate (X0, Y0) is determined and recorded from the movement distance of the stage 14 to the position indicated by the drive signal given to the stage 14 and the known X-direction position of the slit 28. .

  Next, the stage 14 is moved, and the slit 28 is relatively moved to the right in FIG. 16 along the Y axis. Then, as indicated by the two-dot chain line in FIG. 16, the stage 14 is stopped when the light at the light spot P (256, 1024) passes through the left slit 28b and is detected by the photodetector. The coordinates (X0, Y1) of the intersection of the slit 28a and the slit 28b at this time are recorded as the position of the light spot P (256, 1024).

  Next, the stage 14 is moved in the opposite direction, and the slit 28 is relatively moved to the left in FIG. 16 along the Y axis. Then, as indicated by a two-dot chain line in FIG. 16, the stage 14 is stopped when the light at the light spot P (256, 1024) passes through the right slit 28a and is detected by the photodetector. The coordinates (X0, Y2) of the intersection of the slit 28a and the slit 28b at this time are recorded as the light spot P (256, 1024).

  From the above measurement results, the coordinates (X, Y) indicating the position of the light spot P (256, 1024) on the exposed surface are calculated as X = X0 + (Y1−Y2) / 2, Y = (Y1 + Y2) / 2. Determined by

-Identification of unused pixel parts-
In the example of FIG. 14, first, the position of the point P of the exposure area _{32 12} (256,1) is detected by a set of slits 28 and a photodetector as the light spot position detecting unit. Subsequently, the position of each light spot on the 256 line of light spots row r of the exposure area _{32 21 (256), P (} 256,1024), to detect the P (256,1023) ··· and order periodically, where the exposure area _{32 21} of point P indicating the exposure area _{32 12} point P (256,1) larger X coordinate than the (256, n) is detected, and terminates the detecting operation. Then, the micro mirrors corresponding to light spots constituting the c (1024) from the light spot column c of the exposure area 32 ₂₁ (n + 1), specifies as a micro-mirror is not used during the exposure (unused pixel parts).
For example, in FIG. 14, the exposure area _{32 21} point P (256,1020) is shows a larger X coordinate than the point P of the exposure area _{32 12} (256,1) of the exposure area _{32 21} spot configuration When P (256,1020) is that the detection operation at the detected ended, the first 1,024 rows from a 1,021 line of exposure area _{32 21,} corresponding to the portion 70 covered with hatched in FIG. 17 The micromirror corresponding to the light spot to be used is specified as a micromirror that is not used during the main exposure.

Next, the number N of the N multiple exposure, the position of the point P of the exposure area _{32 12} (256, N) is detected. In this embodiment (2), since N = 2, the position of the light spot P (256, 2) is detected.
Then, among the light spot columns of the exposure area 32 _21, except those identified as light spots string corresponding to the micromirrors is not used during the exposure in the above, the position of the light spot constituting the rightmost 1020 column a, P (1,1020) in order from P (1,1020), P (2,1020 ) ··· and continue to detection, greater than the point P of the exposure area _{32 12} (256,2) X When the light spot P (m, 1020) indicating the coordinates is detected, the detection operation is terminated.
Thereafter, the connected operational devices to said light detector, and X-coordinate of the exposure area _{32 12} of the light spot P (256, two), point P of the exposure area _{32 21} (m, 1020) and P (m- and X-coordinate of 1,1020) are compared, if the direction of the X coordinate of the point P of the exposure area _{32 21} (m, 1020) is closer to the X coordinate of the point P in the exposure area _{32 12} (256, 2) a micro mirror corresponding to P (m-1,1020) from point P of the exposure area _{32 21} (1,1020) is identified as a micro-mirror is not used during the exposure.
Also, if the direction of the X coordinate of the point P of the exposure area _{32 21} (m-1,1020) is close to the X-coordinate of the point P in the exposure area _{32 12} (256, 2), the light of the exposure area _{32 21} Micromirrors corresponding to points P (1, 1020) to P (m−2, 1020) are specified as micromirrors that are not used for the main exposure.
Furthermore, the position of the point P of the exposure area _{32 12 (256, N-1} ) That point P (256,1), the position of each point constituting the first 1019 column is the next row of the exposure area _{32 21} The same detection process and identification of micromirrors that are not used are also performed.

  As a result, for example, micromirrors corresponding to the light spots that form the shaded area 72 in FIG. 17 are added as micromirrors that are not used during actual exposure. These micromirrors are always signaled to set the micromirror angle to the off-state angle, and these micromirrors are substantially not used for exposure.

As described above, the micromirrors that are not used at the time of actual exposure are identified, and the micromirrors that are not used at the time of actual exposure are selected as the micromirrors that are used at the time of actual exposure, whereby the exposure areas 32 ₁₂ and 32 ₂₁ In the connecting area between the heads, the total area of the overexposed area and the underexposed area with respect to the ideal double exposure can be minimized. As shown in the lower part of FIG. Uniform exposure extremely close to double exposure can be realized.

In the above example, upon the particular light spots constituting the regions 72 covered with hatched in FIG. 17, the X coordinate of the point P in the exposure area _{32 12} (256, 2), the exposure area _{32 21} of the light spot P (m, 1020) and P (m-1,1020) without comparison of the X-coordinate of the immediately, P from point P of the exposure area _{32 21 (1,1020) (m-} 2 , 1020) may be specified as a micromirror that is not used during the main exposure. In that case, in the connecting area between the heads, a micromirror is actually used that minimizes the area of an overexposed area with respect to an ideal double exposure and does not cause an underexposed area. It can be selected as a micromirror.
Further, the micro-mirrors corresponding to P (m-1,1020) from point P of the exposure area _{32 21} (1,1020), it may be specified as micro mirrors not used in this exposure. In that case, in the connecting region between the heads, a micromirror is actually used in which the area of the region that is underexposed with respect to the ideal double exposure is minimized and the region that is not overexposed does not occur. It can be selected as a micromirror.
Further, in the connecting area between the heads, the number of pixel units (the number of light spots) in an area that is overexposed with respect to an ideal double drawing and the number of pixel units (the number of light spots) in an area that is underexposed. It is good also as selecting the micromirror actually used so that it may become equal.

  As described above, according to the specification method of the used pixel part of the present embodiment (2) using the pattern forming apparatus 10, the resolution variation caused by the relative position shift in the X-axis direction of the plurality of exposure heads Density unevenness can be reduced, and ideal N-fold exposure can be realized.

(3) Specification method of used pixel parts between a plurality of exposure heads <2>
In this embodiment (3), the pattern forming apparatus 10 performs double exposure on the photosensitive material 12 and is a head that is an overlapped exposure region on the exposed surface formed by a plurality of exposure heads 30. In the intermittent region, the deviation of the relative positions of the two exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) in the X-axis direction from the ideal state, the mounting angle error of each exposure head, and the two exposure heads A description will be given of a method for designating a used pixel part for reducing the variation in resolution and density unevenness caused by the relative mounting angle error between them and realizing ideal double exposure.

The set tilt angle of each exposure head 30, that is, each DMD 36, can be used in an ideal state where there is no mounting angle error of the exposure head 30. ) Is used, and an angle slightly larger than the angle θ _ideal that is exactly double exposure is adopted.
This angle θ _ideal is a value obtained in the same manner as the above embodiment (1) using the above equations 1 to 3, and in this embodiment, s = 256 and N = 2 as described above. The angle θ _ideal is about 0.45 degrees. Therefore, for example, an angle of about 0.50 degrees may be employed as the set inclination angle θ. It is assumed that the pattern forming apparatus 10 is initially adjusted so that the mounting angle of each exposure head 30, that is, each DMD 36 is close to the set inclination angle θ within an adjustable range.

FIG. 18 shows a mounting angle error of two exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) in the pattern forming apparatus 10 in which the mounting angle of each exposure head 30, that is, each DMD 36 is initially adjusted as described above, the influence of the deviation of the relative mounting angle error and the relative position between the exposure heads 30 ₁₂ and 30 ₂₁ is an explanatory view showing an example of unevenness that occurs in the pattern on the exposed surface.

