JP2006350038A - Pattern forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pattern forming method for elaborately shaping a resist pattern after developed, removing a residue of the resist, forming a permanent pattern such as a wiring pattern with high definition and high efficiency, and achieving high resolution and high adhesiveness between a substrate and a photosensitive layer without causing chipping, peeling or swelling in a crosslinked portion (cured film) of the resist. <P>SOLUTION: The pattern forming method is carried out by using a pattern forming material having at least a photosensitive layer on a supporting body, and includes steps of laminating the photosensitive layer on a substrate to be processed, exposing and developing the photosensitive layer to form a resist pattern, and shaping the resist pattern by a dry process on the resist pattern. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a pattern forming method for efficiently forming a high-definition permanent pattern suitable for a dry film resist (DFR) or the like in the field of printed wiring boards including package substrates.

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

  However, a resin residue may remain in the gap of the resist pattern during the development. Due to the presence of the residue, in the subsequent etching process, an etching solution does not enter the gap between the resist patterns well, and a portion where etching is hindered is generated. In particular, since the gap is narrow and dense in a wiring pattern or the like, the inhibition of the flow of the etching solution into the gap becomes remarkable due to the residue remaining, and the etching progress varies depending on the portion of the substrate. Furthermore, in the wiring pattern, the thickness of the resist pattern is as thick as 10 μm or more, and curing on the side closer to the light source is promoted, so that the cross-sectional shape of the resist pattern has a wide inverted trapezoidal shape on the side opposite to the substrate As a result, the gap on the surface side of the resist pattern becomes narrower and the inflow of the etching solution is more easily prevented. As a result, etching is not performed satisfactorily, and the line width of the wiring circuit becomes thick and non-uniform, resulting in a decrease in resolution and a problem that a fine permanent pattern cannot be formed. Therefore, it is required to arrange the inverted trapezoidal resist pattern into a rectangle so as not to hinder the etching.

In order to eliminate the problem caused by this residue, conventionally, means for extending the development time has been taken, but by immersing in a developer such as an aqueous solution of Na ₂ CO ₃ for a long time, the cross-linked site is swollen by exposure, As a result, it becomes difficult for the developer to enter the development site, and as a result, the residue may not be sufficiently removed. Further, the extension of the development time makes the cross-linked portion of the resist brittle, and there is a possibility that the resist is chipped or peeled off from the substrate, leading to a decrease in the quality of the resist pattern product.
Further, Patent Documents 2 and 3 disclose a method of removing a resin residue in a through-hole formed in a resin layer by dry desmear treatment. However, the through-hole is not shaped only by removing the residue. There is no disclosure about shaping of the resist pattern.
Therefore, by shaping the resist pattern after development and removing the resist residue, a permanent pattern such as a wiring pattern can be formed with high definition and efficiency, and the resist bridging portion is not chipped. At present, no satisfactory pattern forming method has been provided that can achieve both high resolution and adhesion between the substrate and the photosensitive layer without causing peeling or swelling.

JP 2003-307845 A JP-A-8-180757 JP 2001-230549 A

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, the present invention can form a permanent pattern such as a wiring pattern with high definition and efficiency by shaping the resist pattern after development by a dry process and removing the residue of the resist. It is an object of the present invention to provide a pattern forming method that is highly compatible with high resolution and adhesion between a substrate and a photosensitive layer, without causing chipping, peeling, swelling, or the like in a crosslinked portion of a resist.

