JP2006160854A - Styrene derivative, polymer, its production method, pattern forming material, permanent pattern, and its production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a styrene derivative excellent in copolymerizability with other monomers and capable of being easily synthesized by a common polymerization means, a polymer using the styrene derivative and being soluble in an alkali before being heated and excellent in alkali resistance after being heated, and its production method and to provide a pattern forming material using the polymer and being soluble in an alkali and excellent in developability and storage stability before being developed and excellent in alkali resistance and insulation properties after being developed, a high-precision permanent pattern, and its efficient formation method. <P>SOLUTION: The styrene derivative represented by formula (1) or formula (2) is obtained. The polymer is synthesized from the styrene derivative, the pattern forming material is formed from the polymer, and the permanent pattern is formed from the pattern forming material. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a styrene derivative, a polymer which is soluble in alkali before heating using the styrene derivative and exhibits excellent alkali resistance after heating, and a method for producing the same. In addition, before development using the pattern forming material formed with this polymer, it is alkali-soluble and excellent in developability and storage stability, and after development, it has high definition that exhibits excellent chemical resistance such as alkali resistance and insulation. The present invention relates to a 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.

As a material for forming such alkali development type photo solder resist, maleic anhydride copolymer, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, partial esterification Examples thereof include a pattern forming material using a copolymer such as a maleic acid copolymer, and an imide ring-closing binder containing a cellulose derivative having a carboxyl group in the side chain (see Patent Documents 1 and 2). Among these, a maleamic acid copolymer having a maleic acid half amide structure obtained by reacting an amine with the anhydride group of the maleic anhydride copolymer is preferable.
Such a binder is alkali-soluble before heating, and maleamic acid is cyclized by heating to form an imide structure, thereby indicating alkali insolubility.

However, maleic anhydride is a polymer handbook-3rd ed. (J. Brandrup, edited by E. H. Immergut, John Wiley & Sons, Inc. (1989)) As is clear from the copolymerization reactivity ratio on page II / 153, homopolymerization is difficult, and copolymerization is also possible. Also exhibits strong alternating copolymerization with certain monomers such as styrene and vinyl acetate, but exhibits special polymerization properties such as poor copolymerization with other monomers, limiting the composition of the copolymer or polymerization. There is a problem that the method is special and time-consuming.
Therefore, after exposure, it is possible to develop with an alkaline aqueous solution advantageous for occupational hygiene or pollution control, and a pattern forming material from which a cured product excellent in chemical resistance such as alkali resistance and insulation can be obtained by heating after development. However, it was difficult to easily manufacture.

JP 2003-313249 A JP 2004-285077 A

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention is excellent in polymerizability with other monomers, and can be easily synthesized by ordinary polymerization means, and is soluble in alkali before heating using this monomer, and has excellent alkali resistance after heating. It aims at obtaining the polymer which shows this, and its manufacturing method. Furthermore, the pattern forming material formed with this polymer, and using this pattern forming material, it is alkali-soluble before development and has excellent developability and storage stability, but after development, excellent chemical resistance such as alkali resistance, It is an object of the present invention to provide a high-definition permanent pattern (protective film, interlayer insulating film, solder resist pattern, etc.) that exhibits insulating properties, and an efficient formation method thereof.

Means for solving the problems are as follows. That is,
<1> A styrene derivative having an amic acid structure in the molecule.
<2> A styrene derivative represented by any one of the following general formula (1) and the following general formula (2).
However, in said general formula (1) and general formula (2), R < ₁ > and R < ₃ > represents either a hydrogen atom or a methyl group. R ₂ represents a functional group including any of linear, branched and cyclic. R ₄ and R ₅ each independently represents a functional group containing any one of a hydrogen atom, a halogen atom, a straight chain, a branched chain and a cyclic group. X ₁ and X ₂ represent an organic connecting chain. A ₁ represents a trivalent organic linking group capable of forming an imide ring by a ring-closing reaction between —COOH— and —CONH—R ₂ . A ₂ represents a divalent organic linking group capable of forming an imide ring by a ring-closing reaction between —COOH— and —NHCO—.
<3> A styrene derivative represented by any one of the following general formula (3) and the following general formula (4).
However, the general formula (3) and general formula (4), R ₅ and R ₇ represent a hydrogen atom or a methyl group. R ₆ represents any one selected from the group consisting of an alkyl group, an aryl group, and a heterocyclic residue, which may have a substituent. R ₈ and R ₉ each independently represents a functional group containing any one of a hydrogen atom, a halogen atom, a straight chain, a branched chain and a cyclic group. X ₃ represents any linking chain selected from an alkylene chain, an arylene chain, —COO—, —OCO—, —CONR ₁₀ —, —COO—R ₁₁ —, and —CONR ₁₂ —R ₁₃ —. X ₄ represents any linking chain selected from an alkylene chain, an arylene chain, —COO—, —OCO—, —CONR ₁₄ —, —COO—R ₁₅ —, and —CONR ₁₆ —R ₁₇ —. R ₁₀ , R ₁₂ , R _14, and R ₁₆ represent any one selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, and a heteryl group. The alkyl group, aryl group, aralkyl group, and heteryl group may each have a branch. R ₁₁ , R ₁₃ , R ₁₅ and R ₁₇ represent a divalent linking group, may have a branch and a substituent, or may be a single bond. A ₃ represents a trivalent organic linking group capable of forming an imide ring by a ring-closing reaction between —COOH— and —CONH—R ₆ . A ₄ represents a divalent organic linking group capable of forming an imide ring by a ring-closing reaction between —COOH— and —NHCO—.
<4> A styrene derivative represented by any one of the following general formula (5) and the following general formula (6) and used for the synthesis of a polymer forming material contained in a pattern forming material.
In the general formula, R ₁₈ and R ₂₀ represents a hydrogen atom or a methyl group. R ₁₉ represents a functional group including any of linear, branched and cyclic. R ₂₁ and R ₂₂ each independently represents a functional group containing any one of a hydrogen atom, a halogen atom, a straight chain, a branched chain and a cyclic group. X ₅ and X ₆ represent either a single bond or an organic linking chain. A ₅ represents a trivalent organic linking group capable of forming an imide ring by a ring-closing reaction between —COOH— and —CONH—R ₁₉ . A ₆ represents a divalent organic linking group capable of forming an imide ring by a ring-closing reaction between —COOH— and —NHCO—.
<5> A polymer comprising a styrene derivative having an amic acid structure in the molecule according to <1>.
<6> The styrene derivative according to any one of <2> to <3> is included in the structural unit, and the structural unit is represented by any one of the following general formula (7) and the following general formula (8). It is a polymer.
In the general formula, R ₂₃ and R ₂₅ represents a hydrogen atom or a methyl group. R ₂₄ represents a functional group including any of linear, branched and cyclic. R ₂₆ and R ₂₇ each independently represents a functional group including any of linear, branched and cyclic. X ₇ and X ₈ represent an organic linking chain. A ₇ represents a trivalent organic linking group capable of forming an imide ring by a ring-closing reaction between —COOH— and —CONH—R ₂₄ . A ₈ represents a divalent organic linking group capable of forming an imide ring by a ring-closing reaction between —COOH— and —NHCO—.
<7> A polymer comprising the styrene derivative according to <4> as a constituent unit, represented by any one of the following general formula (9) and the following general formula (10), and used for a pattern forming material: It is.
In the general formula, R ₂₈ and R ₃₀ represents a hydrogen atom or a methyl group. R ₂₉ represents a functional group including any of linear, branched and cyclic. R ₃₁ and R ₃₂ each independently represents a functional group including any of linear, branched and cyclic. X ₉ and X ₁₀ represent either a single bond or an organic linking chain. A ₉ represents a trivalent organic linking group capable of forming an imide ring by a ring-closing reaction between —COOH— and —CONH—R ₂₉ . A ₁₀ represents a divalent organic linking group capable of forming an imide ring by a ring-closing reaction between —COOH— and —NHCO—.
<8> The polymer according to any one of <5> to <7>, which is alkali-soluble at normal temperature and becomes an alkali-resistant compound when heated to 50 ° C to 250 ° C.
<9> The method for producing a polymer according to any one of <5> to <6>, wherein the styrene structure according to any one of <1> to <3> is used to form an imide structure by heating. It is a method for producing a polymer characterized by forming.
<10> A method for producing a polymer used for the pattern forming material according to <7>, wherein the styrene structure according to <4> is used to form an imide structure by heating. It is a manufacturing method.
<11> A pattern forming material comprising at least the polymer according to any one of <5> to <7>.
<12> It has at least a photosensitive layer on a support, and the photosensitive layer contains a binder containing at least the polymer described in <5> to <7>, a polymerizable compound, and a photopolymerization initiator. A pattern forming material characterized by the following.
<13> After the photosensitive layer modulates the light from the light irradiation means by the light modulation means having n drawing parts for receiving and emitting the light from the light irradiation means, the emission surface in the drawing part The pattern forming material according to <12>, wherein the pattern forming material is exposed with light passing through a microlens array in which microlenses having aspherical surfaces capable of correcting an aberration due to distortion of the lens are arranged. In the pattern forming material according to <13>, the light irradiation unit irradiates light toward the light modulation unit. The n picture elements in the light irradiation means receive and emit light from the light irradiation means, thereby modulating the light received from the light irradiation means. The light modulated by the light modulation means passes through the aspherical surface in the microlens array, so that the aberration due to the distortion of the exit surface in the pixel portion is corrected, and the image formed on the photosensitive layer is distorted. It is suppressed. As a result, the photosensitive layer is exposed with high definition. Thereafter, when the photosensitive layer is developed, a high-definition permanent pattern is formed.
<14> The pattern forming material according to any one of <11> to <13>, wherein the binder has an acidic group.
<15> The pattern forming material according to any one of <11> to <14>, wherein the binder includes a vinyl copolymer.
<16> The pattern forming material according to any one of <11> to <15>, wherein the binder has an acid value of 70 to 250 (mgKOH / g).
<17> The pattern forming material according to any one of <11> to <16>, wherein the polymerizable compound includes a monomer having at least one of a urethane group and an aryl group.