In the example of FIG. 18, as in the example of FIG. 14, as a result of the shift of the relative positions of the exposure heads 30 ₁₂ and 30 _{21 in} the X-axis direction, exposure by every other light spot group (pixel column groups A and B) is performed. In both exposure patterns 32 ₁₂ and 32 ₂₁ , the exposure amount overlaps on the coordinate axis perpendicular to the scanning direction of the exposure head on the exposed surface of the exposure areas 32 ₁₂ and 32 ₂₁ , which is more than the ideal double exposure state. A region 74 is generated, which causes uneven density.
Furthermore, in the example of FIG. 18, it is difficult to finely adjust the result of setting the tilt angle θ of each exposure head to be slightly larger than the angle θ _ideal satisfying the formula (1) and the mounting angle of each exposure head. Therefore, as a result of the actual mounting angle deviating from the set inclination angle θ, even in regions other than the exposure region overlapping on the coordinate axis perpendicular to the scanning direction of the exposure head on the exposed surface, In the connection region between the pixel part columns, which is an overlapped exposure region on the exposed surface, formed by a plurality of pixel part columns, both in the exposure pattern by every other light spot group (pixel column group A and B). A region 76 that is overexposed than the ideal double exposure state is generated, and this causes further density unevenness.

In this embodiment (3), first, the use pixel selection process for reducing the uneven density due to the influence of the deviation of the mounting angle error and relative mounting angle of the exposure heads 30 ₁₂ and 30 _21.
Specifically, a set of a slit 28 and a photodetector is used as the light spot position detecting means, and an actual inclination angle θ ′ is specified for each of the exposure heads 30 ₁₂ and 30 ₂₁ , and the actual inclination angle θ ′ is set. Based on this, it is assumed that processing for selecting a micromirror to be used for actual exposure is performed using an arithmetic unit connected to a photodetector as the pixel part selection means.

-Specification of actual inclination angle θ'-
The actual inclination angle θ ′ is specified with respect to the positions of the light spots P (1, 1) and P (256, 1) in the exposure area 32 ₁₂ for the exposure head 30 _{12 and in the} exposure area 32 ₂₁ for the exposure head 30 ₂₁ . The positions of the light spots P (1,1024) and P (256,1024) are detected by the combination of the slit 28 and the photodetector used in the above-described embodiment (2), and the inclination angle of the straight line connecting them. And the angle formed by the scanning direction of the exposure head.

-Identification of unused pixel parts-
The arithmetic device connected to the photodetector using the actual inclination angle θ ′ thus specified is similar to the following equation 4 similar to the arithmetic device in the embodiment (1) described above.
ttanθ ′ = N (Formula 4)
The natural number T closest to the value t satisfying the above relationship is derived for each of the exposure heads 30 ₁₂ and 30 ₂₁ , and the micromirrors in the (T + 1) th to 256th rows on the DMD 36 are not used for the main exposure. Processing to identify as a micromirror is performed.
For example, T = 254 for the exposure head _{30 12,} when T = 255 was derived for the exposure head _3O21, micro mirrors corresponding to light spots constituting the parts 78 and 80 covered with hatched in FIG. 19 These are specified as micromirrors that are not used for the main exposure. As a result, in each of the exposure areas 32 ₁₂ and 32 ₂₁ other than the head-to-head connection area, the total area of the overexposed area and the underexposed area with respect to the ideal double exposure is minimized. be able to.

Here, instead of deriving the natural number closest to the above value t, the minimum natural number greater than or equal to the value t may be derived. In this case, exposure is performed for ideal double exposure in each of the exposure areas 32 ₁₂ and 32 ₂₁ other than the head-to-head connection area, which is an overlapping exposure area on the exposed surface formed by a plurality of exposure heads. It is possible to minimize the area where the amount is excessive and to prevent an area where the exposure amount is insufficient.
Or it is good also as deriving the maximum natural number below value t. In this case, exposure is performed for ideal double exposure in each of the exposure areas 32 ₁₂ and 32 ₂₁ other than the head-to-head connection area, which is an overlapping exposure area on the exposed surface formed by a plurality of exposure heads. It is possible to minimize the area of the insufficient region and prevent the region from being overexposed.
In each area other than the head-to-head connection area, which is an overlapping exposure area on the exposed surface formed by a plurality of exposure heads, the number of pixel units (light It is also possible to identify micromirrors that are not used during the main exposure so that the number of pixel units (the number of light points) in the underexposed region is equal to the number of points.

Thereafter, with respect to the micromirrors corresponding to the light spots other than the light spots constituting the regions 78 and 80 covered with diagonal lines in FIG. 19, the same processing as that of the present embodiment (3) described with reference to FIGS. In FIG. 19, the micromirrors corresponding to the light spots constituting the shaded area 82 and the shaded area 84 are identified and added as micromirrors that are not used during the main exposure.
With respect to the micromirrors that are specified not to be used at the time of exposure, a signal for setting the angle of the always-off state is sent by the pixel element control means, and these micromirrors are substantially exposed. Not involved.

  As described above, according to the method for designating the used picture element portion of the present embodiment (3) using the pattern forming apparatus 10, the relative position shift in the X-axis direction of the plurality of exposure heads and the attachment of each exposure head Variations in resolution and density unevenness due to angle errors and relative mounting angle errors between exposure heads can be reduced, and ideal N-fold exposure can be realized.

  As described above, the method for designating the used pixel portion by the pattern forming apparatus 10 has been described in detail. However, the above-described embodiments (1) to (3) are merely examples, and various modifications can be made without departing from the scope of the present invention. It is.

  In the above embodiments (1) to (3), as a means for detecting the position of the light spot on the exposed surface, a set of the slit 28 and the single cell type photodetector is used. The present invention is not limited to this, and any form may be used. For example, a two-dimensional detector may be used.

  Further, in the above embodiments (1) to (3), the actual inclination angle θ ′ is obtained from the position detection result of the light spot on the exposed surface by the combination of the slit 28 and the photodetector, and the actual inclination angle θ ′ is obtained. The micromirrors to be used are selected based on the above, but a usable micromirror may be selected without the derivation of the actual inclination angle θ ′. Furthermore, for example, the reference exposure using all available micromirrors is performed, and the micromirror used by the operator is manually specified by checking the resolution and density unevenness by visual observation of the reference exposure results. It is included in the scope of the invention.

In addition to the angular distortion described in the above example, there are various forms of pattern distortion that can occur on the exposed surface.
As an example, as shown in FIG. 20A, there is a form of magnification distortion in which light rays from each micromirror 58 on the DMD 36 reach the exposure area 32 on the exposure surface at different magnifications.
As another example, as shown in FIG. 20B, there is a form of beam diameter distortion in which the light from each micromirror 58 on the DMD 36 reaches the exposure area 32 on the exposed surface with a different beam diameter. . These magnification distortion and beam diameter distortion are mainly caused by various aberrations and alignment deviation of the optical system between the DMD 36 and the exposed surface.
As yet another example, there is a form of light amount distortion in which light beams from the micromirrors 58 on the DMD 36 reach the exposure area 32 on the exposed surface with different light amounts. In addition to various aberrations and misalignment, this light amount distortion includes the positional dependency of the transmittance of the optical element between the DMD 36 and the exposed surface (for example, the lenses 52 and 54 in FIG. Caused by unevenness. These forms of pattern distortion also cause unevenness in resolution and density in the pattern formed on the exposed surface.

  According to the above embodiments (1) to (3), the residual elements of pattern distortion in these forms after selecting the micromirrors actually used for the main exposure are the same as the residual elements of angular distortion described above. It is possible to level out by the effect of filling by multiple exposure, and the unevenness of resolution and density can be reduced over the entire exposure area of each exposure head.

<< Reference exposure >>
As a modified example of the above embodiments (1) to (3), among available micromirrors, it corresponds to (N-1) every micromirror column or 1 / N rows of all light spot rows. A reference exposure is performed using only a group of micromirrors constituting an adjacent row, and among the micromirrors used for the reference exposure, micromirrors that are not used at the time of actual exposure are specified so that uniform exposure can be realized. It is good as well.
The result of the reference exposure by the reference exposure means is output as a sample, and the output reference exposure result is analyzed to confirm resolution variation and density unevenness and to estimate the actual inclination angle. The analysis of the result of the reference exposure may be a visual analysis by an operator.

FIG. 21 is an explanatory diagram showing an example of a form in which reference exposure is performed using only (N-1) rows of micromirrors using a single exposure head.
In this example, it is assumed that double exposure is performed during main exposure, and therefore N = 2. First, reference exposure is performed using only the micromirrors corresponding to the odd-numbered light spot arrays indicated by the solid lines in FIG. 21A, and the reference exposure results are output as samples. Based on the reference exposure result outputted from the sample, it is possible to specify a micromirror to be used in the main exposure by confirming variations in resolution and density unevenness, or estimating an actual inclination angle.
For example, micromirrors other than the micromirror corresponding to the light spot array shown by hatching in FIG. 21B are designated as actually used in the main exposure among the micromirrors constituting the odd light spot array. . For even-numbered light spot arrays, reference exposure may be performed separately in the same manner, and the micromirror used during the main exposure may be designated, or the same pattern as that for the odd-numbered light spot arrays may be applied. Good.
By specifying the micromirrors used in the main exposure as described above, in the main exposure using both the odd-numbered and even-numbered micromirrors, a state close to ideal double exposure can be realized.