Means for solving the problems are as follows. That is,
<1> The photosensitive layer in a pattern forming material having at least a photosensitive layer on a support is laminated on a substrate to be processed, and the photosensitive layer is exposed and developed to form a resist pattern. On the other hand, a resist pattern shaping step is performed by a dry process. In the pattern forming method according to <1>, by performing a resist pattern shaping process by a dry process, a resist pattern is swollen or chipped by a so-called wet process using a developer such as an aqueous Na ₂ CO ₃ solution, A resist pattern having an inverted trapezoidal cross-sectional shape can be shaped into a rectangle without peeling off from the substrate, and the resist residue can be removed well. As a result, an etchant or the like can easily enter the gap between the resist patterns, the etching process is performed well, and a permanent resist pattern such as a wiring pattern can be formed with high definition.
<2> The pattern forming method according to <1>, wherein the resist pattern shaping step is performed by a plasma etching process. In the pattern forming method according to <2>, since the plasma etching process is performed at a temperature lower than the melting temperature of the pattern forming material, the resist pattern does not melt and cause damage or the like. Pattern shaping can be performed with high accuracy, and residues can be removed well.
<3> The pattern forming method according to <2>, wherein the plasma etching process is performed under reduced pressure. Since the <3> pattern forming method is performed in a vacuum state, it is possible to improve the processing capability of plasma etching.
<4> The pattern forming method according to <1>, wherein the resist pattern shaping step is performed by an atmospheric pressure ozone surface treatment.
<5> The pattern forming method according to <4>, wherein the atmospheric pressure ozone surface treatment is performed under an atmospheric pressure. In the pattern forming method according to <3>, vacuuming is not required, and the processing time of the resist pattern shaping step can be shortened to increase efficiency.
<6> The pattern forming method according to any one of <1> to <5>, wherein the substrate is a printed wiring board manufacturing substrate.
<7> The pattern forming method according to any one of <1> to <6>, wherein a permanent pattern is formed after the resist pattern shaping step is performed.
<8> The pattern forming method according to <7>, wherein the permanent pattern is a wiring pattern, and the formation of the permanent pattern is performed by at least one of an etching process and a plating process.
<9> The pattern forming method according to <8>, wherein the wiring pattern is formed by one of a subtractive method and a semi-additive method.
<10> The pattern forming method according to any one of <1> to <9>, wherein the photosensitive layer includes a polymerizable compound, a binder, and a photopolymerization initiator.
<11> The pattern according to <10>, wherein the polymerizable compound has at least one selected from a compound containing a propylene oxide group, a compound containing an ethylene oxide group, a compound containing a urethane group, and a compound containing an aryl group. It is a forming method.
<12> The pattern forming method according to <10> to <11>, wherein the polymerizable compound includes at least a compound containing a propylene oxide group, a compound containing a urethane group, and a compound containing an aryl group.
<13> The pattern forming method according to any one of <10> to <12>, wherein the polymerizable compound has a bisphenol skeleton.
<14> The pattern forming method according to any one of <10> to <13>, wherein the binder has an acidic group.
<15> The pattern forming method according to any one of <10> to <14>, wherein the binder includes a vinyl copolymer.
<16> The pattern forming method according to any one of <10> to <15>, wherein the binder includes a copolymer of at least one of styrene and a styrene derivative.
<17> The pattern forming method according to any one of <10> to <16>, wherein the binder has an acid value of 70 to 250 (mgKOH / g).
<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 method according to any one of <10> to <17>.
<19> The pattern formation method according to any one of <10> to <18>, wherein the photopolymerization initiator includes hexaarylbiimidazole.
<20> The pattern forming method according to any one of <1> to <19>, wherein the photosensitive layer has a thickness of 1 to 100 μm.
<21> From the above <1> to <20, 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 method according to any one of the above.
<22> The pattern forming material according to any one of <1> to <21>, wherein the support has a long shape.
<23> The pattern forming material according to any one of <1> to <22>, wherein the pattern forming material has a long shape and is wound in a roll shape.
<24> The pattern forming material according to any one of <1> to <23>, wherein the pattern forming material has a protective film on the photosensitive layer.
<25> Any of the above <1> to <24>, having a protective film on the photosensitive layer, wherein the protective film contains at least one selected from polypropylene resin, ethylene-propylene copolymer resin, and polyethylene terephthalate resin The pattern forming material according to any one of the above.
<26> After the light is modulated by the light modulation unit having n number of pixel portions that receive and emit light from the light irradiation unit, the light is emitted from the light irradiation unit. The pattern forming method according to any one of <1> to <25>, wherein the pattern forming method includes at least a microlens array in which microlenses having aspheric surfaces capable of correcting aberration due to distortion are arranged. In the pattern forming method according to <26>, 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 is imaged on the pattern forming material. Is suppressed. As a result, the pattern forming material is exposed with high definition. For example, a high-definition pattern is formed by developing the photosensitive layer thereafter.
<27> The pattern forming method according to <26>, wherein the aspherical surface is a toric surface. In the pattern forming method according to <27>, since the aspherical surface is a toric surface, the aberration due to the distortion of the radiation surface in the pixel portion is efficiently corrected, and an image formed on the pattern forming material is formed. Is efficiently suppressed. As a result, the pattern forming material is exposed with high definition. For example, a high-definition pattern is formed by developing the photosensitive layer thereafter.
<28> The pattern forming method according to any one of <1> to <27>, wherein the exposure is performed through an aperture array. In the pattern forming method according to <28>, the extinction ratio is improved by performing exposure through the aperture array. As a result, the exposure is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.
<29> The pattern forming method according to any one of <1> to <28>, wherein the exposure is performed while relatively moving the exposure light and the photosensitive layer. In the pattern forming method according to <29>, exposure is performed at high speed by performing exposure while relatively moving the modulated light and the photosensitive layer. For example, when the photosensitive layer is subsequently developed, a high-definition pattern is formed.
<30> The pattern forming method according to any one of <1> to <29>, wherein the exposure is performed on a partial region of the photosensitive layer.