<18> The photopolymerization initiator includes at least one selected from halogenated hydrocarbon derivatives, hexaarylbiimidazoles, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, and metallocenes. The pattern forming material according to any one of <11> to <17>.
<19> The pattern forming material according to any one of <11> to <18>, wherein the photosensitive layer has a thickness of 1 to 100 μm.
<20> From the above <11> to <19, wherein the photosensitive layer contains 30 to 90% by mass of the binder, 5 to 60% by mass of the polymerizable compound, and 0.1 to 30% by mass of the photopolymerization initiator. > The pattern forming material according to any one of the above.
<21> The pattern forming material according to any one of <12> to <20>, wherein the support includes a synthetic resin and is transparent.
<22> The pattern forming material according to any one of <12> to <21>, wherein the support has a long shape.
<23> The pattern forming material according to any one of <12> to <22>, wherein the pattern forming material is long and wound in a roll shape.
<24> The pattern forming material according to any one of <12> to <23>, comprising a protective film on the photosensitive layer in the pattern forming material.
<25> A permanent pattern forming method comprising at least exposing the pattern forming material according to any one of <11> to <24>.
<26> A permanent pattern forming method, wherein the pattern forming material according to <11> is applied to a surface of a substrate, dried to form a photosensitive layer, and then exposed and developed. In the permanent pattern forming method according to <26>, the pattern forming material is applied to the surface of the substrate. The applied pattern forming material is dried to form the photosensitive layer. The photosensitive layer is exposed. The exposed photosensitive layer is developed. As a result, the cured film has a high film hardness, and a permanent pattern optimum for the protective film, insulating film, or solder resist pattern is formed.
<27> A photosensitive film using the pattern forming material according to any one of <12> to <24> is laminated on the surface of the substrate under at least one of heating and pressurization, and then exposed. , Developing a permanent pattern. In the permanent pattern forming method according to <25>, the photosensitive film is laminated on the surface of the base material under heating and pressure. The photosensitive layer in the laminated photosensitive film is exposed. The exposed photosensitive layer is developed. As a result, the film hardness itself of the cured film is improved, and a permanent pattern optimum for the protective film, the insulating film, or the solder resist pattern is formed.
<28> The permanent pattern forming method according to any one of <26> to <27>, wherein the base material is a printed wiring board on which wiring is formed. In the permanent pattern forming method according to <28>, 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.
<29> The method for forming a permanent pattern according to any one of <25> to <28>, wherein the exposure is performed imagewise based on pattern information to be formed.
<30> The permanent pattern according to any one of <25> to <29>, wherein the exposure is performed using light that is generated based on pattern information to be formed and modulated according to the control signal It is a forming method.
<31> From <25> to <30, wherein exposure is performed using light irradiation means for irradiating light and light modulation means for modulating light emitted from the light irradiation means based on pattern information to be formed. The permanent pattern forming method according to any one of the above.
<32> The light modulation unit further includes a pattern signal generation unit that generates a control signal based on pattern information to be formed, and the pattern signal generation unit generates light emitted from the light irradiation unit. The method for forming a permanent pattern according to <31>, wherein modulation is performed according to a signal.
<33> The light modulation means has n pixel parts, and forms any less than n pixel parts continuously arranged from the n pixel parts. The permanent pattern forming method according to any one of <31> to <32>, which is controllable according to pattern information. In the method for forming a permanent pattern according to <33>, any less than n pixel portions arranged continuously from n pixel portions in the light modulation unit are controlled according to pattern information. By doing so, the light from the light irradiation means is modulated at high speed.
<34> The method for forming a permanent pattern according to any one of <31> to <33>, wherein the light modulator is a spatial light modulator.
<35> The method for forming a permanent pattern according to <34>, wherein the spatial light modulation element is a digital micromirror device (DMD).
<36> The permanent pattern forming method according to any one of <33> to <35>, wherein the picture element portion is a micromirror.
<37> Exposure is performed through a microlens array in which microlenses having aspherical surfaces capable of correcting aberrations due to distortion of the exit surface of the picture element portion in the light modulation means after the light is modulated by the light modulation means. The method for forming a permanent pattern according to any one of <33> to <36>.
<38> The method for forming a permanent pattern according to <37>, wherein the aspherical surface is a toric surface. In the method for forming a permanent pattern according to <38>, since the aspherical surface is a toric surface, aberration due to distortion of the radiation surface in the pixel portion is efficiently corrected, and an image is formed on the photosensitive layer. Image distortion is efficiently suppressed. As a result, the photosensitive layer is exposed with high definition. Thereafter, the photosensitive layer is developed to form a high-definition permanent pattern.
<39> The method for forming a permanent pattern according to any one of <26> to <38>, wherein the exposure is performed through an aperture array. In the method for forming a permanent pattern according to <39>, the extinction ratio is improved by performing exposure through the aperture array. As a result, the exposure is performed with extremely high definition. Thereafter, the photosensitive layer is developed to form a very fine permanent pattern.
<40> The permanent pattern forming method according to any one of <26> to <39>, wherein the exposure is performed while relatively moving the exposure light and the photosensitive layer. In the method for forming a permanent pattern according to <32>, exposure is performed at a high speed by performing exposure while relatively moving the modulated light and the photosensitive layer.
<41> The permanent pattern forming method according to any one of <26> to <40>, wherein the exposure is performed on a partial region of the photosensitive layer.
<42> The method for forming a permanent pattern according to any one of <26> to <41>, wherein the light irradiation unit can synthesize and irradiate two or more lights. In the method for forming a permanent pattern according to <42>, the light irradiation unit can synthesize and irradiate two or more lights, so that exposure is performed with exposure light having a deep focal depth. As a result, the exposure of the photosensitive layer is performed with extremely high definition. Thereafter, the photosensitive layer is developed to form a very fine permanent pattern.
<43> The 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. The permanent pattern forming method according to any one of <31> to <42>. In the method for forming a permanent pattern according to <43>, the laser light emitted from each of the plurality of lasers is condensed by the collective optical system by the light irradiation unit and can be coupled to the multimode optical fiber. By doing so, exposure is performed with exposure light having a deep focal depth. As a result, the exposure of the photosensitive layer is performed with extremely high definition. Thereafter, the photosensitive layer is developed to form a very fine permanent pattern.
<44> The method for forming a permanent pattern according to any one of <26> to <43>, wherein the exposure is performed using a laser beam having a wavelength of 395 to 415 nm.
<45> The method for forming a permanent pattern according to any one of <26> to <44>, wherein the photosensitive layer is subjected to a curing treatment after development. In the method for forming a permanent pattern described in <45>, after the development, the curing process is performed on the photosensitive layer. As a result, the film strength of the cured region of the photosensitive layer is increased.
<46> The method for forming a permanent pattern according to <45>, wherein the curing treatment is at least one of a whole surface exposure treatment and a whole surface heat treatment performed at 120 to 200 ° C. In the permanent pattern forming method according to <46>, curing of the resin in the photosensitive composition is promoted in the overall exposure process. Moreover, the film | membrane intensity | strength of a cured film is raised in the whole surface heat processing performed on the said temperature conditions.
<47> The method for forming a permanent pattern according to any one of <26> to <46>, wherein at least one of a protective film, an interlayer insulating film, and a solder resist pattern is formed. In the method for forming a permanent pattern according to <47>, at least one of a protective film, an interlayer insulating film, and a solder resist pattern is formed. Protected from impact and bending.
<48> A permanent pattern formed by the method for forming a permanent pattern according to any one of <25> to <47>. Since the permanent pattern described in <48> is formed by the permanent pattern forming method, it is excellent in chemical resistance such as alkali resistance, film hardness of a cured film, heat resistance, insulation, and the like, and has high definition. It is useful for high-density mounting of semiconductors and components on multilayer wiring boards and build-up wiring boards.
<49> The permanent pattern according to <48>, which is at least one of a protective film, an interlayer insulating film, and a solder resist pattern. Since the permanent pattern according to <49> is at least one of a protective film, an interlayer insulating film, and a solder resist pattern, due to the insulating property, heat resistance, etc. of the film, the wiring is subject to external impact, bending, etc. Protected from.

  According to the present invention, conventional problems can be solved, a styrene derivative that is excellent in polymerizability with other monomers and can be easily synthesized by ordinary polymerization means, and before heating using this styrene derivative It is possible to obtain a polymer that is soluble in alkali and exhibits excellent alkali resistance after heating, and a method for forming the polymer. In addition, the pattern forming material formed with this polymer and the pattern forming material are soluble in alkali before development and have excellent developability and storage stability, but after development, chemical resistance such as alkali resistance, insulation It is possible to provide a high-definition permanent pattern (such as a protective film, an interlayer insulating film, and a solder resist pattern) that is excellent in the above and an efficient formation method thereof.

(Styrene derivatives)
Examples of the styrene derivative in the present invention include the following first to fourth embodiments. Hereinafter, these styrene derivatives will be described.
-First embodiment-
The 1st aspect of the styrene derivative in this invention has an amic acid structure in a molecule | numerator.
-Second aspect-
The 2nd aspect of the styrene derivative in this invention is represented by either the following general formula (1) and the following general formula (2).

However, in said general formula (1) and general formula (2), R < ₁ > and R < ₃ > represents either a hydrogen atom or a methyl group. R ₂ represents a functional group including any of linear, branched and cyclic. R ₄ and R ₅ each independently represents a functional group containing any one of a hydrogen atom, a halogen atom, a straight chain, a branched chain and a cyclic group. X ₁ and X ₂ represent an organic connecting chain. A ₁ represents a trivalent organic linking group capable of forming an imide ring by a ring-closing reaction between —COOH— and —CONH—R ₂ . A ₂ represents a divalent organic linking group capable of forming an imide ring by a ring-closing reaction between —COOH— and —NHCO—.

In the general formulas (1) and (2), specific examples of R ₂ include, for example, methyl, ethyl, propyl, iso-propyl, butyl, tertiary butyl, secondary butyl, pentyl, hexyl, cyclohexyl, heptyl. Octyl, 2-ethylhexyl, lauryl, benzyl, phenethyl, phenyl, tolyl, octylphenyl, methoxyphenyl, 4-chlorophenyl, 1-naphthyl, methoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, Examples include 2-butoxyethyl, 2-cyclohexyloxyethyl, 3-ethoxypropyl, 3-propoxypropyl, 3-isopropoxypropyl, adamantyl, and the like.
Specific examples of R ₄ and R ₅ include, for example, a hydrogen atom, a halogen atom, methyl, ethyl, propyl, iso-propyl, butyl, tertiary butyl, secondary butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl, lauryl, benzyl, phenethyl, phenyl, tolyl, octylphenyl, methoxyphenyl, 4-chlorophenyl, 1-naphthyl, methoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 2-butoxy Examples include ethyl, 2-cyclohexyloxyethyl, 3-ethoxypropyl, 3-propoxypropyl, 3-isopropoxypropyl, adamantyl and the like.

Preferred examples of X ₁ and X ₂ include alkylenes such as methylene and ethylene, branched alkylenes such as isopropylidene, ether group-containing alkylenes such as polyethylene oxide, branched ether group-containing alkylenes such as propylene oxide, and arylenes such as phenylene and biphenylene. , arylene represented by the following structural formula, aralkylene, and the like, further, -CONH -, - CONMe -, - CONPh -, - CON (CH 2 CH 2 OMe) -, - COO-Z -, - COO -Z-OCO-, -COO-Z-CO-, -COO-Z-O-, -COO-Z-S-, -CONH-Z-, -CONH-Z-OCO-, -CONH-Z-CO -, -CONH-Z-O-, -CONH-Z-S-, -CONMe-Z-, -CONMe-Z-OCO-, CONMe-Z-O-, and the like.

  Here, as Z, alkylene such as methylene and ethylene, branched alkylene such as isopropylidene, ether group-containing alkylene such as polyethylene oxide, branched ether group-containing alkylene such as propylene oxide, arylene such as phenylene and biphenylene, and the above structure Examples include arylene and aralkylene represented by the formula.

Specific examples of A ₁ include groups having the following structural formulas.