FIG. 22 is an explanatory diagram showing an example of a form in which reference exposure is performed using only a plurality of (N-1) rows of micromirrors using a plurality of exposure heads.
In this example, it is assumed that double exposure is performed during main exposure, and therefore N = 2. First, reference is made using only the micromirrors corresponding to the odd-numbered light spot rows of two exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) adjacent to each other in the X-axis direction, which are indicated by solid lines in FIG. Exposure is performed, and a reference exposure result is output as a sample. Based on the output reference exposure result, the variation in resolution and density unevenness in the area other than the joint area between the heads formed on the exposed surface by the two exposure heads are confirmed, or the actual inclination angle is estimated. Thus, the micromirror to be used at the time of the main exposure can be designated.
For example, the micromirrors other than the micromirrors corresponding to the light spot rows in the area 86 shown by hatching in FIG. 22 and the shaded area 88 are among the micromirrors constituting the odd-numbered light spots, during the main exposure. Specified as actually used. For even-numbered light spot arrays, reference exposure may be performed separately in the same manner, and a micromirror used in the main exposure may be designated, or the same pattern as that for the odd-numbered pixel columns may be applied. Good.
In this way, in the main exposure using both the odd-numbered and even-numbered micromirrors by designating the micromirrors that are actually used during the main exposure, the two exposure heads form the surface to be exposed. A state close to ideal double exposure can be realized in a region other than the head-to-head connection region.

FIG. 23 is an explanatory diagram showing an example of a form in which reference exposure is performed using a single exposure head and using only micromirror groups constituting adjacent rows corresponding to 1 / N rows of the total light spot rows. It is.
In this example, it is assumed that double exposure is performed during main exposure, and therefore N = 2. First, reference exposure is performed using only micromirrors corresponding to the light spots in the first to 128 (= 256/2) rows indicated by the solid line in FIG. 23A, and the reference exposure results are output as samples. Based on the reference exposure result outputted from the sample, a micromirror to be used in the main exposure can be designated.
For example, a micromirror other than the micromirror corresponding to the light spot group indicated by hatching in FIG. 23B is designated as actually used in the main exposure among the micromirrors in the first to 128th rows. Can be done. For the micromirrors in the 129th to 256th rows, reference exposure may be separately performed in the same manner, and the micromirrors used in the main exposure may be designated, or the micromirrors in the first to 128th rows may be designated. The same pattern as that for the mirror may be applied.
By designating the micromirror to be used at the time of the main exposure in this way, a state close to an ideal double exposure can be realized in the main exposure using the entire micromirror.

FIG. 24 uses a plurality of exposure heads, and two adjacent exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) adjacent to each other in the X-axis direction are adjacent to each other corresponding to 1 / N rows of the total number of light spots. It is explanatory drawing which showed an example of the form which performs reference exposure using only the micromirror group which comprises a line.
In this example, it is assumed that double exposure is performed during main exposure, and therefore N = 2. First, reference exposure is performed using only the micromirrors corresponding to the light spots in the first to 128th (= 256/2) rows indicated by solid lines in FIG. 24, and the reference exposure results are output as samples. . Based on the reference exposure result outputted from the sample, it is possible to realize the main exposure in which the variation in resolution and the density unevenness in the region other than the joint region between the heads formed on the exposed surface by the two exposure heads are minimized. In addition, it is possible to designate a micromirror to be used during the main exposure.
For example, micromirrors other than the micromirrors corresponding to the light spot arrays in the region 90 shown by hatching in FIG. 24 and the region 92 shown by shading are included in the micromirrors in the first to 128th rows. Designated as actually used at the time of exposure. For the micromirrors in the 129th to 256th rows, reference exposure may be separately performed in the same manner, and the micromirrors used for the main exposure may be designated, or the micromirrors in the first to 128th rows may be designated. The same pattern as that for the mirror may be applied.
In this way, by specifying the micromirror to be used during the main exposure, a state close to ideal double exposure is realized in an area other than the inter-head connecting area formed on the exposed surface by two exposure heads. it can.

  In the above embodiments (1) to (3) and the modified examples, the case where the main exposure is the double exposure has been described. However, the present invention is not limited to this, and any multiple exposure more than the double exposure may be used. . In particular, by setting the exposure to about 3 to 7 exposures, high resolution can be secured, and exposure with reduced variations in resolution and density unevenness can be realized.

  Further, in the exposure apparatus according to the embodiment and the modified example, the dimension of the predetermined part of the two-dimensional pattern represented by the image data is matched with the dimension of the corresponding part that can be realized by the selected use pixel. A mechanism for converting image data is preferably provided. By converting the image data in this way, a high-definition pattern according to a desired two-dimensional pattern can be formed on the exposed surface.

<Development process>
The developing step is a step of forming a pattern by exposing the photosensitive layer by the exposing step, curing the exposed region of the photosensitive layer, and then developing the uncured region 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. For example, alkali metal or alkaline earth metal hydroxide or carbonate, hydrogen carbonate, aqueous ammonia, quaternary ammonium salt An aqueous solution of Among these, an aqueous sodium carbonate solution is particularly preferable.

  Examples of the developer include a surfactant, an antifoaming agent, an organic base (for example, benzylamine, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.) In order to accelerate development, an organic solvent (for example, alcohols, ketones, esters, ethers, amides, lactones, etc.) may be used in combination. 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 further includes a heat treatment as a curing treatment step, and further includes a whole surface exposure treatment as necessary.
The curing treatment step is a step of performing a curing treatment on the photosensitive layer in the formed pattern after the development step is performed.
-Heat treatment-
The heat treatment is performed in order to sufficiently improve the film hardness due to the thermal crosslinking effect of the thermal crosslinking agent having a softening point or melting point of 50 to 250 ° C. contained in the photosensitive composition of the present invention. The heat treatment may be a whole surface heat treatment or may be a heat treatment performed in a pattern, and among these, the whole surface heat treatment is preferable.
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. The entire surface heating promotes the crosslinking reaction of the thermal crosslinking agent having a softening point or melting point of 50 to 250 ° C., and increases the film strength of the surface of the permanent pattern.
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 crosslinking reactivity of the resin in the photosensitive composition by the thermal crosslinking agent having the softening point or melting point of 50 to 250 ° C. is lowered, and the film strength is improved by the heat treatment. If it exceeds 250 ° C., the resin in the photosensitive composition may be decomposed, and the film quality may be weak and brittle.
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.

-Full exposure process-
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.

When the substrate is a printed wiring board such as a multilayer wiring board, the pattern of the present invention can be formed on the printed wiring board, and further soldered as follows.
That is, the hardened layer which is the said pattern is formed by the said image development process, and a metal layer is exposed to the surface of the said printed wiring board. Gold plating is performed on the portion of the metal layer exposed on the surface of the printed wiring board, and then soldering is performed. Then, a semiconductor or a component is mounted on the soldered portion. At this time, the pattern of the hardened layer exhibits a function as a protective film or an insulating film (interlayer insulating film), and an external impact and conduction between adjacent electrodes are prevented.

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

  By using the photosensitive film of the present invention, the permanent pattern forming method of the present invention does not react at low temperature or normal temperature during storage, has excellent storage stability, has low surface tackiness, and forms a film. Good laminating and handling properties, excellent peelability from protective film and support, high sensitivity and excellent developability, excellent chemical resistance, surface hardness, heat resistance, dielectric properties after development In addition, since electrical insulation and the like can be obtained, and the pattern can be formed with high definition and efficiency, it can be suitably used for forming various patterns that require high-definition exposure. It can be suitably used for forming high-definition patterns such as protective films, interlayer insulating films, and solder resist patterns.

  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 was prepared based on the following composition. Note that methyl ethyl ketone was used as a dispersion solvent, and the solid content concentration was adjusted to 55% by mass. Dispersion was performed using a bead mill, and the obtained dispersion was confirmed to be free from aggregation by a particle gauge.
[Composition of photosensitive composition solution]
Barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., B30) 33.4 parts by mass Binder represented by the following structural formula (46) 40.0 parts by mass Epoxy resin compound represented by the structural formula (i) (heat Crosslinking agent) 15.7 parts by mass, dipentaerythritol hexaacrylate 16.0 parts by mass, IRGACURE 819 (manufactured by Ciba Specialty Chemicals) 5.8 parts by mass, hydroquinone monomethyl ether 0.056 parts by mass, dicyandiamide 0.77 parts by mass Part
2MAOK ^{* 1} 0.47 parts by mass * 1: 2MAOK is 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s- represented by the following structural formula (47) It is an isocyanuric acid adduct of triazine (manufactured by Shikoku Kasei Kogyo Co., Ltd.).