  According to the present invention, conventional problems can be solved, and the resist pattern after development is finely shaped, and the resist residue is removed, so that a permanent pattern such as a wiring pattern can be obtained with high definition and A pattern forming method that can be formed efficiently and that achieves a high level of compatibility between the high resolution and the adhesion between the substrate and the photosensitive layer without causing chipping, peeling or swelling in the crosslinked portion (cured film) of the resist. Can be provided.

(Pattern formation method)
In the pattern forming method of the present invention, the photosensitive layer in a pattern forming material having at least a photosensitive layer on a support is laminated on a substrate to be processed (lamination step), and the photosensitive layer is exposed (exposure step). After developing to form a resist pattern (development process), the process includes at least a resist pattern shaping process performed by a dry process on the resist pattern, and includes other processes selected as appropriate.

[Lamination process]
The method for forming the laminate in the lamination step is not particularly limited and may be appropriately selected depending on the intended purpose. However, the pattern forming material is laminated on the substrate while at least one of heating and pressing. It is preferable to do.
There is no restriction | limiting in particular as said heating temperature, Although it can select suitably according to the objective, For example, 50-140 degreeC is preferable and 60-120 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, 0.1-1.0 MPa is preferable and 0.2-0.8 MPa is more preferable.
Moreover, there is no restriction | limiting in particular in the speed | rate to laminate | stack, Although it can select suitably according to the objective, For example, 0.1-4 m / min is preferable and 1-3 m / min 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, a laminator, a vacuum laminator, etc. are mentioned suitably.

  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, a laminator (For example, Taisei Laminator company make, VP-II) etc. are suitable. Can be mentioned.

  There is no restriction | limiting in particular as a layer structure in the said laminated body, Although it can select suitably according to the objective, For example, the layer structure which has the said base | substrate, the said photosensitive layer, and the said support body in this order is preferable.

<Substrate>
The substrate is not particularly limited, and can be appropriately selected from known materials having high surface smoothness to those having an uneven surface. A plate-like substrate (substrate) is preferable, and Specifically, a known printed wiring board forming substrate (for example, a copper-clad laminate), a glass plate (for example, a soda glass plate), a synthetic resin film, paper, a metal plate, and the like can be given.

  Preferred examples of the printed wiring board forming substrate include a glass epoxy substrate, an epoxy-impregnated aramid nonwoven fabric, a surface of an insulating layer such as polyimide, and a copper foil layer provided as a plating foil or a sputtered foil. When the sputter foil is provided, another metal foil (Ni, Cr, etc.) may be provided as a base layer for the purpose of improving the adhesion between the copper foil and the insulating layer.

  The surface of the substrate may be formed with unevenness of about 0.5 to 2 μm by a method such as chemical polishing for the purpose of improving adhesion with the pattern forming material to be laminated.

<Pattern forming material>
The pattern forming material is not particularly limited as long as it has at least a photosensitive layer on a support, and can be appropriately selected according to the purpose. The photosensitive layer is preferably formed on a support, and a cushion layer may be provided between the support and the photosensitive layer, or a protective film may be formed on the photosensitive layer. Good. Furthermore, other layers appropriately selected may be provided.