Specific examples of A ₂ include ethylene, propylene, —CH═CH—, and groups represented by the following structural formula.

  Specific examples of the styrene derivative represented by the general formula (1) include compounds represented by the following structural formula (1), but the present invention is not limited to these.

  Specific examples of the styrene derivative represented by the general formula (2) include compounds represented by the following structural formulas (2) to (5), but the present invention is not limited to these. .

-Third embodiment-
The 3rd aspect of the styrene derivative in this invention is represented by either the following general formula (3) and the following general formula (4).

However, the general formula (3) and general formula (4), R ₅ and R ₇ represent a hydrogen atom or a methyl group. R ₆ represents any one selected from the group consisting of an alkyl group, an aryl group, and a heterocyclic residue, which may have a substituent. R ₈ and R ₉ each independently represents a functional group containing any one of a hydrogen atom, a halogen atom, a straight chain, a branched chain and a cyclic group. X ₃ represents any linking chain selected from an alkylene chain, an arylene chain, —COO—, —OCO—, —CONR ₁₀ —, —COO—R ₁₁ —, and —CONR ₁₂ —R ₁₃ —. X ₄ represents any linking chain selected from an alkylene chain, an arylene chain, —COO—, —OCO—, —CONR ₁₄ —, —COO—R ₁₅ —, and —CONR ₁₆ —R ₁₇ —. R ₁₀ , R ₁₂ , R _14, and R ₁₆ represent any one selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, and a heteryl group. The alkyl group, aryl group, aralkyl group, and heteryl group may each have a branch. R ₁₁ , R ₁₃ , R ₁₅ and R ₁₇ represent a divalent linking group, may have a branch and a substituent, or may be a single bond. A ₃ represents a trivalent organic linking group capable of forming an imide ring by a ring-closing reaction between —COOH— and —CONH—R ₆ . A ₄ represents a divalent organic linking group capable of forming an imide ring by a ring-closing reaction between —COOH— and —NHCO—.

In general formula (3) and general formula (4), R ₆ has the same meaning as R ₂ , and R ₈ and R ₉ have the same meaning as R ₄ and R ₅ . Specific examples of R ₆ include, for example, methyl, ethyl, allyl, benzyl and the like. Specific examples of R ₈ and R ₉ include a hydrogen atom, a chlorine atom, and a methyl group. Specific examples of A ₃ and A ₄ include those similar to A ₁ and A ₂ . In R ₁₀ , R ₁₂ , R _14, and R ₁₆ , the alkyl group, aryl group, aralkyl group, and heteryl group which may have a branch are further an alkyl group having 1 to 4 carbon atoms, or a group having 1 to 6 carbon atoms. It may be substituted with an alkoxy group, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a hydroxyl group, a halogen atom, or a combination of two or more thereof. Specific examples of R ₁₀ , R ₁₂ , R ₁₄ and R ₁₆ include, for example, methyl, ethyl, butyl, octyl, allyl, benzyl, hydroxyethyl, phenyl, and the like.
In R ₁₁ , R ₁₃ , R _15, and R ₁₇ , an alkylene group, an arylene group, and an aralkylene group that may have a branch are also represented by —O—, —S—, —OCO—, —COO—, It may be through a group selected from the group of —CONH—, —NHCO—, —SO ₂ —, —SO ₂ NH—, and —NHSO ₂ — or a combination of two or more thereof, and further has 1 to 4 carbon atoms. Or an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a halogen atom, or a combination of two or more thereof. Specific examples of R ₁₁ , R ₁₃ , R ₁₅ and R ₁₇ include methylene, ethylene, propylene, phenylene, m-xylene, p-xylene and the like.

Specific examples of X ₃ include methylene, ethylene, —OCO—, —CONH—, —COO—, and the like. Specific examples of X ₄ include methylene, ethylene, —COOCH ₂ CH ₂ CH ₂ —, OCOCH ₂ CH ₂ —, and the like.

  Specific examples of the styrene derivative represented by the general formula (3) or the general formula (4) include the following compounds, but the present invention is not limited thereto.

-Fourth aspect-
The 4th aspect of the styrene derivative in this invention is represented by either the following general formula (5) and the following general formula (6), and is used for the synthesis | combination of the polymer formation material contained in pattern formation material.

In the general formula, R ₁₈ and R ₂₀ represents a hydrogen atom or a methyl group. R ₁₉ represents a functional group including any of linear, branched and cyclic. R ₂₁ and R ₂₂ each independently represents a functional group containing any one of a hydrogen atom, a halogen atom, a straight chain, a branched chain and a cyclic group. X ₅ and X _{6 each} represent a single bond or an organic linking chain. A ₅ represents a trivalent organic linking group capable of forming an imide ring by a ring-closing reaction between —COOH— and —CONH—R ₁₉ . A ₆ represents a divalent organic linking group capable of forming an imide ring by a ring-closing reaction between —COOH— and —NHCO—.

In the general formulas (5) and (6), specific examples of R ₁₉ include the same as those described for R ₂ . Specific examples of R ₂₁ and R ₂₂ include the same as R ₄ and R ₅ . Specific examples of A ₅ and A ₆ include those similar to A ₁ and A ₂ .

Specific examples of X ₅ include the same organic linking groups as those described above for X ₁ and X ₃ . Specific examples of X ₆ include the same organic linking groups as those described for X ₂ and X ₄ .

  Specific examples of the styrene derivative represented by the general formula (5) or the general formula (6) include the following structural formulas (7) to (8) in addition to the structural formulas (2) to (5). In the present invention, the compounds are not limited to these.

(polymer)
Examples of the polymer in the present invention include the following first to third embodiments. Hereinafter, these polymers will be described.
-First embodiment-
The 1st aspect of the polymer in this invention comprises the styrene derivative which has an amic acid structure in a molecule | numerator in a structural unit.
As a method for producing the polymer, a styrene derivative having an amic acid structure in the molecule is used to close maleamic acid by heating to form an imide structure. A polymer having excellent chemical properties can be obtained.

-Second aspect-
In the second aspect of the polymer in the present invention, any one of the following general formula (7) and the following general formula (8) containing the styrene derivative according to any one of the general formulas (1) to (4) as a structural unit. It is represented by
As a method for producing the polymer, by using the styrene derivative according to any one of the general formulas (1) to (4), the maleamic acid is cyclized by heating to form an imide structure, thereby providing excellent insulation. Thus, it becomes insoluble in alkali and excellent in chemical resistance, and a polymer represented by any one of the following general formula (7) and the following general formula (8) can be obtained.

In the general formula, R ₂₃ and R ₂₅ represents a hydrogen atom or a methyl group. R ₂₄ represents a functional group including any of linear, branched and cyclic. R ₂₆ and R ₂₇ each independently represents a functional group containing any one of a hydrogen atom, a halogen atom, a straight chain, a branched chain and a cyclic group. X ₇ and X ₈ represent an organic linking chain. A ₇ represents a trivalent organic linking group capable of forming an imide ring by a ring-closing reaction between —COOH— and —CONH—R ₂₄ . A ₈ represents a divalent organic linking group capable of forming an imide ring by a ring-closing reaction between —COOH— and —NHCO—.

-Third embodiment-
A third aspect of the polymer in the present invention includes the styrene derivative according to any one of the general formulas (5) to (6) as a constituent unit, and includes any one of the following general formula (9) and the following general formula (10). It is used as a pattern forming material.
As a method for producing the polymer, by using the styrene derivative according to any one of the general formulas (5) to (6), the maleamic acid is cyclized by heating to form an imide structure, thereby providing excellent insulation. The polymer is insoluble in alkali and excellent in chemical resistance, and a polymer represented by any one of the following general formula (9) and the following general formula (10) can be obtained.

In the general formula, R ₂₈ and R ₃₀ represents a hydrogen atom or a methyl group. R ₂₉ represents a functional group including any of linear, branched and cyclic. R ₃₁ and R ₃₂ each independently represents a functional group containing any one of a hydrogen atom, a halogen atom, a straight chain, a branched chain and a cyclic group. X ₉ and X ₁₀ represent either a single bond or an organic linking chain. A ₉ represents a trivalent organic linking group capable of forming an imide ring by a ring-closing reaction between —COOH— and —CONH—R ₂₉ . A ₁₀ represents a divalent organic linking group capable of forming an imide ring by a ring-closing reaction between —COOH— and —NHCO—.

  The polymer may be a homopolymer (polymer) obtained by polymerizing only one of the styrene derivatives, or may be a copolymer (copolymer) obtained by polymerizing two or more selected from the styrene derivatives. Alternatively, it may be a copolymer obtained by polymerizing at least one selected from the styrene derivatives and another monomer.

The polymer is alkali-soluble at room temperature, and preferably becomes an alkali-resistant compound by heating to 50 ° C to 250 ° C. Here, room temperature represents room temperature 25 ° C. By making it alkali-soluble at room temperature, development with an alkaline developer is easy after exposure, and the cured film formed by heating after development becomes alkali-resistant, resulting in chemical resistance and film hardness of the cured film. In addition, it is possible to obtain a permanent pattern excellent in insulating properties.
When the heating temperature is less than 50 ° C., the imide ring is not sufficiently formed and the alkali resistance after curing may not be improved. When the heating temperature exceeds 250 ° C., the heating work takes time, The cured film may become brittle, and the film hardness and insulation may not be improved.

(Pattern forming material)
The pattern forming material of the present invention includes at least a polymer derived from the styrene derivative, and further includes other components appropriately selected as necessary.
Preferably, the support has at least a photosensitive layer containing at least a polymer derived from the styrene derivative, and may have other layers appropriately selected.

<Photosensitive layer>
The photosensitive layer comprises (A) at least a polymer (binder) derived from the styrene derivative, (B) a polymerizable compound, and (C) a photopolymerization initiator, and preferably contains a thermal crosslinking agent. Further, it contains other components such as coloring pigments, extender pigments, thermal polymerization inhibitors and surfactants as necessary.

[(A) Binder]
The binder preferably has at least a polymer derived from the styrene derivative of the present invention and is soluble in an alkaline aqueous solution.
As a binder which shows solubility with respect to the alkaline aqueous solution, for example, those having an acidic group are preferably exemplified.

The binder comprises at least a maleamic acid unit A having a maleic acid half amide structure and a unit B not having the maleic acid half amide structure, represented by any of the following structural formulas (9) and (10): It is preferably a maleamic acid copolymer.
The unit B may be one type or two or more types. For example, when the unit A is one type, when the unit B is one type, the maleamic acid copolymer means a binary copolymer, and the unit B is 2 When it is a seed, the maleamic acid-based copolymer means a terpolymer.
As the unit B, a combination of an aryl group which may have a substituent and a vinyl monomer described later is preferably exemplified.

However, in said structural formula (9) and (10), R _<33> , R _<35 > represents either a hydrogen atom or a methyl group. R ₃₄ represents a functional group including any of linear, branched and cyclic. R ₃₆ and R ₃₇ each independently represents a functional group containing any one of a hydrogen atom, a halogen atom, a straight chain, a branched chain and a cyclic group. X ₁₁ and X ₁₂ have the same meanings as X ₇ and X ₈ described above. A ₁₁ has the same meaning as A ₉ described above, and A ₁₂ has the same meaning as A ₁₀ described above.
Moreover, x and y represent the mole fraction of a repeating unit, for example, when the said unit B is 1 type, x is 10-100 mol% and y is 90-0 mol%.
If the x is less than 10 mol% or the y exceeds 90 mol%, the development time during alkali development may become longer, and further development may be impossible.