-Synthesis of epoxy resin compound represented by structural formula (i)-
The epoxy resin compound represented by the structural formula (i) was synthesized as follows.
5 parts by mass of 4,4′-thiodiphenol and 13.6 parts by mass of methyl epichlorohydrin were placed in a reaction kettle and heated to 80 ° C. An aqueous solution of 4.2 parts by mass of 48% NaOH aqueous solution and 4 parts by mass of water was dropped into the reaction kettle over 2 hours. Thereafter, the reaction was allowed to proceed for 10 hours. After allowing to cool, the reaction product was extracted with 100 parts by mass of ethyl acetate, separated with saturated brine, and the organic phase was dried over magnesium sulfate. The solvent of the organic phase was distilled off, and the residue was purified by silica gel chromatography (developing solvent: hexane / ethyl acetate = 7/3) to obtain 2.8 parts by mass (yield 34%) of an oily substance.
The product was identified by ¹ H-NMR (300 MHz: CDCl ₃ ). Each peak of the spectrum is 7.27 (d, 4H), 6.85 (d, 4H), 3.97 (q, 4H), 2.86 (d, 2H), 2.74 (d, 2H). , 1.48 (s, 6H).
Moreover, content in the photosensitive composition of the thermal crosslinking agent represented by the said structural formula (i) is 14 mass%, and melting | fusing point is 58-60 degreeC.

-Production of photosensitive film-
The obtained photosensitive composition 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 30 μm. Next, a 12 μm-thick polypropylene film was laminated as a protective film on the photosensitive layer to produce a photosensitive film.

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

<Evaluation of tackiness>
The tackiness of the surface of the photosensitive layer in the laminate obtained as described above was evaluated based on the following criteria. The results are shown in Table 3.
〔Evaluation methods〕
A sample cut out from the laminate to a width of 4.5 cm and a length of 8 cm was fixed on a pedestal so that the support was on the surface side, and the support was pulled from the sample at a rate of 160 cm / min. Peeled off in the direction. At that time, the peeling force per 4.5 cm length of the sample between the photosensitive layer and the support was measured, and the tack of the photosensitive layer after peeling was visually observed.
〔Evaluation criteria〕
A: The peel force was 1 g or more and 40 g or less, and no strong tackiness was observed on the surface of the photosensitive layer.
(Triangle | delta): Peeling force was more than 40g and 100g or less, and the tackiness was recognized for the surface of the photosensitive layer a little.
X: The peeling force was more than 100 g, and strong tackiness was recognized on the surface of the photosensitive layer.

--Exposure process--
Irradiate the photosensitive layer in the prepared laminate from the polyethylene terephthalate film (support) side with a laser exposure device so as to obtain a pattern in which holes having different diameters are formed. 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. Then, shower development was performed at a spray pressure of 0.2 MPa and 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 manufactured photosensitive film was evaluated for exposure sensitivity, resolution, exposure speed, and storage stability, and the formed permanent pattern was evaluated for pencil hardness and dielectric properties. 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 required for curing the photosensitive layer was 30 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 resolution was 70 μm.

<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 prepared 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.

<Storage stability>
After the forced aging of the produced photosensitive film at 40 ° C. for 3 days, the development time of the unexposed film was measured, and the storage stability was evaluated based on the following criteria.
〔Evaluation criteria〕
A: Development time is within 30 seconds, and storage stability is extremely excellent.
○: The development time is more than 30 seconds and within 45 seconds, and the storage stability is excellent.
Δ: Development time exceeds 45 seconds and within 60 seconds, and storage stability is poor.
X: The development time exceeds 60 seconds, and the storage stability is extremely poor.

<Pencil hardness>
The printed wiring board on which the permanent pattern had been formed was subjected to gold plating according to a conventional method and then subjected to a water-soluble flux treatment. Subsequently, it was immersed three times in a solder bath set at 260 ° C. for 5 seconds, and the flux was removed by washing with water. And the pencil hardness was measured about the permanent pattern after this flux removal based on JISK-5400.
As a result, the pencil hardness was 5H. Further, when visually observed, no peeling, blistering, or discoloration of the cured film in the permanent pattern was observed.

<Measurement of dielectric properties>
The dielectric properties of the cured film having a thickness of 500 μm were measured at 25 ° C. using an LCR meter manufactured by Agilent Technologies and a 4291A type solid electrode. As a result, the dielectric constant at 1 GHz was 3.3 and the dielectric loss tangent was 0.3. 012.

(Example 2)
A photosensitive composition was prepared based on the following composition, and a photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern.
Further, the tackiness, exposure sensitivity, resolution, exposure speed, and storage stability of the photosensitive composition and photosensitive film produced in the same manner as in Example 1 were evaluated, and the pencil hardness of the formed permanent pattern was evaluated. And dielectric properties were evaluated. As a result, the exposure sensitivity was 30 mJ / cm ² , the resolution was 70 μm, and the exposure speed was 13 mm / sec. Other results are shown in Table 3.
[Composition of photosensitive composition solution]
-33.4 parts by mass of barium sulfate-Styrene / maleic anhydride / butyl acrylate copolymer (molar ratio 40/32/28)
Reaction product of benzylamine and benzylamine (1.0 equivalent to the anhydride group of the copolymer) ^{* 2}
40.0 parts by mass-Thermal crosslinking agent represented by the structural formula (i) 15.7 parts by mass-Dipentaerythritol hexaacrylate 16.0 parts by mass-IRGACURE 819 (manufactured by Ciba Specialty Chemicals) 5.8 parts by mass Parts ・ Hydroquinone monomethyl ether 0.056 parts by mass ・ Dicyandiamide 0.77 parts by mass
-2MAOK 0.47 mass part * 2: It is a maleamic acid type copolymer which has the unit A and the unit B which are represented by following structural formula (VII). The unit A consists of two structural units, R ¹ in one of the structural units of which are phenyl, R ¹ in the other structural units are butyloxycarbonyl, R ³ and R ⁴ are hydrogen atoms. R ² in unit B is benzyl. The mole fraction x of the repeating unit in the unit A is 40 mol% for the one constituent unit, and 28 mol% for the other constituent unit, and the mole fraction y of the repeating unit in the unit B is Is 32 mol%. The reaction amount of the benzylamine with respect to the anhydride group of the styrene / maleic anhydride / butyl acrylate copolymer is 1.0 equivalent.
The glass transition temperature (Tg) of the homopolymer of butyl acrylate which is the vinyl monomer is -54 ° C.
In Example 2, the content of the thermal crosslinking agent represented by the structural formula (i) in the photosensitive composition is 14% by mass.

(Example 3)
In Example 1, the addition amount of the thermal crosslinking agent represented by the structural formula (i) in the photosensitive composition is 0.8 parts by mass, and the photosensitivity of the thermal crosslinking agent represented by the structural formula (i). A photosensitive composition was prepared in the same manner as in Example 1 except that the content in the composition was 0.8% by mass (less than 1% by mass). A laminate was prepared to form a permanent pattern.
Moreover, tackiness, exposure sensitivity, resolution, exposure speed, and storage stability were evaluated for the produced photosensitive film in the same manner as in Example 1, and pencil hardness and dielectric properties of the formed permanent pattern were evaluated. Evaluation was performed. As a result, the exposure sensitivity was 30 mJ / cm ² , the resolution was 70 μm, and the exposure speed was 13 mm / sec. Other results are shown in Table 3.

Example 4
In Example 1, the addition amount of the thermal crosslinking agent represented by the structural formula (i) in the photosensitive composition is 100 parts by mass, and the photosensitive composition of the thermal crosslinking agent represented by the structural formula (i) is used. A photosensitive composition was prepared in the same manner as in Example 1 except that the content was 51% by mass (over 50% by mass), and a photosensitive film and a laminate were prepared in the same manner as in Example 1. Then, a permanent pattern was formed.
Moreover, tackiness, exposure sensitivity, resolution, exposure speed, and storage stability were evaluated for the produced photosensitive film in the same manner as in Example 1, and pencil hardness and dielectric properties of the formed permanent pattern were evaluated. Evaluation was performed. As a result, the exposure sensitivity was 30 mJ / cm ² , the resolution was 70 μm, and the exposure speed was 13 mm / sec. Other results are shown in Table 3.