<< Photosensitive layer >>
The photosensitive layer contains a polymerizable compound, a binder, and a photopolymerization initiator, and may contain a sensitizer and other components appropriately selected as necessary.

-Polymerizable compound-
The polymerizable compound is not particularly limited and may be appropriately selected depending on the intended purpose. However, at least selected from an alkylene oxide group having 3 or more carbon atoms, a compound containing a urethane group, and a compound containing an aryl group. It preferably has one kind, and more preferably includes at least a compound containing a propylene oxide group, a compound containing a urethane group, and a compound containing an aryl group.

The polymerizable compound having an alkylene oxide group having 3 or more carbon atoms is preferably at least one selected from a diacrylate compound partially containing bisphenol A and a diacrylate compound partially containing a urethane bond. .
Moreover, the said polymeric compound may be used individually by 1 type, may use 2 or more types together, Furthermore, you may use together with another polymeric compound.

  The alkylene oxide group having 3 or more carbon atoms is preferably, for example, an alkylene oxide group having 3 to 6 carbon atoms, specifically, a propylene oxide group (n-propylene oxide group, isopropylene oxide group), butylene oxide group. (N-butylene oxide group, isobutylene oxide group), pentylene oxide group, hexylene oxide group, a group combining these (which may be combined in any of random and block), and the like. Among these, a propylene oxide group is more preferable in that generation of scum during development can be suppressed.

  Examples of the other alkylene oxide groups include a methylene oxide group and an ethylene oxide group. Among these, an ethylene oxide group is preferable.

For example, the polymerizable compound preferably has one or more polymerizable groups, more preferably two or more. Moreover, it is also preferable that the said polymeric compound has a urethane group and an aryl group, for example.
Examples of the polymerizable group include a (meth) acrylate group, a vinyl ether group, a vinyl ester group, an alicyclic ether group (for example, an epoxy group, an oxetane group, etc.), and among these, a (meth) acrylate Groups are preferred.

When the alkylene oxide group having 3 or more carbon atoms is X ¹ and the other alkylene oxide group is X ² , the combination of the polymerizable group, the X ¹ and the X ² is particularly limited. The polymerizable group may be appropriately selected depending on the purpose. For example, a polymerizable group-(X ¹ ) _m- , a polymerizable group-(X ¹ ) _m- (X ² ) _n- , a polymerizable group-( X ² ) _n- (X ¹ ) _m- , and the like. The end of the connection may further have an organic group. Moreover, when the said polymeric group is two or more, this polymeric group may mutually adjoin and may be connected through the bivalent organic group.

Examples of the divalent organic group include an alkylene group, an arylene group, an alkenylene group, an alkynylene group, a carbonyl group (—CO—), an oxygen atom (—O—), a sulfur atom (—S—), an imino group ( -NH-), substituted imino group wherein a hydrogen atom of the imino group is substituted with a monovalent hydrocarbon group, sulfonyl group (-SO 2 _-) or a group comprising a combination thereof (e.g., a urethane group, an ester group, a ureido group , An amide group, etc.) are preferable. Among these, an alkylene group, an arylene group, or a group (for example, a urethane group, an ester group, a ureido group, an amide group, etc.) that combines these is preferable.

  Examples of the polymerizable compound include a compound represented by the following structural formula (1), 2,2-bis (4-((meth) acryloxypolyalkoxy) phenyl) propane (for example, 2,2-bis ( 4-((meth) acryloxypolypropoxy) phenyl) propane), polyalkylene glycol diacrylate (for example, polypropylene glycol diacrylate), polyalkylene oxide group-modified urethane di (meth) acrylate (for example, polypropylene oxide group-modified urethane di) (Meth) acrylate, polyethylene, propylene oxide group-modified urethane di (meth) acrylate, and the like).

In the structural formula (1), R may be the same as or different from each other, and each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, EO represents an ethylene glycol chain, and PO represents a propylene glycol chain. M ⁵ and m ⁶ each represent an integer of 0 to 30, and n ⁵ and n ⁶ each represent an integer of 1 to 30.