In the structural formulas (9) and (10), as R _{38 and} R ₄₁ , for example, (—COOR ₄₄ ), (—CONR ₄₅ R ₄₆ ), an aryl group which may have a substituent, (— And substituents such as OCOR ₄₇ ), (—OR ₄₈ ) and (—COR ₄₉ ). Wherein said R ₄₄ to R ₄₉ is a hydrogen atom (-H), which may have a substituent alkyl group, an aryl group and aralkyl group. The alkyl group, aryl group and aralkyl group may have a cyclic structure or a branched structure.
Examples of R _{44 to} R ₄₉ include methyl, ethyl, normal-propyl, iso-propyl, normal-butyl, iso-butyl, secondary butyl, tertiary butyl, pentyl, allyl, normal-hexyl, cyclohexyl, Examples include 2-ethylhexyl, dodecyl, methoxyethyl, phenyl, methylphenyl, methoxyphenyl, benzyl, phenethyl, naphthyl, and chlorophenyl.
Specific examples of R ₃₈ and R ₄₁ include benzene derivatives such as phenyl, α-methylphenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl and 2,4-dimethylphenyl; normal-propyl Examples include oxycarbonyl, normal-butyloxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, normal-butyloxycarbonyl, normal-hexyloxycarbonyl, 2-ethylhexyloxycarbonyl, methyloxycarbonyl and the like.

Examples of R ₃₄ 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 ₃₄ 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-fur Rophenyl) ethyl, 4-fluoro α, α-dimethylphenethyl, 2-methoxybenzyl, 3-methoxybenzyl, 4-methoxybenzyl, 2-ethoxybenzyl, 2-methoxyphenethyl, 3-methoxyphenethyl, 4-methoxyphenethyl, methyl , Ethyl, propyl, 1-propyl, butyl, tertiary butyl, secondary 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 vinyl monomer contained in the preferred combination of the unit B is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include normal-propyl acrylate (Tg of homopolymer = −37 ° C.), normal -Butyl acrylate (homopolymer Tg = -54 ° C), pentyl acrylate, or hexyl acrylate (homopolymer Tg = -57 ° C), normal-butyl methacrylate (homopolymer Tg = -24 ° C), normal-hexyl methacrylate (Homopolymer Tg = −5 ° C.), methyl methacrylate (homopolymer Tg = 105 ° C.), cyclohexyl methacrylate (homopolymer Tg = 83 ° C.), isobornyl methacrylate, adamantyl methacrylate, and the like. These may be used individually by 1 type and may use 2 or more types together.
Further, the unit B may contain an aromatic vinyl monomer. The aromatic vinyl monomer is not particularly limited and may be appropriately selected depending on the intended purpose. However, the surface hardness of the photosensitive layer formed using the photosensitive composition of the present invention may be increased. A compound having a homopolymer glass transition temperature (Tg) of 80 ° C. or higher is preferable, and a compound having a temperature 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.

  The molecular weight of the binder is preferably 3,000 to 500,000, and 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.

  As described above, the binder includes at least the polymer derived from the styrene derivative of the present invention, and may be formed of the polymer derived from the styrene derivative alone or in combination with a polymer other than the polymer derived from the styrene derivative. May be. In any case, the total binder solid content in the pattern forming material solid content is preferably 5 to 70 mass%, more preferably 10 to 50 mass%. 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 intended purpose. A compound is preferable, and 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.

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

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

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

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

  Wakabayashi et al., Bull. Chem. Soc. As a compound described in Japan, 42, 2924 (1969), for example, 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-chlorophenyl) -4,6 -Bis (trichloromethyl) -1,3,5-triazine, 2- (4-tolyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxyphenyl)- 4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,4-dichlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2, 4,6-tris (trichloromethyl) -1,3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2-normal-nonyl-4,6- Bis (Trichlorme Le) -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-normal-butoxystyryl) -1,3,4-oxadiazole, 2-tripromemethyl-5-styryl-1,3,4 Oxadiazole and the like).

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

  Further, as photopolymerization initiators other than the above, acridine derivatives (for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N-phenylglycine, and the like, polyhalogen compounds (for example, Carbon tetrabromide, phenyltribromomethylsulfone, phenyltrichloromethylketone, etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) ) Coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis (5 , 7-di-normal-propoxycoumarin), 3,3′-carboni Rubis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3 -(3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, JP-A-5-19475, JP-A-7-271028, JP-A-2002- 363206, JP-A-2002-363207, JP-A-2002-363208, JP-A-2002-363209, etc.), amines (for example, ethyl 4-dimethylaminobenzoate, 4-dimethylamino) Normal-butyl benzoate, phenethyl 4-dimethylaminobenzoate 4-dimethylaminobenzoic acid 2-phthalimidoethyl, 4-dimethylaminobenzoic acid 2-methacryloyloxyethyl, pentamethylenebis (4-dimethylaminobenzoate), phenethyl of 3-dimethylaminobenzoic acid, pentamethylene ester, 4 -Dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylaminobenzyl alcohol, ethyl (4-dimethylaminobenzoyl) acetate, 4-piperidinoacetophenone, 4-dimethylaminobenzoin, N, N-dimethyl -4-Toluidine, N, N-diethyl-3-phenetidine, tribenzylamine, dibenzylphenylamine, N-methyl-N-phenylbenzylamine, 4-bromo-N, N-dimethylaniline, tridodecyl Amines, aminofluorans (ODB, ODBII, etc.), crystal violet lactone, leuco crystal violet, etc.), acylphosphine oxides (for example, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, etc.), metallocenes (for example, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6- Difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), etc.), JP-A-53-133428 Gazette, Japanese Patent Publication No.57-1819 The 57-6096 and JP include compounds described in U.S. Patent No. 3,615,455.

  Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzolphenone, benzophenonetetracarboxylic acid or tetramethyl ester thereof, 4,4′-bis (dialkylamino) benzophenone (for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′- Bisdicyclohexylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4′-dimethylamino Nzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-tertiarybutylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chloro -Thioxanthone, 2,4-diethylthioxanthone, fluorenone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether) , Benzoin propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloro acridone, N- methyl acridone, N- butyl acridone, N- butyl - such as chloro acrylic pyrrolidone.

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

  The sensitizer is not particularly limited and may be appropriately selected from known sensitizers. For example, known polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, , Fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, indocarbocyanine, thiacarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, Methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squariums (eg, squalium), acridones (eg, acridone, chloroacrine) Don, N-methylacridone, N-butylacridone, N-butyl-chloroacridone, etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl)- 7- (1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3 '-Carbonylbis (5,7-di-normal-propoxycoumarin), 3,3'-carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7- Diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminoc Examples thereof include phosphorus, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, and others, and JP-A-5-19475, JP-A-7-271028, JP 2002-363206, JP-A-2002-363207, JP-A-2002-363208, JP-A-2002-363209, and the like.

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

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

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

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

(Thermal crosslinking agent)
The thermal cross-linking agent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an epoxy resin compound having at least two oxirane groups in one molecule and an oxetane compound having at least two oxetanyl groups in one molecule can be used.
Examples of the epoxy resin compound include a bixylenol type or biphenol type epoxy resin (“YX4000; manufactured by Japan Epoxy Resin Co., Ltd.”) or a mixture thereof, a heterocyclic epoxy resin having an isocyanurate skeleton (“TEPIC; Nissan”). Chemical Industries, "Araldite PT810; Ciba Specialty Chemicals, etc.), bisphenol A type epoxy resin, novolac type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, glycidylamine type epoxy Resin, hydantoin type epoxy resin, alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol S type epoxy resin, bisphenol A novolac type epoxy resin, tetraphenylolethane type Poxy resin, glycidyl phthalate resin, tetraglycidyl xylenoylethane resin, naphthalene group-containing epoxy resin (“ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.”, “HP-4032, EXA-4750, EXA-4700; large Nippon Ink Chemical Co., Ltd. ”), epoxy resins having a dicyclopentadiene skeleton (“ HP-7200, HP-7200H; manufactured by Dainippon Ink & Chemicals ”etc.), glycidyl methacrylate copolymer epoxy resin (“ CP -50S, CP-50M; manufactured by NOF Corporation, etc.), a copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, and the like, but is not limited thereto. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.

  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 or oligomers or copolymers thereof, oxetane groups and novolak resins , Poly (p-hydroxystyrene), cardo-type bisphe And ether compounds with hydroxyl groups, such as siloles, calixarenes, calixresorcinarenes, silsesquioxanes, and the like, as well as unsaturated monomers having an oxetane ring and alkyl (meth) acrylates. And a copolymer thereof.

Moreover, in order to accelerate the thermosetting of the epoxy resin compound or the oxetane compound, for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethyl Amine compounds such as benzylamine and 4-methyl-N, N-dimethylbenzylamine; quaternary ammonium salt compounds such as triethylbenzylammonium chloride; blocked isocyanate compounds such as dimethylamine; imidazole, 2-methylimidazole and 2-ethylimidazole , 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, etc. 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 S-triazine derivatives such as adducts can be used. These may be used alone or in combination of two or more. The epoxy resin compound or the oxetane compound is a curing catalyst, or any compound that can accelerate the reaction between the epoxy resin compound and the oxetane compound and a carboxyl group. May be.
Solid content in the said pattern formation material solid content of the said epoxy resin, the said oxetane compound, and the compound which can accelerate | stimulate thermosetting with these and carboxylic acid is 0.01-15 mass% normally.

  Further, as the thermal crosslinking agent, a polyisocyanate compound described in JP-A-5-9407 can be used, and the polyisocyanate compound is aliphatic, cycloaliphatic or aromatic containing at least two isocyanate groups. It may be derived from a group-substituted aliphatic compound. Specifically, 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 .; bifunctional isocyanates, trimethylolpropane, pentalysitol, glycerin, etc. An alkylene oxide adduct of the polyfunctional alcohol and an adduct of the bifunctional isocyanate; hexamethylene diisocyanate, hexamethylene-1,6-diisocyanate Cyclic trimers, such as preparative and derivatives thereof; and the like.

Furthermore, for the purpose of improving the storage stability of the pattern forming material of the present invention, a compound obtained by reacting a blocking agent with the isocyanate group of the polyisocyanate and its derivative may be used.
Examples of the isocyanate group blocking agent include alcohols such as isopropanol and tertiary butanol; lactams such as ε-caprolactam; phenol, cresol, p-tertiary butylphenol, p-secondary butylphenol, p-secondary amylphenol, and p-octylphenol. Phenols such as p-nonylphenol; heterocyclic hydroxyl compounds such as 3-hydroxypyridine and 8-hydroxyquinoline; active methylene compounds such as dialkylmalonate, methylethylketoxime, acetylacetone, alkylacetoacetate oxime, acetoxime and cyclohexanone oxime And so on. 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 hexamethoxymethylol melamine is particularly preferable in that it has good storage stability and is effective in improving the surface hardness of the photosensitive layer or the film strength itself of the cured film.