(Examples 5 to 11)
In Example 1, the thermal crosslinking agent represented by the structural formula (i) in the photosensitive composition is changed to the thermal crosslinking agent represented by the structural formulas (ii) to (viii) as shown in Table 3. Except having changed, the photosensitive composition was prepared like Example 1, the photosensitive film and the laminated body were prepared like Example 1, and the permanent pattern was formed.
Moreover, tackiness, exposure sensitivity, resolution, exposure speed, and storage stability were evaluated for the produced photosensitive film in the same manner as in Example 1, and pencil hardness and dielectric properties of the formed permanent pattern were evaluated. Evaluation was performed. As a result, in Examples 5 to 11, the exposure sensitivity was 30 mJ / cm ² , the resolution was 70 μm, and the exposure speed was 13 mm / sec. The other results of each example are shown in Table 3.
The thermal crosslinking agent represented by the structural formulas (ii) to (viii) was synthesized as follows.

-Synthesis of epoxy resin compound represented by structural formula (ii)-
5 parts by mass of 1,1′-biphenyl-4,4′-diol and 16 parts by mass of methyl epichlorohydrin were placed in a reaction kettle and heated to 80 ° C. An aqueous solution of 4.2 parts by mass of 48% NaOH aqueous solution and 4 parts by mass of water was dropped into the reaction kettle over 2 hours. Thereafter, the reaction was allowed to proceed for 10 hours. After standing to cool, it was put in 50 parts by mass of water to obtain a precipitate. The precipitate was filtered and washed with 100 parts by mass of a hexane / ethyl acetate = 1/1 solution to obtain 6.3 parts by mass (yield 72%) of a white solid. The melting point of the white solid, that is, the thermal crosslinking agent represented by the structural formula (ii) was 190 to 193 ° C.
The product was identified by ¹ H-NMR (300 MHz: CDCl ₃ ). Each peak of the spectrum is 7.48 (d, 4H), 7.00 (d, 4H), 4.05 (q, 6H), 2.91 (d, 2H), 2.77 (d, 2H). 1.52 (s, 6H).

-Synthesis of epoxy resin compound represented by structural formula (iii)-
5 parts by mass of 1,1,1-tris (4-hydroxyphenyl) ethane and 14.6 parts by mass of methyl epichlorohydrin were placed in a reaction kettle and heated to 80 ° C. An aqueous solution of 4.5 parts by mass of 48% NaOH aqueous solution and 4.5 parts by mass of water was dropped into the reaction kettle over 2 hours. Thereafter, the reaction was allowed to proceed for 10 hours. After allowing to cool, the reaction product was extracted with 100 parts by mass of ethyl acetate, separated with saturated brine, and the organic phase was dried over magnesium sulfate. The solvent of the organic phase was distilled off and purified by silica gel chromatography (developing solvent: hexane / ethyl acetate = 1/1) to obtain 3.4 parts by mass (yield 40%) of a white solid. The melting point of the white solid, that is, the thermal crosslinking agent represented by the structural formula (iii) was 126-128 ° C.
The product was identified by ¹ H-NMR (300 MHz: CDCl ₃ ). Each peak of the spectrum is 6.97 (d, 6H), 6.79 (d, 6H), 3.96 (q, 6H), 2.86 (d, 3H), 2.73 (d, 3H). , 2.19 (s, 3H), 1.48 (s, 9H).

-Synthesis of epoxy resin compound represented by structural formula (iv)-
3,3 ′, 5,5′-tetramethyl (1,1′-biphenyl) -4,4′-diol (5 parts by mass) and methyl epichlorohydrin (12.3 parts by mass) were placed in a reaction kettle and brought to 80 ° C. Heated. An aqueous solution of 3.8 parts by mass of 48% NaOH aqueous solution and 4 parts by mass of water was dropped into the reaction kettle over 2 hours. Thereafter, the reaction was allowed to proceed for 10 hours. After allowing to cool, the reaction product was extracted with 100 parts by mass of ethyl acetate, separated with saturated brine, and the organic phase was dried over magnesium sulfate. The solvent of the organic phase was distilled off, and the precipitated solid was recrystallized from methanol to obtain 1.6 parts by mass (yield 20%) of a brown solid. The melting point of the brown solid, that is, the thermal crosslinking agent represented by the structural formula (iv) was 122 to 125 ° C.
The product was identified by ¹ H-NMR (300 MHz: CDCl ₃ ). Each peak of the spectrum is 7.17 (s, 4H), 3.80 (q, 4H), 2.89 (d, 2H), 2.75 (d, 2H), 2.33 (s, 12H). , 1.58 (s, 6H).

-Synthesis of epoxy resin compound represented by structural formula (v)-
5 masses of 4,4′-dihydroxyphenyl ether and 14.8 mass parts of methyl epichlorohydrin were placed in a reaction kettle and heated to 80 ° C. An aqueous solution of 4.5 parts by mass of 48% NaOH solution and 5 parts by mass of water was dropped into the reaction kettle over 2 hours. Thereafter, the reaction was allowed to proceed for 10 hours. After allowing to cool, the reaction product was extracted with 100 parts by mass of ethyl acetate, separated with saturated brine, and the organic phase was dried over magnesium sulfate. The solvent of the organic phase was distilled off and purified by silica gel chromatography (developing solvent: hexane / ethyl acetate = 7/3) to obtain 2.8 parts by mass (yield 33%) of a white solid. The melting point of the white solid, that is, the thermal crosslinking agent represented by the structural formula (v), was 78-80 ° C.
The product was identified by ¹ H-NMR (300 MHz: CDCl ₃ ). Each peak of the spectrum is 6.88 (d, 4H), 3.96 (q, 4H), 2.86 (d, 2H), 2.73 (d, 2H), 1.49 (s, 6H). Met.

-Synthesis of thermal crosslinking agent represented by structural formula (vi)-
40 parts by mass of bis (4-hydroxyphenyl) methanone and 111 parts by mass of methyl epichlorohydrin were placed in a reaction kettle and heated to 80 ° C. An aqueous solution containing 34.3 parts by mass of 48% NaOH aqueous solution and 30 parts by mass of water was dropped into the reaction kettle over 2 hours. Thereafter, the reaction was allowed to proceed for 10 hours. After allowing to cool, the reaction product was placed in 500 parts by mass of water to obtain a precipitate. The precipitate was filtered and recrystallized from methanol to obtain 31.5 parts by mass (yield 48%) of a white solid. The melting point of the white solid, that is, the thermal crosslinking agent represented by the structural formula (vi) was 114 to 116 ° C.
The product was identified by ¹ H-NMR (300 MHz: CDCl ₃ ). Each peak of the spectrum is 7.78 (d, 4H), 6.98 (d, 2H), 4.08 (q, 4H), 2.90 (d, 2H), 2.77 (d, 2H). 1.51 (s, 6H).

-Synthesis of thermal crosslinking agent represented by structural formula (vii)-
30 parts by mass of 4,4 ′-(1-methylethylidene) bis [2-cyclohexylphenol], 23.2 parts by mass of potassium carbonate, and 120 parts by mass of dimethylacetamide were placed in a reaction kettle and heated to 80 ° C. 26 parts by mass of 3-chloro-2-methyl-1-propene was added dropwise to the reaction kettle over 0.5 hours. Thereafter, the reaction was allowed to proceed for 10 hours. After allowing to cool, the reaction product was extracted with 100 parts by mass of ethyl acetate, separated with saturated brine, and the organic phase was dried over magnesium sulfate. The solvent of the organic phase was distilled off and recrystallization was performed to obtain 31.5 parts by mass of an intermediate product (yield 82%).
Next, 30 parts by mass of the intermediate product, 250 parts by mass of ethyl acetate, 50.3 parts by mass of sodium hydrogen carbonate, 200 parts by mass of water, and 70 parts by mass of acetone were placed in a reaction kettle. An aqueous solution in which 83 parts by mass of OXONE was dissolved in 400 parts by mass of water was dropped into the reaction kettle over 1 hour. Thereafter, the reaction was allowed to proceed for 7 hours. To the reaction kettle, 300 parts by mass of 10% aqueous sodium thiosulfate solution was added, stirred for 1 hour, separated with saturated brine, and the organic phase was dried over magnesium sulfate. The organic phase solvent was distilled off, and the precipitate was recrystallized from methanol to obtain 17.6 parts by mass (yield 56%) of a white solid. The melting point of the white solid, that is, the thermal crosslinking agent represented by the structural formula (vii) was 80-82 ° C.
The product was identified by ¹ H-NMR (300 MHz: CDCl ₃ ). Each peak of the spectrum is 7.03 (s, 4H), 6.96 (d, 2H), 6.37 (d, 2H), 3.95 (q, 4H), 2.88 (d, 2H). , 2.74 (d, 2H), 1.82-1.20 (m, 32H).