  Examples of 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane represented by the structural formula (1) include 2,2-bis (4-((meth) acrylic). Loxydiethoxyoctapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth) acrylohexaethoxyhexa) And propoxy) phenyl) propane. These may be used alone or in combination of two or more.

  Examples of the 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydipropoxy) phenyl) propane and 2,2 -Bis (4-((meth) acryloxytripropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meta ) Acryloxypentapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptapropoxy) phenyl) Propane, 2,2-bis (4-((meth) acryloxyoctapropoxy) phenyl) propane, 2,2-bis (4-((meth) a) Liloxynonapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecapropoxy) phenyl) Propane, 2,2-bis (4-((meth) acryloxydodecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetradecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecapropoxy) phenyl) propane, 2,2-bis (4-((meta And acryloxyhexadecapropoxy) phenyl) propane. These may be used alone or in combination of two or more.

  Examples of the polypropylene glycol diacrylate include dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, pentapropylene glycol diacrylate, hexapropylene glycol diacrylate, heptapropylene glycol diacrylate, and octapropylene glycol diacrylate. Acrylate, nonapropylene glycol diacrylate, decapropylene glycol diacrylate, undecapropylene glycol diacrylate, dodecapropylene glycol diacrylate, tridecapropylene glycol diacrylate, tetradecapropylene glycol diacrylate, pentadecapropylene glycol diacrylate, hexadeca Propi Glycol diacrylate, heptadecapropylene glycol diacrylate, octadecapropylene glycol diacrylate, nonadeca propylene glycol diacrylate, eicosa propylene glycol diacrylate, etc. Among them, propylene glycol units in the molecule are 2 to 14 Those having one are preferred.

Examples of the polyalkylene oxide group-modified urethane di (meth) acrylate include those in which at least a part of the ethylene oxide group of the compound represented by the following structural formula (5) is substituted with a propylene oxide group. For example, n = 5 in which all ethylene oxide groups are substituted with propylene oxide groups, and those having a structure in which three ethylene oxide groups and three propylene oxide groups are linked.

Further, examples of the polymerizable compound also include compounds represented by the following structural formulas (2) to (4). These may be used alone or in combination of two or more.
In the structural formula (2), R may be the same as or different from each other, and each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, EO represents an ethylene glycol chain, and PO represents a propylene glycol chain. M ¹ , m ² and n ¹ each represents an integer of 1 to 30.

In the structural formula (3), R may be the same as or different from each other, and each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, EO represents an ethylene glycol chain, and PO represents a propylene glycol chain. M ³ , n ² and n ³ each represents an integer of 1 to 30.

In the structural formula (4), R may be the same as or different from each other, and each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, EO represents an ethylene glycol chain, and PO represents a propylene glycol chain. the stands, ^{m 4,} and ^{n 4} each represents an integer of 1 to 30.

Examples of the alkyl group having 1 to 3 carbon atoms in the structural formula (1), the structural formula (2), the structural formula (3), and the structural formula (4) include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Is mentioned.
The total number of ethylene glycol chains (m ¹ + m ² , m ³ , m ⁴ and m ⁵ + m ⁶ ) in the structural formula (1), structural formula (2), structural formula (3) and structural formula (4) is 1 respectively. It is an integer of -30, It is preferable that it is an integer of 1-10, It is preferable that it is an integer of 4-9, It is especially preferable that it is an integer of 5-8. When this integer exceeds 30, the tent reliability and the resist shape tend to deteriorate.
The total number of propylene glycol chains (n ¹ , n ² + n ³ , n ⁴ and n ⁵ + n ⁶ ) in the structural formula (1), the structural formula (2), the structural formula (3), and the structural formula (4) is 1 respectively. It is an integer of -30, It is preferable that it is an integer of 5-20, It is preferable that it is an integer of 8-16, It is especially preferable that it is an integer of 10-14. If this integer exceeds 30, the resolution tends to deteriorate and scum (developer contamination) tends to occur.