  1-40 mass% is preferable and, as for solid content in the said pattern formation material solid content of the said thermal crosslinking agent, 3-20 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 40% by mass, the developability and the exposure sensitivity may be lowered.

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

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

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

-Color pigment-
There is no restriction | limiting in particular as said coloring pigment, According to the objective, it can select suitably, For example, Victoria pure blue BO (CI. 42595), auramine (CI. 41000), fat black HB (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.

  The solid content of the color pigment in the solid content of the pattern forming material can be determined in consideration of the exposure sensitivity and resolution of the photosensitive layer during permanent pattern formation, and varies depending on the type of the color pigment. However, generally 0.05-10 mass% is preferable, and 0.1-5 mass% is more preferable.

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

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

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

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

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

  The method for preparing the pattern forming material is not particularly limited and can be appropriately selected from known methods according to the purpose. For example, a polymerization mechanism such as a radical polymerization method, a cation polymerization method, an anion polymerization method, etc. Can be prepared by a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, a dropping polymerization method, or the like. Among these, a radical polymerization method is preferable. In the present invention, since a polymer using a styrene derivative is contained in the pattern forming material, a special polymerization method is not required, the composition of the pattern forming material is not limited, and is appropriately selected according to the purpose. Therefore, the pattern forming material can be easily prepared. And maleamic acid is ring-closed by heating and forms an imide structure, thereby having excellent alkali resistance.

As an example of a preparation method using the radical polymerization method, a general-purpose radical polymerization initiator is added to an organic solvent containing general-purpose monomers such as styrene and methyl methacrylate, and the copolymer is prepared by polymerization. can do. In this case, other addition polymerizable unsaturated compounds can be added and prepared by the same method as described above.
Apart from the preparation method, the copolymer can also be prepared by photopolymerization in the presence of a photosensitizer or photoinitiator or by polymerization using radiation or heat as an energy source.

  The pattern forming material of the present invention has a low surface tackiness, good laminating properties and handling properties, and contains a polymer using a styrene derivative that closes to an imide ring by heat, so that it is soluble in alkali before development. It has excellent developability and storage stability, and is excellent in chemical resistance such as alkali resistance, surface hardness, heat resistance and insulation after development. For this reason, it is widely used for the formation of permanent patterns such as printed wiring boards (multilayer wiring boards, build-up wiring boards, etc.), color filters, pillar materials, rib materials, spacers, partition walls, and other display members, holograms, micromachines, and proofs. In particular, it can be suitably used for the permanent pattern and the method for forming the same according to the present invention.

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

[Support]
The support is not particularly limited and may be appropriately selected depending on the intended purpose. However, it is preferable that the photosensitive layer can be peeled off and that light transmittance is good, and that the surface is smooth. 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, a cellulose film, and a nylon film, are mentioned, Among these, polyethylene terephthalate is particularly preferable. These may be used alone or in combination of two or more.
As the support, for example, the support described in JP-A-4-208940, JP-A-5-80503, JP-A-5-173320, JP-A-5-72724, or the like is used. You can also.

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

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

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

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

  As the method for forming the photosensitive layer, a pattern forming material solution is prepared by dissolving, emulsifying or dispersing the pattern forming material of the present invention in water or a solvent on the support, and directly applying the solution. And a method of laminating by drying.

  The solvent for the pattern forming material solution is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include methanol, ethanol, normal-propanol, isopropanol, normal-butanol, secondary butanol, and normal-hexanol. Alcohols; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone; ethyl acetate, butyl acetate, acetic acid-normal-amyl, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxypropyl Esters such as acetate; aromatic hydrocarbons such as toluene, xylene, benzene and ethylbenzene; carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, salt Halogenated hydrocarbons such as methylene and monochlorobenzene; ethers such as tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethylsulfoxide, Examples include sulfolane. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.

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

〔Protective film〕
The protective film has a function of preventing and protecting the photosensitive layer from being stained and damaged.
There is no restriction | limiting in particular as a location provided in the said photosensitive film of the said protective film, Although it can select suitably according to the objective, Usually, it is provided on the said photosensitive layer.
Examples of the protective film include those used for the support, silicone paper, polyethylene, paper laminated with polypropylene, polyolefin or polytetrafluoroethylene sheet, and among these, polyethylene film, Polypropylene film is preferred.
There is no restriction | limiting in particular as thickness of the said protective film, Although it can select suitably according to the objective, For example, 5-100 micrometers is preferable and 8-30 micrometers is more preferable.
When the protective film is used, it is preferable that the adhesive force A between the photosensitive layer and the support and the adhesive force B between the photosensitive layer and the protective film satisfy the relationship of adhesive force A> adhesive force B.
Examples of the combination of the support and the protective film (support / protective film) include polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate, and the like. . Moreover, the relationship of the above adhesive forces can be satisfy | filled by surface-treating at least any one of a support body and a protective film. The surface treatment of the support may be performed in order to increase the adhesive force with the photosensitive layer. For example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow treatment Examples thereof include 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, and when it exceeds 1.4, it is difficult to wind into a good roll. Sometimes.

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

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

The photosensitive film using the pattern forming material of the present invention has a small surface tackiness, good laminating properties and handling properties, is alkali-soluble before development, has excellent developability and storage stability, and has alkali resistance after development. It has a photosensitive layer on which a pattern forming material excellent in chemical resistance, surface hardness, heat resistance, insulation and the like is laminated. For this reason, it can be widely used for the formation of permanent patterns such as printed wiring boards, color filters, pillar materials, rib materials, spacers, partition walls, holograms, micromachines, proofs, and the like. It can be suitably used for the forming method.
In particular, since the photosensitive film of the present invention has a uniform thickness, the film is more precisely laminated on the substrate when forming a permanent pattern.

(Permanent pattern and permanent pattern forming method)
The permanent pattern of the present invention is obtained by the permanent pattern forming method of the present invention.
The permanent pattern forming method of the present invention includes at least performing exposure on the pattern forming material of the present invention.
Specifically, in the first aspect of the method for forming a permanent pattern of the present invention, the pattern forming material of the present invention is applied to the surface of a substrate, dried to form a photosensitive layer, and then exposed. develop.
Further, in the permanent pattern forming method of the present invention, as a second aspect, the photosensitive film using the pattern forming material of the present invention is laminated on the surface of the substrate under at least one of heating and pressurization. , Expose and develop.
Hereinafter, the details of the permanent pattern of the present invention will be clarified through the description of the method for forming a permanent pattern of the present invention.

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

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

-Laminate-
There is no restriction | limiting in particular as a formation method of the laminated body of the said 1st aspect, Although it can select suitably according to the objective, The photosensitive material formed by apply | coating and drying the said pattern formation material on the said base material. It is preferable to laminate the layers.
The application and drying method is not particularly limited and may be appropriately selected depending on the purpose. For example, the application of the pattern forming material solution and the formation of the photosensitive layer in the photosensitive film may be performed. For example, a method of applying the pattern forming material solution using a spin coater, a slit spin coater, a roll coater, a die coater, a curtain coater, or the like can be used.

There is no restriction | limiting in particular as a formation method of the laminated body of the said 2nd aspect, Although it can select suitably according to the objective, At least any one of a heating and pressurization of the said photosensitive film on the said base material is carried out. It is preferable to laminate while performing. In addition, when the said photosensitive film has the said protective film, it is preferable to peel this protective film and to laminate | stack so that the said photosensitive layer may overlap with the said base material.
There is no restriction | limiting in particular as said heating temperature, Although it can select suitably according to the objective, For example, 70-130 degreeC is preferable and 80-110 degreeC is more preferable.
There is no restriction | limiting in particular as a pressure of the said pressurization, Although it can select suitably according to the objective, For example, 0.01-1.0 MPa is preferable and 0.05-1.0 MPa is more preferable.

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

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

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

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

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

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

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

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

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

The light modulation means preferably includes pattern signal generation means for generating a control signal based on pattern information to be formed. In this case, the light modulation unit modulates light according to the control signal generated by the pattern signal generation unit.
There is no restriction | limiting in particular as said control signal, According to the objective, it can select suitably, For example, a digital signal is mentioned suitably.

Hereinafter, an example of the light modulation means will be described with reference to the drawings.
As shown in FIG. 1, in the DMD 50, a large number (eg, 1024 × 768) of micromirrors (micromirrors) 62, each constituting a pixel (pixel), are arranged in a lattice pattern on an SRAM cell (memory cell) 60. It is a mirror device arranged. In each pixel, a micromirror 62 supported by a support column is provided at the top, and a material having high reflectance such as aluminum is deposited on the surface of the micromirror 62. The reflectance of the micromirror 62 is 90% or more, and the arrangement pitch is 13.7 μm as an example in both the vertical and horizontal directions. A silicon gate CMOS SRAM cell 60 manufactured in a normal semiconductor memory manufacturing line is disposed directly below the micromirror 62 via a support including a hinge and a yoke, and the entire structure is monolithic. ing.

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

  FIG. 1 shows an example of a state in which a part of the DMD 50 is enlarged and the micromirror 62 is controlled to + α degrees or −α degrees. The on / off control of each micromirror 62 is performed by a controller 302 (see FIG. 12) connected to the DMD 50. Further, a light absorber (not shown) is arranged in the direction in which the laser beam B reflected by the off-state micromirror 62 travels.

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

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

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

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

  In this example, as shown in FIGS. 4A and 4B, in the DMD 50, 768 sets of micromirror arrays in which 1024 micromirrors are arranged in the main scanning direction are arranged in the subscanning direction. In this example, the controller 302 (see FIG. 12) controls so that only a part of the micromirror rows (eg, 1024 × 256 rows) are driven.

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

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

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

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

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

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

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

  In addition, as shown in FIG. 5, the entire surface of the photosensitive layer 150 may be exposed by a single scan in the X direction by the scanner 162, and as shown in FIGS. After scanning the photosensitive layer 150 in the X direction, the scanner 162 is moved one step in the Y direction, and scanning in the X direction is repeated, so that the entire surface of the photosensitive layer 150 is scanned by a plurality of scans. You may make it expose. In this example, the scanner 162 includes 18 exposure heads 166. Note that the exposure head includes at least the light irradiation unit and the light modulation unit.

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

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

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

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

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

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

As shown in FIGS. 10 and 11, each of the exposure heads 166 _{11 to} 166 _mn serves as the light modulation means (spatial light modulation element that modulates each pixel) according to the pattern information. A digital micromirror device (DMD) 50 manufactured by Texas Instruments, USA is provided. The DMD 50 is connected to the controller 302 (see FIG. 12) including a data processing unit and a mirror drive control unit. The data processing unit of the controller 302 generates a control signal for driving and controlling each micromirror in the area to be controlled by the DMD 50 for each exposure head 166 based on the input pattern information. The area to be controlled will be described later. The mirror drive control unit controls the angle of the reflection surface of each micromirror of the DMD 50 for each exposure head 166 based on the control signal generated by the pattern information processing unit. The control of the angle of the reflecting surface will be described later.