-Synthesis of thermal crosslinking agent represented by structural formula (viii)-
30 parts by mass of phenolphthalein, 28.6 parts by mass of potassium carbonate, and 120 parts by mass of dimethylacetamide were placed in a reaction kettle and heated to 80 ° C. To the reaction kettle, 25.6 parts by mass of 3-chloro-2-methyl-1-propene was added dropwise over 0.5 hours. Thereafter, the reaction was allowed to proceed for 10 hours. After allowing to cool, the reaction product was extracted with 100 parts by mass of ethyl acetate, separated with saturated brine, and the organic phase was dried over magnesium sulfate. The solvent of the organic phase was distilled off and recrystallized to obtain 40 parts by mass of an intermediate product (yield 99%).
Next, 30 parts by mass of the intermediate product, 250 parts by mass of ethyl acetate, 59.1 parts by mass of sodium bicarbonate, 200 parts by mass of water, and 86 parts by mass of acetone were placed in a reaction kettle. An aqueous solution prepared by dissolving 105 parts by mass of OXONE in 400 parts by mass of water was dropped into the reaction kettle after 1 hour. Thereafter, the reaction was allowed to proceed for 7 hours. To the reaction kettle, 300 parts by mass of 10% aqueous sodium thiosulfate solution was added and stirred for 1 hour, followed by separation with saturated brine and drying of the organic phase over magnesium sulfate. The solvent of the organic phase was distilled off, and the residue was purified by silica gel chromatography (developing solvent: hexane / ethyl acetate = 5/5) to obtain 24.5 parts by mass (yield 76%) of a white solid. The melting point of the white solid, that is, the thermal crosslinking agent represented by the structural formula (viii) was 106-108 ° C.
The product was identified by ¹ H-NMR (300 MHz: CDCl ₃ ). Each peak of the spectrum is 7.93 (d, 1H), 7.68 (t, 1H), 7.53 (q, 2H), 7.27-7.21 (m, 5H), 6.86 ( d, 4H), 3.98 (q, 4H), 2.84 (d, 2H), 2.72 (d, 2H), 1.47 (s, 6H).

(Example 12)
In Example 1, 40.0 parts by mass of the binder represented by the structural formula (46) in the photosensitive composition, and 20.0 parts by mass of the binder represented by the structural formula (46) are shown below. A photosensitive composition was prepared in the same manner as in Example 1 except that it was changed to 20 parts by mass of the acrylic resin (B1) having an unsaturated group obtained in Synthesis Example a. A permanent film and a laminate were prepared to form a permanent pattern.
Moreover, tackiness, exposure sensitivity, resolution, exposure speed, and storage stability were evaluated for the produced photosensitive film in the same manner as in Example 1, and pencil hardness and dielectric properties of the formed permanent pattern were evaluated. Evaluation was performed. As a result, the exposure sensitivity was 30 mJ / cm ² , the resolution was 70 μm, and the exposure speed was 13 mm / sec. Other results are shown in Table 3.

-Synthesis example a (Synthesis of acrylic resin (B1))-
A mixed solution consisting of 45.1 parts by weight of methyl methacrylate, 47.3 parts by weight of methacrylic acid, 1 part by weight of azoisovaleronitrile, and 215 parts by weight of propylene glycol monomethyl ether was placed in a 90 ° C. reaction vessel in a nitrogen gas atmosphere for 3 hours. It was dripped over. It reacted for 4 hours after dripping and obtained acrylic resin (A1).
Next, 54.7 parts by mass of cyclomer A200 (manufactured by Daicel Chemical Industries, Ltd.), 0.2 part by mass of hydroquinone monomethyl ether, and 1 part by mass of triphenylphosphine were added to the obtained acrylic resin (A1) solution. And an acrylic resin (B1) solution having an unsaturated group (solid content acid value: 111, Mw; 18,000, double bond equivalent: 2.3 mmol / g, propylene) Glycol monomethyl ether 41 mass% solution) was obtained.

(Example 13)
In Example 1, 40.0 parts by mass of the binder represented by the structural formula (46) in the photosensitive composition and 20.0 parts by mass of the binder represented by the structural formula (46) are shown below. A photosensitive composition was prepared in the same manner as in Example 1 except that the amount was changed to 20 parts by mass of the acrylic resin (B2) having an unsaturated group obtained in Synthesis Example b. A permanent film and a laminate were prepared to form a permanent pattern.
Moreover, tackiness, exposure sensitivity, resolution, exposure speed, and storage stability were evaluated for the produced photosensitive film in the same manner as in Example 1, and pencil hardness and dielectric properties of the formed permanent pattern were evaluated. Evaluation was performed. As a result, the exposure sensitivity was 30 mJ / cm ² , the resolution was 70 μm, and the exposure speed was 13 mm / sec. Other results are shown in Table 3.

-Synthesis example b (synthesis of acrylic resin (B2))-
A mixed solution consisting of 45.1 parts by weight of methyl methacrylate, 47.3 parts by weight of methacrylic acid, 1 part by weight of azoisovaleronitrile, and 215 parts by weight of propylene glycol monomethyl ether was placed in a 90 ° C. reaction vessel in a nitrogen gas atmosphere for 3 hours. It was dripped over. It reacted for 4 hours after dripping and obtained acrylic resin (A2).
Next, 35.9 parts by mass of glycidyl methacrylate, 0.2 part by mass of hydroquinone monomethyl ether, and 1 part by mass of triphenylphosphine are added to the obtained acrylic resin (A2) solution, and air is blown at 80 ° C. for 8 hours. An acrylic resin (B2) solution having an unsaturated group (solid content acid value; 104, Mw; 20,000, double bond equivalent 2.0)
mmol / g, 37% by mass solution of propylene glycol monomethyl ether).

(Examples 14 to 17)
In Examples 1, 8, 10 and 11, the photosensitive composition and the photosensitive film produced in the same manner as in Example 1 except that the exposure apparatus was replaced with the pattern forming apparatus described below. Then, exposure sensitivity, resolution, and exposure speed were evaluated, and pencil hardness and dielectric characteristics of the formed permanent pattern were evaluated. In Examples 14 to 17, the exposure sensitivity is 30 mJ / cm ² , the resolution is 70 μm, and the exposure speed is 7 mm / sec. Table 3 shows the results of pencil hardness, dielectric properties, and storage stability.

<< Pattern Forming Apparatus >>
The combined laser light source shown in FIGS. 8-9 and 25-29 as the light irradiating means, and 1,024 micromirrors 58 arranged in the main scanning direction schematically shown in FIG. 6 as the light modulating means. Among the 768 microarrays arranged in the sub-scanning direction, the DMD 36 controlled to drive only 1,024 × 256 rows and the light shown in FIG. 5 are imaged on the pattern forming material. A pattern forming apparatus 10 having an exposure head 30 having an optical system was used.

As the set inclination angle of each exposure head 30, that is, each DMD 36, an angle slightly larger than the angle θ _{ideal at} which double exposure is performed using a usable micromirror 58 of 1,024 columns × 256 rows was adopted. This angle θ _ideal is equal to the number N of N double exposures, the number s of usable micromirrors 58 in the column direction, the interval p of usable micromirrors 58 in the column direction, and the microscopic exposure head 30 in a tilted state. For the pitch δ of the scanning line formed by the mirror,
spsinθ _ideal ≧ Nδ (Formula 1)
Given by. As described above, the DMD 36 according to the present embodiment includes a large number of micromirrors 58 having equal vertical and horizontal arrangement intervals arranged in a rectangular lattice shape.
pcosθ _ideal = δ (Formula 2)
And the above equation 1 is
stanθ _ideal = N (Formula 3)
Since s = 256 and N = 2, the angle θ _ideal is about 0.45 degrees. Therefore, for example, 0.50 degrees is adopted as the set inclination angle θ.

First, the state of the exposure pattern on the exposed surface was examined in order to correct the variation in resolution and uneven exposure in double exposure. The results are shown in FIG. In FIG. 18, the light spot group from the micromirror 58 that can be used by the DMD 36 of the exposure heads 30 ₁₂ and 30 ₂₁ projected onto the exposed surface of the pattern forming material 12 with the stage 14 being stationary. Showed the pattern. The state of the exposure pattern formed on the exposed surface when the stage 14 is moved and the continuous exposure is performed with the light spot group pattern as shown in the upper part appearing in the lower part. Are shown for exposure areas 32 ₁₂ and 32 ₂₁ . In FIG. 18, for convenience of explanation, every other exposure pattern of the micromirrors 58 that can be used is divided into an exposure pattern based on the pixel column group A and an exposure pattern based on the pixel column group B. The actual exposure pattern on the exposed surface is a superposition of these two exposure patterns.