  Examples of the polymerizable compound include a compound obtained by reacting a compound having a glycidyl group with an α, β-unsaturated carboxylic acid, γ-chloro-β-hydroxypropyl-β ′-(meth) -acryloyloxyethyl. -O-phthalate, [beta] -hydroxypropyl- [beta] '-(meth) -acryloyloxyethyl-o-phthalate, and the like are also included. In addition, structural formulas (20), (23), and (25) described later, and urethane monomers using these as raw materials are also included.

-Other polymerizable compounds-
The other polymerizable compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a monomer or oligomer having at least one of a urethane group and an aryl group, and the other alkylene oxide group A monomer or oligomer having These preferably have two or more polymerizable groups. The polymerizable group is as described above.

  Examples of the monomer having a urethane group include JP-B-48-41708, JP-A-51-37193, JP-B-5-50737, JP-B-7-7208, JP-A-2001-154346, JP-A-2001-356476, and the like. And the like. Examples thereof include adducts of a polyisocyanate compound having two or more isocyanate groups in the molecule and a vinyl monomer having a hydroxyl group in the molecule.

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

  Examples of the vinyl monomer having a hydroxyl group in the molecule include 2-hydroxyethyl (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, and octaethylene. Examples include glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, and pentaerythritol tri (meth) acrylate.

  In addition, examples of the monomer having a urethane group include compounds having an isocyanurate ring such as tri ((meth) acryloyloxyethyl) isocyanurate, di (meth) acrylated isocyanurate, and tri (meth) acrylate of ethylene oxide-modified isocyanuric acid. Is mentioned. Among these, compounds represented by the following structural formulas (5) to (15) are preferable. Moreover, these compounds may be used individually by 1 type, and may use 2 or more types together.

  However, in said structural formula (5)-(15), n, n1, n2 and m mean 1-60, l means 1-20, R represents a hydrogen atom or a methyl group. .

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

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

  Specific examples of the monomer having an aryl group include, for example, the above-described polymerizable compound having an aryl group and an ethylene oxide group, 2,2-bis [4-((meth) acryloxyethoxy) phenyl] propane, phenolic 2,2-bis (4-((meth) acryloyloxypolyethoxy) phenyl) propane (for example, 2,2-bis (4- ((Meth) acryloyloxydiethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxypentaethoxy) ) Phenyl) propane, 2,2-bis (4-((meth) acryloyloxydecaethoxy) phenyl) propane 2,2-bis (4 - ((meth) acryloyloxy-pentadecanoyl) phenyl) propane), and the like. These compounds may be compounds obtained by changing the part derived from the bisphenol A skeleton to bisphenol F or bisphenol S.

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

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

  Examples of the monomer of the ester of the unsaturated carboxylic acid and the aliphatic polyhydric alcohol compound include (meth) acrylic acid ester, ethylene glycol di (meth) acrylate, and polyethylene glycol having 2 to 18 ethylene groups. Di (meth) acrylate (for example, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, dodecaethylene glycol di (meth) acrylate , Tetradecaethylene glycol di (meth) acrylate, etc.), trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri ((meth)) (Chloroyloxypropyl) ether, trimethylolethane tri (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) Acrylate, 1,6-hexanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, 1,2,4-butanetriol tri (meth) acrylate, 1 , 5-Bentanediol (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipe Taerythritol hexa (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol penta (meth) acrylate, sorbitol hexa (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, tricyclode Candi (meth) acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate, glycerin tri (meth) acrylate, xylenol di (meth) acrylate, etc. Can be mentioned.

  Among the (meth) acrylic acid esters, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra ( (Meth) acrylate, pentaerythritol triacrylate, pentaerythritol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, diglycerin di (meth) acrylate, 1, 3-propanediol di (meth) acrylate, 1,2,4-butanetriol tri (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, , 5-pentanediol (meth) acrylate, neopentyl glycol di (meth) acrylate, tri (meth) acrylic acid esters of trimethylolpropane which is ethylene oxide adducts are preferred.