  On the light incident side of the DMD 50, a fiber array light source 66 including a laser emitting section in which emission ends (light emitting points) of an optical fiber are arranged in a line along a direction corresponding to the long side direction of the exposure area 168, a fiber A lens system 67 for correcting the laser light emitted from the array light source 66 and condensing it on the DMD, and a mirror 69 for reflecting the laser light transmitted through the lens system 67 toward the DMD 50 are arranged in this order. In FIG. 10, the lens system 67 is schematically shown.

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

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

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

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

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

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

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

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

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

As a wavelength of the ultraviolet to visible light, for example, 300 to 1500 nm is preferable, 320 to 800 nm is more preferable, and 330 nm to 650 nm is particularly preferable.
As a wavelength of the said laser beam, 200-1500 nm is preferable, for example, 300-800 nm is more preferable, 330 nm-500 nm is still more preferable, 395 nm-415 nm is especially preferable.

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

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

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

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

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

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

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

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

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

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

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

  As shown in FIGS. 30 and 31, the combined laser light source is housed in a box-shaped package 40 having an upper opening together with other optical elements. The package 40 includes a package lid 41 created so as to close the opening thereof. After the deaeration process, a sealing gas is introduced, and the package 40 and the package lid 41 are closed by closing the opening of the package 40 with the package lid 41. 41. The combined laser light source is hermetically sealed in a closed space (sealed space) formed by 41.

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

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

  In FIG. 31, in order to avoid complication of the figure, only the GaN-based semiconductor laser LD7 among the plurality of GaN-based semiconductor lasers is numbered, and only the collimator lens 17 among the plurality of collimator lenses is numbered. is doing.

  FIG. 32 shows the front shape of the attachment part of the collimator lenses 11-17. Each of the collimator lenses 11 to 17 is formed in a shape obtained by cutting a region including the optical axis of a circular lens having an aspherical surface into a long and narrow plane. This elongated collimator lens can be formed, for example, by molding resin or optical glass. The collimator lenses 11 to 17 are closely arranged in the arrangement direction of the light emitting points so that the length direction is orthogonal to the arrangement direction of the light emitting points of the GaN-based semiconductor lasers LD1 to LD7 (left and right direction in FIG. 32).

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

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

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

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

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

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

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

  As the light irradiation means, the multi-cavity laser 110 or a plurality of multi-cavity lasers 110 on the heat block 100 as shown in FIG. 34 (B) has the same direction as the arrangement direction of the light emitting points 110a of each chip. A multi-cavity laser array arranged in the above can be used as a laser light source.

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

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

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

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

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

  In the above configuration, each of the laser beams B emitted from each of the plurality of light emitting points 10a of the plurality of multi-cavity lasers 110 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 condensed by the condenser lens 120 and enters the core 130a of the multimode optical fiber 130. The laser light incident on the core 130a propagates in the optical fiber, is combined into one, and is emitted.

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

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

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

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

  In the above configuration, each of the laser beams B emitted from each of the plurality of light emitting points 10a of the plurality of multicavity lasers 110 arranged on the laser blocks 180 and 182 is collimated by the collimating lens array 184 and condensed. The light is condensed by the lens 120 and enters the core 130 a of the multimode optical fiber 130. The laser light incident on the core 130a propagates in the optical fiber, is combined into one, and is emitted.

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

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

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

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

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

  In each laser module, when the coupling efficiency of the laser beams B1 to B7 to the multimode optical fiber 30 is 0.85 and each output of the GaN-based semiconductor lasers LD1 to LD7 is 30 mW, the light arranged in an array For each of the fibers 31, a combined laser beam B with an output of 180 mW (= 30 mW × 0.85 × 7) can be obtained. Therefore, the output from the laser emitting unit 68 in which the six optical fibers 31 are arranged in an array is about 1 W (= 180 mW × 6).

  In the laser emitting portion 68 of the fiber array light source 66, light emission points with high luminance are arranged in a line along the main scanning direction as described above. A conventional fiber light source that couples laser light from a single semiconductor laser to a single optical fiber has a low output, so that a desired output cannot be obtained unless multiple rows are arranged. Since the laser light source has a high output, a desired output can be obtained even with a small number of columns, for example, one column.

For example, in a conventional fiber light source in which a semiconductor laser and an optical fiber are coupled on a one-to-one basis, a laser having an output of about 30 mW (milliwatt) is usually used as the semiconductor laser, and the core diameter is 50 μm and the cladding diameter is 125 μm. Since a multimode optical fiber having a numerical aperture (NA) of 0.2 is used, if an output of about 1 W (watt) is to be obtained, 48 multimode optical fibers (8 × 6) must be bundled. Since the area of the light emitting region is 0.62 mm ² (0.675 mm × 0.925 mm), the luminance at the laser emitting portion 68 is 1.6 × 10 ⁶ (W / m ² ) and one optical fiber is used. The luminance per hit is 3.2 × 10 ⁶ (W / m ² ).

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

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

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

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

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

  When the DMD 50 is irradiated with laser light from the fiber array light source 66, the laser light reflected when the micromirror of the DMD 50 is in the on state forms an image on the exposed surface 56 of the photosensitive layer 150 by the lens systems 54 and 58. Is done. In this manner, the laser light emitted from the fiber array light source 66 is turned on / off for each pixel, and the photosensitive layer 150 is exposed in approximately the same number of pixel units (exposure area 168) as the number of pixels used in the DMD 50. Further, when the photosensitive layer 150 is moved at a constant speed together with the stage 152, the photosensitive layer 150 is sub-scanned in the direction opposite to the stage moving direction by the scanner 162, and a strip-shaped exposed area 170 is formed for each exposure head 166. Is done.

<Microlens array>
The exposure is preferably performed through the microlens array with the modulated light, and may be performed through an aperture array, an imaging optical system, or the like.

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

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

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

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

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

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

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

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

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

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

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

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

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

  In addition, when the magnitude relation of the distortion of the central part in the x direction and the y direction of the micromirror 62 is opposite to the above, the focal length in the cross section parallel to the x direction is If the microlens is composed of a toric lens that is smaller than the focal length, similarly, a higher-definition image without distortion can be exposed on the photosensitive layer 150.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[Curing process]
The permanent pattern forming method of the present invention preferably further includes a curing treatment step.
The curing treatment step is a step of performing a curing treatment on the photosensitive layer in the formed permanent pattern after the development step is performed.

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

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

Examples of the entire surface heat treatment method include a method of heating the entire surface of the laminate on which the permanent pattern is formed after the developing step. The entire surface heating increases the film strength of the surface of the permanent pattern. In the present invention, since a pattern forming material containing a polymer derived from a styrene derivative is used, maleamic acid is ring-closed by heating to form an imide structure, thereby exhibiting alkali insolubility. Therefore, a permanent pattern that is particularly excellent in chemical resistance such as alkali resistance and insulation can be obtained.
As heating temperature in the said whole surface heating, 120-250 degreeC is preferable and 120-200 degreeC is more preferable. When the heating temperature is less than 120 ° C., the film strength may not be improved by heat treatment. When the heating temperature exceeds 250 ° C., the resin in the pattern forming material is decomposed, and the film quality is weak and brittle. There is. In addition, as a styrene derivative, what is alkali-soluble at normal temperature and turns into an alkali-resistant compound by heating at 50 to 250 degreeC is preferable.
The heating time in the entire surface heating is preferably 10 to 120 minutes, and more preferably 15 to 60 minutes.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface heating, According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, IR heater etc. are mentioned.

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

  In the permanent pattern forming method of the present invention, it is preferable to form at least one of a protective film, an interlayer insulating film, and a solder resist pattern. When the permanent pattern formed by the permanent pattern forming method is the protective film or the interlayer insulating film, the wiring can be protected from external impact and bending by improving the insulating property. If it is, it will be excellent in durability that can be stored for a long time by improving chemical resistance such as alkali resistance, especially in the case of the interlayer insulating film, for example, a multilayer wiring board, a build-up wiring board, etc. It is useful for high-density mounting of semiconductors and components on

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

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

Example 1
-Preparation of pattern forming material-
A pattern forming material (solution) was prepared based on the following composition.
24.75 parts by mass of barium sulfate dispersion 35% by mass of a copolymer of styrene derivative and butyl acrylate represented by the following structural formula (11) and represented by the above structural formula (2) (molar ratio 72/28) Methyl ethyl ketone solution 13.36 parts by mass R712 (manufactured by Nippon Kayaku Co., Ltd., bifunctional acrylic monomer) 3.06 parts by mass Dipentaerythritol hexaacrylate 4.59 parts by mass IRGACURE819
(Manufactured by Ciba Specialty Chemicals) 1.98 parts by mass MW30HM
(Sanwa Chemical Co., Hexamethylated methylol melamine) 5.00 parts by mass F780F (Dainippon Ink Co., Ltd.) 30% by mass methyl ethyl ketone solution 0.066 parts by mass Hydroquinone monomethyl ether 0.024 parts by mass Methyl ethyl ketone 8.60 parts by mass

The barium sulfate dispersion is composed of 30 parts by mass of barium sulfate (manufactured by Sakai Chemical Co., Ltd., B30) and a copolymer of styrene derivative and butyl acrylate represented by the general formula (2) (molar ratio 72/28). ) Was mixed in advance with 35.71 parts by mass of 1-methoxy-2-propylacetate, and then with a motor mill M-200 (manufactured by Eiger), the diameter was 1. A 0 mm zirconia bead was used and dispersed for 3.5 hours at a peripheral speed of 9 m / s.

In the copolymer of Example 1 represented by the structural formula (11), in the structural formula (10), R ₃₅ and R ₃₇ are hydrogen atoms. X ₁₂ is methylene, and A ₁₂ is an organic linking group represented by the following structural formula (12).

  Moreover, molecular weight evaluation was performed about the copolymer of Example 1 represented by the said Structural formula (11). The results are shown in Table 3.

-Production of photosensitive film-
The obtained pattern forming material solution was applied onto a PET (polyethylene terephthalate) film having a thickness of 20 μm as the support and dried to form a photosensitive layer having a thickness of 35 μm. Next, a 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 (MVLP500, manufactured by Meiki Seisakusho Co., Ltd.) was used on the copper clad laminate while peeling off the protective film on the photosensitive film so that the photosensitive layer of the photosensitive film was in contact with the copper clad laminate. Lamination was performed to prepare a laminate in which the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) were laminated in this order.
The pressure bonding conditions were a pressure bonding temperature of 90 ° C., a pressure bonding pressure of 0.4 MPa, and a laminating speed of 1 m / min.
When the protective film on the photosensitive film was peeled off, the surface of the photosensitive layer did not have strong tackiness, and the peeling itself could be performed smoothly.

--Exposure process--
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 part of the photosensitive layer was cured.