As shown in FIG. 18, as a result of the deviation of the relative position between the exposure heads 30 ₁₂ and 30 ₂₁ from the ideal state, both the exposure pattern by the pixel column group A and the exposure pattern by the pixel column group B are both. Thus, it can be seen that, in the exposure areas overlapping on the coordinate axes orthogonal to the scanning direction of the exposure head in the exposure areas 32 ₁₂ and 32 ₂₁ , an overexposed area is generated as compared with the ideal double exposure state.

The use of a set of slits 28 and a photodetector as a light spot position detection means, the position of the point P of the exposure head _{30 12} For the exposure area _{32 12} (1,1) and P (256,1), the exposure head For 30 ₂₁ , the positions of the light spots P (1,1024) and P (256, 1024) in the exposure area 32 ₂₁ are detected, and the angle formed by the inclination angle of the straight line connecting them and the scanning direction of the exposure head is determined. It was measured.

Using the actual inclination angle θ ′, the following equation 4
ttanθ ′ = N (Formula 4)
The natural number T closest to the value t satisfying the relationship is derived for each of the exposure heads 30 ₁₂ and 30 ₂₁ . T = 254 for the exposure head _{30 12,} the exposure head _{30 21} T = 255 was derived respectively. As a result, the micromirrors constituting the portions 78 and 80 covered with diagonal lines in FIG. 19 were identified as micromirrors that are not used during the main exposure.

Thereafter, the micromirrors corresponding to the light spots other than the light spots constituting the regions 78 and 80 covered by the oblique lines in FIG. 19 were similarly covered by the shaded areas 82 and the shaded areas in FIG. Micromirrors corresponding to the light spots constituting the region 84 were identified and added as micromirrors that are not used during the main exposure.
With respect to the micromirrors that are specified not to be used at the time of exposure, a signal for setting the angle of the always-off state is sent by the pixel element control means, and these micromirrors are substantially exposed. It was controlled not to be involved.
As a result, in each of the exposure areas 32 ₁₂ and 32 ₂₁ , an ideal double exposure is performed in each area other than the inter-head connection area, which is an overlapping exposure area on the exposed surface formed by the plurality of exposure heads. Thus, the total area of the overexposed region and the underexposed region can be minimized.

(Comparative Example 1)
In Example 1, except that the compound represented by the structural formula (i) in the photosensitive composition was changed to 2,2′-bis (4-glycidylphenyl) propane (oily substance). A photosensitive composition was prepared in the same manner as in Example 1, and a photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern.
Moreover, tackiness, exposure sensitivity, resolution, exposure speed, and storage stability were evaluated for the produced photosensitive film in the same manner as in Example 1, and pencil hardness and dielectric properties of the formed permanent pattern were evaluated. Evaluation was performed. In Comparative Example 1 and subsequent Comparative Examples 2 and 3, the exposure sensitivity was 30 mJ / cm ² , the resolution was 70 μm, and the exposure speed was 13 mm / sec. Other results are shown in Table 3.

(Comparative Example 2)
In Example 1, except that the compound represented by the structural formula (i) in the photosensitive composition was changed to Epicoat YX4000 (manufactured by Japan Epoxy Resin, epoxy resin, melting point 110 ° C.), Example 1 A photosensitive composition was prepared in the same manner as in Example 1. A photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern.
Moreover, tackiness, exposure sensitivity, resolution, exposure speed, and storage stability were evaluated for the produced photosensitive film in the same manner as in Example 1, and pencil hardness and dielectric properties of the formed permanent pattern were evaluated. Evaluation was performed. Table 3 shows results other than exposure sensitivity, resolution, and exposure speed.

(Comparative Example 3)
In Example 1, except that the compound represented by the structural formula (i) in the photosensitive composition was changed to TEPIC (manufactured by Nissan Chemical Industries, Ltd., epoxy resin, melting point 125 ° C.) A photosensitive composition was prepared in the same manner, and a photosensitive film and a laminate were prepared in the same manner as in Example 1 to form a permanent pattern.
Moreover, tackiness, exposure sensitivity, resolution, exposure speed, and storage stability were evaluated for the produced photosensitive film in the same manner as in Example 1, and pencil hardness and dielectric properties of the formed permanent pattern were evaluated. Evaluation was performed. Table 3 shows results other than exposure sensitivity, resolution, and exposure speed.

From the results in Table 3, the photosensitive layer in the photosensitive film produced using the photosensitive composition of Examples 1 to 18 containing a thermal cross-linking agent having a melting point of 50 to 250 ° C. and soluble in a solvent, Comparative example using a conventionally known epoxy resin compound as a thermal cross-linking agent, which has excellent tackiness, exposure sensitivity and resolution, has a surface hardness and a dielectric property of a cured layer in a permanent pattern formed using the photosensitive film, Compared to the photosensitive films 1 to 3, it was confirmed that the storage stability was extremely excellent. In particular, the photosensitive films of Examples 1 and 2 and 5 to 17 in which the content of the thermal crosslinking agent in the photosensitive composition is 1 to 15% by mass are extremely excellent in both storage stability and dielectric properties. I found out.
In Examples 15 to 18 using the same photosensitive film as in Examples 1, 8, 10 and 11, in the permanent pattern forming method of the present invention, resolution variations and exposure unevenness in double exposure were corrected. Therefore, it was confirmed that a high-definition pattern with high resolution can be obtained.
On the other hand, in Comparative Examples 1-3, it turned out that storage stability is very inferior.

The photosensitive film of the present invention has a softening point and a melting point of 50 to 250 ° C., and contains a thermal crosslinking agent that is soluble in a solvent, thereby causing a reaction at a low temperature or a normal temperature during storage. Excellent storage stability, low surface tack, good laminating and handling properties when filmed, excellent peelability from protective film and support, high sensitivity and excellent developability Excellent chemical resistance, surface hardness, heat resistance, dielectric properties, electrical insulation, etc. after development, can form high-definition patterns, and is suitable for manufacturing printed wiring boards including package substrates It can be widely used for the formation of permanent patterns (interlayer insulating film, protective film, solder resist pattern, etc.) in high-definition permanent patterns in the semiconductor field. It can be suitably used for the permanent pattern forming method.
By using the photosensitive composition of the present invention, the photosensitive film of the present invention does not react at a low temperature or normal temperature during storage, is excellent in storage stability, has a small surface tackiness, and is formed into a film. Good laminating and handling properties, excellent peelability from protective film and support, high sensitivity and excellent developability, excellent chemical resistance after development, surface hardness, heat resistance, dielectric properties, Electrical insulation can be obtained, and high-definition patterns can be formed. Patterns suitable for manufacturing printed circuit boards including package substrates, or permanent patterns (interlayer insulation) in high-definition permanent patterns in the semiconductor field Film, protective film, solder resist pattern, etc.) and can be suitably used for the permanent pattern forming method of the present invention.
By using the photosensitive composition or photosensitive film of the present invention, the permanent pattern forming method of the present invention does not cause a reaction at low or normal temperature during storage, has excellent storage stability, and has a surface tackiness. Small, good laminating and handling properties when made into a film, excellent peelability from protective film and support, high sensitivity and excellent developability, excellent chemical resistance, surface hardness, heat resistance after development Characteristics, dielectric properties, electrical insulation, etc., and a high-definition pattern can be formed. Therefore, a pattern suitable for manufacturing a printed wiring board including a package substrate or a high-definition permanent pattern (interlayer insulation) in the semiconductor field. Film, protective film, solder resist pattern, etc.) can be formed with high definition and efficiency, which is favorable for the formation of various patterns that require high-definition exposure. Can be used for, it can be suitably used especially formation of high-definition permanent pattern.