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

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

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

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

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

  In addition to the above, examples of the polymerizable monomer include butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, hexanediol diglycidyl ether, Compounds obtained by adding an α, β-unsaturated carboxylic acid to a glycidyl group-containing compound such as methylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, glycerin triglycidyl ether, JP-A-48-64183, JP-B-49 -43191, Japanese Patent Publication No. 52-30490, polyester acrylates and polyester (meth) acrylate oligomers, epoxy compounds (for example, (Butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, diethylene glycol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, glycerin triglycidyl ether) and (meta ) Photofunctional monomers and oligomers described in polyfunctional acrylates and methacrylates such as epoxy acrylates reacted with acrylic acid, Journal of Japan Adhesion Association Vol. 20, No. 7, pages 300 to 308 (1984), allyl Esters such as diallyl phthalate, diallyl adipate, diallyl malonate, diallylamide (eg diallylacetamide), cationically polymerizable divinyl acetate (For example, butanediol-1,4-divinyl ether, cyclohexanedimethanol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, hexanediol divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, glycerin trivinyl ether, etc. ), Epoxy compounds (for example, butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol Tetraglycidyl ether, glycerin Liglycidyl ether, etc.), oxetanes (eg, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, etc.), epoxy compounds, oxetanes (eg, compounds described in WO01 / 22165) , N-β-hydroxyethyl-β- (methacrylamido) ethyl acrylate, N, N-bis (β-methacryloxyethyl) acrylamide, allyl methacrylate, and other compounds having two or more different ethylenically unsaturated double bonds Etc.

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

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

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

As content of the polymeric compound in the said photosensitive layer, 5-90 mass% is preferable, for example, 15-60 mass% is more preferable, and 20-50 mass% is especially preferable.
If the content is 5% by mass, the strength of the tent film may be reduced, and if it exceeds 90% by mass, edge fusion during storage (exudation failure from the end of the roll) may be deteriorated. .
Moreover, as content of the polyfunctional monomer which has 2 or more of the said polymeric groups in a polymeric compound, 5-100 mass% is preferable, 20-100 mass% is more preferable, 40-100 mass% is especially preferable. .

-Binder-
The binder is preferably, for example, swellable with an alkaline liquid, and more preferably soluble in an alkaline liquid.
As the binder exhibiting swellability or solubility with respect to the alkaline liquid, for example, those having an acidic group are preferably mentioned.

There is no restriction | limiting in particular as said acidic group, According to the objective, it can select suitably, For example, a carboxyl group, a sulfonic acid group, a phosphoric acid group etc. are mentioned, Among these, a carboxyl group is preferable.
Examples of the binder having a carboxyl group include a vinyl copolymer having a carboxyl group, a polyurethane resin, a polyamic acid resin, and a modified epoxy resin. Among these, the solubility in a coating solvent, the solubility in an alkali developer, and the like. A vinyl copolymer having a carboxyl group is preferable from the viewpoint of solubility, suitability for synthesis, ease of adjustment of film properties, and the like.

  The vinyl copolymer having a carboxyl group can be obtained by copolymerization of at least (1) a vinyl monomer having a carboxyl group, and (2) a monomer copolymerizable therewith.

Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, and hydroxyl group. An addition reaction product of a monomer (for example, 2-hydroxyethyl (meth) acrylate) and a cyclic anhydride (for example, maleic anhydride, phthalic anhydride, cyclohexanedicarboxylic anhydride), ω-carboxy-polycaprolactone mono Examples include (meth) acrylate. Among these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like.
Moreover, you may use the monomer which has anhydrides, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group.

  The other copolymerizable monomer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, and maleic acid diesters. , Fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile, heterocyclic groups substituted with vinyl groups (eg, vinylpyridine, Vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinylcaprolactone, 2-acrylamido-2-methylpropanesulfonic acid, phosphoric acid mono (2-acryloyloxyethyl ester), phosphorus Acid mono (1- Chill-2-acryloyloxyethyl ester), functional groups (e.g., a urethane group, a urea group, a sulfonamide group, a phenol group and a vinyl monomer are mentioned having an imide group), styrene is preferred among these.

  Examples of the (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) ) Acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, t-octyl (meth) acrylate, Dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meta ) Acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monophenyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate , Polyethylene glycol monoethyl ether (meth) acrylate, β-phenoxyethoxyethyl acrylate, Nylphenoxypolyethylene glycol (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) Examples thereof include acrylate, perfluorooctylethyl (meth) acrylate, tribromophenyl (meth) acrylate, and tribromophenyloxyethyl (meth) acrylate.