--Development process--
After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) is peeled off from the laminate, and a 1% by mass aqueous sodium carbonate solution is used as an alkaline developer on the entire surface of the photosensitive layer on the copper clad laminate. Developed at 30 ° C. for 60 seconds to dissolve and remove uncured regions. Thereafter, it was washed with water and dried to form a permanent pattern.
In this development step, the alkali solubility before heating was evaluated. As an evaluation standard, when the uncured region can be removed by the shower development, the alkali solubility is good. The results are shown in Table 3.

-Curing process-
The entire surface of the laminate on which the permanent pattern was formed was heated at 160 ° C. for 30 minutes to cure the surface of the permanent pattern and increase the film strength. The obtained permanent pattern was evaluated for alkali resistance and solvent resistance after heating. The results are shown in Table 3.

<Alkali resistance>
The obtained the permanent pattern, using a 1% Na ₂ CO ₃ aqueous solution as an alkaline solution, a melt and floating of cured film was immersed for 2 minutes in the alkaline solution, was visually observed, based on the following criteria The alkali resistance was evaluated.
〔Evaluation criteria〕
◎: There is no melting or floating of the cured film, and the alkali resistance is particularly excellent. ○: The surface of the cured film is white, but there is no melting or floating, and the alkali resistance is excellent. △: A part of the cured film is dissolved. There is no melting or floating that is a problem in practical use, and it has alkali resistance. ×: The cured film is dissolved, and the alkali resistance is extremely poor.

With respect to the obtained permanent pattern, isopropanol was used as a solvent, and the melt and float of the cured film after being immersed in the solvent for 30 minutes were visually observed, and the solvent resistance was evaluated based on the following criteria.
〔Evaluation criteria〕
○: The cured film is not melted or floated, and the solvent resistance is high. Δ: A part of the cured film is dissolved and the solvent resistance is poor. ×: The cured film is dissolved and the solvent resistance is extremely poor.

(Example 2)
-Preparation of pattern forming material-
In Example 1, a copolymer of a styrene derivative and butyl acrylate represented by the structural formula (11) and represented by the structural formula (2) is represented by the following structural formula (13), and the structural formula A pattern forming material was prepared by the same formulation and method as in Example 1 except that the copolymer of styrene derivative and butyl acrylate represented by (3) was used. Further, the molecular weight of the copolymer represented by the following structural formula (13) was evaluated. The results are shown in Table 3.

In the copolymer of Example 2 represented by the structural formula (13), in the structural formula (10), R ₃₅ and R ₃₇ are hydrogen atoms. X ₁₂ is methylene, and A ₁₂ is —CH ₂ CH ₂ .

-Production of photosensitive film-
A photosensitive film was produced by the same method as in Example 1 using the obtained pattern forming material.

-Formation of permanent pattern-
Using the obtained photosensitive film, a permanent pattern was formed by the same method as in Example 1, and alkali solubility was evaluated during shower development. The obtained permanent pattern was evaluated for alkali resistance and solvent resistance after heating by the same method as in Example 1. The results are shown in Table 3.

(Example 3)
-Preparation of pattern forming material-
In Example 1, a copolymer of a styrene derivative represented by the structural formula (11) and the structural formula (2) and butyl acrylate is represented by the following structural formula (14), and the structural formula A pattern forming material was prepared by the same formulation and method as in Example 1 except that the copolymer of styrene derivative and butyl acrylate represented by (4) was used. Further, the molecular weight of the copolymer represented by the following structural formula (14) was evaluated. The results are shown in Table 3.

In the copolymer of Example 3 represented by the structural formula (14), in the structural formula (10), R ₃₅ and R ₃₇ are hydrogen atoms. X ₁₂ is methylene, and A ₁₂ is an organic linking group represented by the following structural formula (15).

-Production of photosensitive film-
A photosensitive film was produced by the same method as in Example 1 using the obtained pattern forming material.

-Formation of permanent pattern-
Using the obtained photosensitive film, a permanent pattern was formed by the same method as in Example 1, and alkali solubility was evaluated during shower development. The obtained permanent pattern was evaluated for alkali resistance and solvent resistance after heating by the same method as in Example 1. The results are shown in Table 3.

Example 4
-Preparation of pattern forming material-
In Example 1, a copolymer of a styrene derivative represented by the structural formula (11) and the structural formula (2) and butyl acrylate is represented by the following structural formula (16), and the structural formula A pattern forming material was prepared by the same formulation and method as in Example 1 except that the copolymer of styrene derivative represented by (5) and butyl acrylate was used. Further, the molecular weight of the copolymer represented by the following structural formula (16) was evaluated. The results are shown in Table 3.

In the copolymer of Example 4 represented by the structural formula (16), in the structural formula (10), R ₃₅ and R ₃₇ are hydrogen atoms. X ₁₂ is methylene, and A ₁₂ is an organic linking group represented by the following structural formula (17).

-Production of photosensitive film-
A photosensitive film was produced by the same method as in Example 1 using the obtained pattern forming material.

-Formation of permanent pattern-
Using the obtained photosensitive film, a permanent pattern was formed by the same method as in Example 1, and alkali solubility was evaluated during shower development. The obtained permanent pattern was evaluated for alkali resistance and solvent resistance after heating by the same method as in Example 1. The results are shown in Table 3.

(Example 5)
-Preparation of pattern forming material-
In Example 1, a copolymer of a styrene derivative and butyl acrylate represented by the structural formula (11) and represented by the structural formula (2) is represented by the following structural formula (18), and the structural formula A pattern forming material was prepared by the same formulation and method as in Example 1 except that the copolymer of styrene derivative and methyl acrylate represented by (2) was used. Further, the molecular weight of the copolymer represented by the following structural formula (18) was evaluated. The results are shown in Table 3.

In the copolymer of Example 5 represented by the structural formula (18), in the structural formula (10), R ₃₅ and R ₃₇ are hydrogen atoms. X ₁₂ is methylene, and A ₁₂ is an organic linking group represented by the structural formula (12).

-Production of photosensitive film-
A photosensitive film was produced by the same method as in Example 1 using the obtained pattern forming material.

-Formation of permanent pattern-
Using the obtained photosensitive film, a permanent pattern was formed by the same method as in Example 1, and alkali solubility was evaluated during shower development. The obtained permanent pattern was evaluated for alkali resistance and solvent resistance after heating by the same method as in Example 1. The results are shown in Table 3.

(Example 6)
-Preparation of pattern forming material-
In Example 1, a copolymer of a styrene derivative represented by the structural formula (11) and the structural formula (2) and butyl acrylate is represented by the following structural formula (19), and the structural formula A pattern forming material was prepared by the same formulation and method as in Example 1 except that the copolymer of styrene derivative and butyl acrylate represented by (1) was used. Further, the molecular weight of the copolymer represented by the following structural formula (19) was evaluated. The results are shown in Table 3.

In the copolymer of Example 6 represented by the structural formula (19), in the structural formula (9), R ₃₄ is benzyl, and R ₃₃ and R ₃₆ are hydrogen atoms. X ₁₁ is —OCO—, and A ₁₁ is an organic linking group represented by the following structural formula (20).

-Production of photosensitive film-
A photosensitive film was produced by the same method as in Example 1 using the obtained pattern forming material.

-Formation of permanent pattern-
Using the obtained photosensitive film, a permanent pattern was formed by the same method as in Example 1, and alkali solubility was evaluated during shower development. The obtained permanent pattern was evaluated for alkali resistance and solvent resistance after heating by the same method as in Example 1. The results are shown in Table 3.

(Example 7)
-Preparation of pattern forming material-
In Example 1, a copolymer of a styrene derivative and butyl acrylate represented by the structural formula (11) and represented by the structural formula (2) is represented by the following structural formula (21), and the structural formula A pattern forming material was prepared by the same formulation and method as in Example 1 except that the copolymer of styrene derivative and butyl acrylate represented by (7) was used. Further, the molecular weight of the copolymer represented by the following structural formula (21) was evaluated. The results are shown in Table 3.

In the copolymer of Example 7 represented by the structural formula (21), R ₃₅ and R ₃₇ in the structural formula (10) are hydrogen atoms. X ₁₂ is a single bond, and A ₁₂ is an organic linking group represented by the structural formula (12).

-Production of photosensitive film-
A photosensitive film was produced by the same method as in Example 1 using the obtained pattern forming material.

-Formation of permanent pattern-
Using the obtained photosensitive film, a permanent pattern was formed by the same method as in Example 1, and alkali solubility was evaluated during shower development. The obtained permanent pattern was evaluated for alkali resistance and solvent resistance after heating by the same method as in Example 1. The results are shown in Table 3.

(Example 8)
-Preparation of pattern forming material-
In Example 1, a copolymer of a styrene derivative and butyl acrylate represented by the structural formula (11) and represented by the structural formula (2) is represented by the following structural formula (22), and the structural formula A pattern forming material was prepared by the same formulation and method as in Example 1 except that the copolymer of styrene derivative and butyl acrylate represented by (8) was used. Further, the molecular weight of the copolymer represented by the following structural formula (22) was evaluated. The results are shown in Table 3.

In the copolymer of Example 8 represented by the structural formula (22), R ₃₅ and R ₃₇ in the structural formula (10) are hydrogen atoms. X ₁₂ is a single bond, and A ₁₂ is —CH ₂ CH ₂ .

-Production of photosensitive film-
A photosensitive film was produced by the same method as in Example 1 using the obtained pattern forming material.

-Formation of permanent pattern-
Using the obtained photosensitive film, a permanent pattern was formed by the same method as in Example 1, and alkali solubility was evaluated during shower development. The obtained permanent pattern was evaluated for alkali resistance and solvent resistance after heating by the same method as in Example 1. The results are shown in Table 3.

Example 9
In Example 2, except that the exposure apparatus was replaced with the pattern forming apparatus described below, the pattern forming material was evaluated for alkali solubility before heating, alkali resistance after heating, and solvent resistance, as in Example 2. Went. The results are shown in Table 3.

<< Pattern Forming Apparatus >>
27 to 32 as the light irradiating means, and 768 pairs of micromirror arrays in which 1024 micromirrors are arranged in the main scanning direction shown in FIG. 4 as the light modulating means are arranged in the sub-scanning direction. The microlens array 472 in which the DMD 50 controlled to drive only 1024 × 256 rows and the microlens 474 whose one surface is a toric surface shown in FIG. 13 are arranged in an array and the microlens A pattern forming apparatus having optical systems 480 and 482 for forming an image of light passing through the array on the photosensitive layer was used.

The toric surface of the microlens described below was used.
First, in order to correct the distortion on the exit surface of the microlens 474 as the picture element portion of the DMD 50, the strain on the exit surface was measured. The results are shown in FIG. In FIG. 14, the same height positions of the reflecting surfaces are shown connected by contour lines, and the pitch of the contour lines is 5 nm. Note that the x direction and the y direction shown in the figure are two diagonal directions of the micromirror 62, and the micromirror 62 rotates around a rotation axis extending in the y direction. 15A and 15B show the height position displacement of the reflecting surface of the micromirror 62 along the x direction and the y direction, respectively.
As shown in FIGS. 14 and 15, there is distortion on the reflection surface of the micromirror 62, and when attention is particularly paid to the center of the mirror, distortion in one diagonal direction (y direction) is different from that in the other diagonal line. It can be seen that the distortion is larger than the distortion in the direction (x direction). Therefore, it can be seen that the shape of the laser beam B collected by the microlens 55a of the microlens array 55 is distorted in this state.