FIG. 1 is a perspective view showing an appearance of an example of a pattern forming apparatus. FIG. 2 is a perspective view showing an example of the configuration of the scanner of the pattern forming apparatus. FIG. 3A is a plan view showing an exposed region formed on the exposed surface of the photosensitive layer. FIG. 3B is a plan view showing an arrangement of exposure areas by each exposure head. FIG. 4 is a perspective view showing an example of a schematic configuration of the exposure head. FIG. 5A is a top view showing an example of a detailed configuration of the exposure head. FIG. 5B is a side view showing an example of a detailed configuration of the exposure head. FIG. 6 is a partially enlarged view showing an example of the DMD of the pattern forming apparatus of FIG. FIG. 7A is a perspective view for explaining the operation of the DMD. FIG. 7B is a perspective view for explaining the operation of the DMD. FIG. 8 is a perspective view showing an example of the configuration of the fiber array light source. FIG. 9 is a front view showing an example of the arrangement of light emitting points in the laser emitting section of the fiber array light source. FIG. 10 is an explanatory diagram showing an example of unevenness that occurs in the pattern on the exposed surface when there is an exposure head mounting angle error and pattern distortion. FIG. 11 is a top view showing a positional relationship between an exposure area by one DMD and a corresponding slit. FIG. 12 is a top view for explaining a method of measuring the position of the light spot on the exposed surface using a slit. FIG. 13 is an explanatory diagram showing a state in which unevenness generated in a pattern on an exposed surface is improved as a result of using only selected micromirrors for exposure. FIG. 14 is an explanatory diagram showing an example of unevenness that occurs in the pattern on the exposed surface when there is a relative position shift between adjacent exposure heads. FIG. 15 is a top view showing the positional relationship between the exposure areas by two adjacent exposure heads and the corresponding slits. FIG. 16 is a top view for explaining a method of measuring the position of the light spot on the exposed surface using a slit. FIG. 17 is an explanatory diagram showing a state in which only the used pixels selected in the example of FIG. 14 are actually moved and the unevenness in the pattern on the exposed surface is improved. FIG. 18 is an explanatory diagram showing an example of unevenness that occurs in the pattern on the exposed surface when there is a relative position shift and a mounting angle error between adjacent exposure heads. FIG. 19 is an explanatory diagram showing exposure using only the used pixel portion selected in the example of FIG. FIG. 20A is an explanatory diagram showing an example of magnification distortion. FIG. 20B is an explanatory diagram showing an example of beam diameter distortion. FIG. 21A is an explanatory view showing a first example of reference exposure using a single exposure head. FIG. 21B is an explanatory diagram showing a first example of reference exposure using a single exposure head. FIG. 22 is an explanatory diagram showing a first example of reference exposure using a plurality of exposure heads. FIG. 23A is an explanatory diagram showing a second example of reference exposure using a single exposure head. FIG. 23B is an explanatory diagram showing a second example of reference exposure using a single exposure head. FIG. 24 is an explanatory view showing a second example of reference exposure using a plurality of exposure heads. FIG. 25 is an example of a diagram illustrating a configuration of a multimode optical fiber. FIG. 26 is an example of a plan view showing the configuration of the combined laser light source. FIG. 27 is an example of a plan view showing the configuration of the laser module. FIG. 28 is an example of a side view showing the configuration of the laser module shown in FIG. FIG. 29 is a partial side view showing the configuration of the laser module shown in FIG. FIG. 30 is an example of a perspective view showing a configuration of a laser array. FIG. 31A is an example of a perspective view showing a configuration of a multi-cavity laser. FIG. 31B is an example of a perspective view of a multi-cavity laser array in which the multi-cavity lasers shown in FIG. 31A are arranged in an array. FIG. 32 is an example of a plan view showing another configuration of the combined laser light source. FIG. 33 is an example of a plan view showing another configuration of the combined laser light source. FIG. 34A is an example of a plan view showing another configuration of the combined laser light source. FIG. 34B is an example of a cross-sectional view along the optical axis of FIG. 34A.

Explanation of symbols

B1 to B7 Laser beam L1 to L7 Collimator lens LD1 to LD7 GaN-based semiconductor laser 10 Pattern forming device 12 Photosensitive layer (photosensitive material)
DESCRIPTION OF SYMBOLS 14 Moving stage 18 Installation stand 20 Guide 22 Gate 24 Scanner 26 Sensor 28 Slit 30 Exposure head 32 Exposure area 36 Digital micromirror device (DMD)
38 Fiber array light source 58 Micro mirror (picture element)
Reference Signs List 60 laser module 62 multimode optical fiber 64 optical fiber 66 laser emitting unit 110 heat block 111 multicavity laser 113 rod lens 114 lens array 140 laser array 200 condenser lens

Claims (21)

  (A) a binder, (B) a polymerizable compound, (C) a photopolymerization initiator, (D) at least one of a softening point and a melting point is 50 to 250 ° C. and is soluble in a solvent. A photosensitive composition comprising at least a thermal crosslinking agent.   (D) The photosensitive composition of Claim 1 whose at least any one of the softening point and melting | fusing point of a thermal crosslinking agent is 70-150 degreeC.   (D) The thermal crosslinking agent is at least one selected from an epoxy compound, an oxetane compound, an isocyanate compound, a cyanate compound, a methylolated melamine compound, a bismaleimide compound, and an oxazoline compound. The photosensitive composition as described.   The photosensitive composition according to claim 3, wherein (D) the thermal crosslinking agent is an epoxy compound.   The photosensitive composition according to claim 4, wherein (D) the thermal crosslinking agent is a β-modified epoxy compound.   The photosensitive composition according to claim 5, wherein (D) the thermal crosslinking agent is a β-position alkyl group-modified epoxy compound containing at least an epoxy group having an alkyl group at the β-position.   The photosensitive composition according to claim 6, wherein (D) the thermal crosslinking agent is a β-position methyl group-modified epoxy compound containing at least an epoxy group having a methyl group at the β-position.   The epoxy group having an alkyl group at the β-position is at least one selected from a β-methylglycidyl group, a β-ethylglycidyl group, a β-propylglycidyl group, and a β-butylglycidyl group. The photosensitive composition in any one. (D) The thermal crosslinking agent has two or more oxirane rings having a substituent at the oxirane ring portion in one molecule, and is represented by any one of the following general formulas (1) and (2): The photosensitive composition in any one of 8.
However, in said general formula (1) and (2), P represents either a single bond, an oxygen atom, a carbonyl group, alkylene, and arylene. Q represents any of alkylene having 2 or more carbon atoms and arylene. A ^{1 to} A ^{5 each} represents a single bond, alkylene, or arylene, and X ^{1 to} X ⁵ each represents a single bond, an oxygen atom, a sulfur atom, an amino group, a carbonyl group, —COO—, —OCO—, It represents either alkylene or arylene. R ^{1 to} R ^{5 each} represents a halogen atom, an alkyl group, or an aryl group.   (D) Content of a thermal crosslinking agent is 1-50 mass%, The photosensitive composition in any one of Claim 1 to 9.   (A) The photosensitive composition in any one of Claim 1 to 10 in which a binder contains an epoxy acrylate compound at least.   The photosensitive composition according to claim 1, wherein (A) the binder is a vinyl copolymer having an acidic group and an ethylenically unsaturated double bond.   (A) The photosensitive composition in any one of Claim 1 to 12 in which a binder contains the vinyl copolymer which has an epoxy acrylate compound and an acidic group and an ethylenically unsaturated double bond.   (C) The photopolymerization initiator is at least 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 13 containing 1 type.   A sensitizer, wherein the sensitizer is at least one selected from a condensed ring compound and an amine compound substituted with at least two aromatic hydrocarbon rings and aromatic heterocyclic rings. The photosensitive composition according to any one of claims 1 to 14.   It has at least a support, a photosensitive layer made of the photosensitive composition according to any one of claims 1 to 15 on the support, and a protective film on the photosensitive layer. Photosensitive film.   A permanent pattern, wherein the photosensitive composition according to any one of claims 1 to 15 is applied to the surface of a substrate, dried to form a photosensitive layer, and then exposed, developed, and heated. Forming method.   A method for forming a permanent pattern, comprising: laminating the photosensitive film according to claim 16 on a surface of a substrate under at least one of heating and pressurization, and then exposing, developing, and heating. For the photosensitive layer,
A light irradiating means, and n (where n is a natural number of 2 or more) two-dimensionally arranged picture elements that receive and emit light from the light irradiating means, and according to the pattern information, An exposure head provided with a light modulation means capable of controlling a picture element portion, the exposure head being arranged so that a column direction of the picture element portion forms a predetermined set inclination angle θ with respect to a scanning direction of the exposure head Using the head
With respect to the exposure head, the usable pixel part designating means designates the pixel part to be used for N double exposure (where N is a natural number of 2 or more) among the usable graphic elements.
For the exposure head, the pixel part control means controls the pixel part so that only the pixel part specified by the used pixel part specifying means is involved in exposure,
The permanent pattern forming method according to claim 17, wherein the exposure is performed by moving the exposure head relative to the photosensitive layer in a scanning direction, and developing.   The permanent pattern forming method according to claim 17, wherein the entire surface of the photosensitive layer is exposed after the development. A pattern formed by the permanent pattern forming method according to claim 17.