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

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

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

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

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

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

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

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

(Comparative Example 1)
-Preparation of pattern forming material-
In Example 1, the copolymer of the styrene derivative represented by the structural formula (11) and the structural formula (2) and butyl acrylate was replaced with the copolymer of the following structural formula (23). Except for the above, a pattern forming material was prepared by the same formulation and method as in Example 1. Further, the molecular weight of the copolymer represented by the following structural formula (23) was evaluated. The results are shown in Table 3.

However, in the above structural formula, Ph represents a phenyl group.

-Production of photosensitive film-
A photosensitive film was produced by the same method as in Example 1 using the obtained pattern forming material.

-Formation of permanent pattern-
Using the obtained photosensitive film, a permanent pattern was formed by the same method as in Example 1, and alkali solubility was evaluated during shower development. The obtained permanent pattern was evaluated for alkali resistance and solvent resistance after heating by the same method as in Example 1. The results are shown in Table 3.

(Evaluation experiment of imide ring closure of polymer)
In the polymer using the styrene derivative of the present invention represented by the following structural formula (24), the consumption amount of COOH is determined by acid value titration with respect to the residual amount of alkali-soluble groups after heating, based on the acid value before heating. Calculated and evaluated. Moreover, the same evaluation was performed on the polymer using the styrene derivative of the present invention represented by the structural formula (21) of Example 7. Further, for comparison, the same evaluation was performed on the conventional polymer represented by the structural formula (23) of Comparative Example 1. In addition, the said heat processing (baking process) was performed at 180 degreeC for 1 hour.
The COOH consumption rate was calculated by dissolving 0.3 g of a polymer sample in 10 mL of THF and diluting this solution in 30 mL of THF and 10 mL of ion-exchanged water. This diluted solution was titrated with 0.1N NaOH aqueous solution, the residual amount of COOH was calculated from the titration amount, the COOH consumption of the sample before heating was taken as 100%, and the consumption rate of COOH was calculated from the decrease rate. . The results are shown in Table 4.
The larger the consumption rate of COOH, the smaller the remaining amount of alkali-soluble groups and the better the alkali resistance. The smaller the consumption rate, the larger the remaining amount of alkali-soluble groups and the poorer the alkali resistance.

From the results of Table 3, it was confirmed that the polymer synthesized using the styrene derivative of the present invention was alkali-soluble before heating and exhibited excellent alkali resistance and solvent resistance after heating. In addition, the photosensitive layer in the photosensitive film produced using the pattern forming material formed of this polymer is alkali-soluble and has excellent developability and storage stability during development, and is formed using the photosensitive film. The permanent pattern was confirmed to be excellent in chemical resistance such as alkali resistance and solvent resistance. Further, from the results of Table 4, the polymer using the styrene derivative of the present invention is excellent in that the residual amount of the alkali-soluble group is small, the polymerizability is excellent, and the ring closure of maleamic acid is promoted to form an imide structure. It was confirmed to show alkali resistance.
In particular, as shown in Examples 1 to 6, by using a styrene derivative in which X ₇ or X ₈ represented by the general formulas (7) to (8) is an organic linking chain, the polymer has excellent polymerizability and high quality. It was confirmed that a simple polymer can be easily synthesized. Furthermore, it was confirmed that by using this polymer as a pattern forming material, a high-definition permanent pattern having excellent insulation and the like can be easily manufactured. In Example 9, since a high-intensity light source and a pattern forming apparatus capable of high-speed modulation were used, it was confirmed that the resolution and the exposure speed were excellent, and it was confirmed that a high-definition permanent pattern was formed.

The styrene derivative of the present invention has excellent polymerizability with other monomers and can be easily synthesized by ordinary polymerization means. A polymer using this styrene derivative is soluble in alkali before heating, and after heating. Excellent alkali resistance. Further, a pattern forming material using this polymer is alkali-soluble before development and excellent in developability and storage stability, and exhibits excellent chemical resistance such as alkali resistance and insulation after development. For this reason, it is widely used for the formation of permanent patterns such as printed wiring boards (multilayer wiring boards, build-up wiring boards, etc.), color filters, pillar materials, rib materials, spacers, partition walls, and other display members, holograms, micromachines, and proofs. be able to.
In addition, the permanent pattern of the present invention has excellent surface hardness, insulation, heat resistance, etc., and can be suitably used as a protective film, an interlayer insulating film, and a solder resist pattern.

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

Explanation of symbols

LD1-LD7 GaN-based semiconductor laser 10 Heat block 11-17 Collimator lens 20 Condensing lens 30-31 Multimode optical fiber 44 Collimator lens holder 45 Condensing lens holder 46 Fiber holder 50 Digital micromirror device (DMD)
52 Lens system 53 Reflected light image (exposure beam)
54 Lens of second imaging optical system 55 Micro lens array 56 Surface to be exposed (scanning surface)
55a Microlens 57 Lens of second imaging optical system 58 Lens of second imaging optical system 59 Aperture array 64 Laser module 66 Fiber array light source 67 Lens system 68 Laser emitting unit 69 Mirror 70 Prism 73 Combination lens 74 Imaging lens 100 Heat block 110 Multi-cavity laser 111 Heat block 113 Rod lens 120 Condensing lens 130 Multimode optical fiber 130a Core 140 Laser array 144 Light irradiation means 150 Photosensitive layer 152 Stage 155a Microlens 156 Installation table 158 Guide 160 Gate 162 Scanner 164 Sensor 166 Exposure head 168 Exposure area 170 Exposed area 180 Heat block 184 Collimating lens array 302 Controller 30 4 Stage Drive Device 454 Lens System 468 Exposure Area 472 Micro Lens Array 476 Aperture Array 478 Aperture 480 Lens System

Claims (13)

  A styrene derivative having an amic acid structure in the molecule. A styrene derivative represented by any one of the following general formula (1) and the following general formula (2).
However, in said general formula (1) and general formula (2), R < ₁ > and R < ₃ > represents either a hydrogen atom or a methyl group. R ₂ represents a functional group including any of linear, branched and cyclic. R ₄ and R ₅ each independently represents a functional group containing any one of a hydrogen atom, a halogen atom, a straight chain, a branched chain and a cyclic group. X ₁ and X ₂ represent an organic connecting chain. A ₁ represents a trivalent organic linking group capable of forming an imide ring by a ring-closing reaction between —COOH— and —CONH—R ₂ . A ₂ represents a divalent organic linking group capable of forming an imide ring by a ring-closing reaction between —COOH— and —NHCO—. A styrene derivative represented by any one of the following general formula (3) and the following general formula (4).
However, the general formula (3) and general formula (4), R ₅ and R ₇ represent a hydrogen atom or a methyl group. R ₆ represents any one selected from the group consisting of an alkyl group, an aryl group, and a heterocyclic residue, which may have a substituent. R ₈ and R ₉ each independently represents a functional group containing any one of a hydrogen atom, a halogen atom, a straight chain, a branched chain and a cyclic group. X ₃ represents any linking chain selected from an alkylene chain, an arylene chain, —COO—, —OCO—, —CONR ₁₀ —, —COO—R ₁₁ —, and —CONR ₁₂ —R ₁₃ —. X ₄ represents any linking chain selected from an alkylene chain, an arylene chain, —COO—, —OCO—, —CONR ₁₄ —, —COO—R ₁₅ —, and —CONR ₁₆ —R ₁₇ —. R ₁₀ , R ₁₂ , R _14, and R ₁₆ represent any one selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, and a heteryl group. The alkyl group, aryl group, aralkyl group, and heteryl group may each have a branch. R ₁₁ , R ₁₃ , R ₁₅ and R ₁₇ represent a divalent linking group, may have a branch and a substituent, or may be a single bond. A ₃ represents a trivalent organic linking group capable of forming an imide ring by a ring-closing reaction between —COOH— and —CONH—R ₆ . A ₄ represents a divalent organic linking group capable of forming an imide ring by a ring-closing reaction between —COOH— and —NHCO—. A styrene derivative represented by any one of the following general formula (5) and the following general formula (6) and used for the synthesis of a polymer forming material contained in a pattern forming material.
In the general formula, R ₁₈ and R ₂₀ represents a hydrogen atom or a methyl group. R ₁₉ represents a functional group including any of linear, branched and cyclic. R ₂₁ and R ₂₂ each independently represents a functional group containing any one of a hydrogen atom, a halogen atom, a straight chain, a branched chain and a cyclic group. X ₅ and X ₆ represent either a single bond or an organic linking chain. A ₅ represents a trivalent organic linking group capable of forming an imide ring by a ring-closing reaction between —COOH— and —CONH—R ₁₉ . A ₆ represents a divalent organic linking group capable of forming an imide ring by a ring-closing reaction between —COOH— and —NHCO—.   The polymer characterized by including the styrene derivative which has an amic acid structure in the molecule | numerator of Claim 1 in a structural unit. A polymer comprising the styrene derivative according to any one of claims 2 to 3 as a constituent unit and represented by any one of the following general formula (7) and the following general formula (8).
In the general formula, R ₂₃ and R ₂₅ represents a hydrogen atom or a methyl group. R ₂₄ represents a functional group including any of linear, branched and cyclic. R ₂₆ and R ₂₇ each independently represents a functional group including any of linear, branched and cyclic. X ₇ and X ₈ represent an organic linking chain. A ₇ represents a trivalent organic linking group capable of forming an imide ring by a ring-closing reaction between —COOH— and —CONH—R ₂₄ . A ₈ represents a divalent organic linking group capable of forming an imide ring by a ring-closing reaction between —COOH— and —NHCO—. A polymer comprising the styrene derivative according to claim 4 in a structural unit, represented by any one of the following general formula (9) and the following general formula (10), and used as a pattern forming material.
In the general formula, R ₂₈ and R ₃₀ represents a hydrogen atom or a methyl group. R ₂₉ represents a functional group including any of linear, branched and cyclic. R ₃₁ and R ₃₂ each independently represents a functional group including any of linear, branched and cyclic. X ₉ and X ₁₀ represent either a single bond or an organic linking chain. A ₉ represents a trivalent organic linking group capable of forming an imide ring by a ring-closing reaction between —COOH— and —CONH—R ₂₉ . A ₁₀ represents a divalent organic linking group capable of forming an imide ring by a ring-closing reaction between —COOH— and —NHCO—.   The polymer according to any one of claims 5 to 7, which is alkali-soluble at room temperature and becomes an alkali-resistant compound when heated to 50 ° C to 250 ° C.   A method for producing a polymer according to any one of claims 5 to 6, wherein the styrene structure according to any one of claims 1 to 3 is used to form an imide structure by heating. Production method.   A method for producing a polymer for use in the pattern forming material according to claim 7, wherein the styrene structure according to claim 4 is used to form an imide structure by heating.   A pattern forming material comprising at least the polymer according to claim 5.   The pattern forming material according to claim 11, comprising at least exposing the pattern forming material. A permanent pattern formed by the pattern forming method according to claim 12.