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

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

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

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

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

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

  Examples of the styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloro Examples include methylstyrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, α-methylstyrene, and the like.

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

  Examples of the method for synthesizing the vinyl monomer having a functional group include an addition reaction of an isocyanate group and a hydroxyl group or an amino group, specifically, a monomer having an isocyanate group and a compound containing one hydroxyl group. Alternatively, an addition reaction with a compound having one primary or secondary amino group, an addition reaction between a monomer having a hydroxyl group or a monomer having a primary or secondary amino group, and a monoisocyanate can be given.

  Examples of the monomer having an isocyanate group include compounds represented by the following structural formulas (16) to (18).

However, in the structural formulas (16) to (18), R ¹ represents a hydrogen atom or a methyl group.

  Examples of the monoisocyanate include cyclohexyl isocyanate, n-butyl isocyanate, toluyl isocyanate, benzyl isocyanate, and phenyl isocyanate.

  Examples of the monomer having a hydroxyl group include compounds represented by the following structural formulas (19) to (27).

However, in the above structural formula (19) ~ (27), R 1 represents a hydrogen atom or a methyl radical, n represents an integer of 1 or more.

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

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

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

  Examples of the other copolymerizable monomers other than those described above include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, and (meth) acrylic. Preferable examples include 2-ethylhexyl acid, styrene, chlorostyrene, bromostyrene, and hydroxystyrene.

  The said other copolymerizable monomer may be used individually by 1 type, and may use 2 or more types together.

  The vinyl copolymer can be prepared by copolymerizing the corresponding monomers by a known method according to a conventional method. For example, it can be prepared by using a method (solution polymerization method) in which the monomer is dissolved in a suitable solvent and a radical polymerization initiator is added thereto to polymerize in a solution. Moreover, it can prepare by utilizing superposition | polymerization by what is called emulsion polymerization etc. in the state which disperse | distributed the said monomer in the aqueous medium.

  The suitable solvent used in the solution polymerization method is not particularly limited and may be appropriately selected depending on the monomer used and the solubility of the copolymer to be produced. For example, methanol, ethanol, propanol, Examples include isopropanol, 1-methoxy-2-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, toluene and the like. These solvents may be used alone or in combination of two or more.

  The radical polymerization initiator is not particularly limited, and examples thereof include 2,2′-azobis (isobutyronitrile) (AIBN) and 2,2′-azobis- (2,4′-dimethylvaleronitrile). Examples thereof include peroxides such as azo compounds and benzoyl peroxide, and persulfates such as potassium persulfate and ammonium persulfate.

There is no restriction | limiting in particular as content rate of the polymeric compound which has a carboxyl group in the said vinyl copolymer, Although it can select suitably according to the objective, For example, 5-50 mol% is preferable, 10-40 mol % Is more preferable, and 15 to 35 mol% is particularly preferable.
If the content is less than 5 mol%, the developability to alkaline water may be insufficient, and if it exceeds 50 mol%, the developer resistance of the cured portion (image portion) may be insufficient.

There is no restriction | limiting in particular as molecular weight of the binder which has the said carboxyl group, Although it can select suitably according to the objective, For example, 2,000-300,000 are preferable as a mass mean molecular weight, 4,000-150 1,000 is more preferable.
When the mass average molecular weight is less than 2,000, the strength of the film tends to be insufficient and stable production may be difficult, and when it exceeds 300,000, developability may be deteriorated.

  The binder which has the said carboxyl group may be used individually by 1 type, and may use 2 or more types together. Examples of the case where two or more binders are used in combination include, for example, a combination of two or more binders composed of different copolymer components, two or more binders having different mass average molecular weights, and two or more binders having different dispersities. Is mentioned.

  The binder having a carboxyl group may be partially or entirely neutralized with a basic substance. The binder may be used in combination with resins having different structures such as polyester resin, polyamide resin, polyurethane resin, epoxy resin, polyvinyl alcohol, and gelatin.

  Moreover, as the binder, a resin soluble in an alkaline liquid described in Japanese Patent No. 2873890 and the like can be used.

There is no restriction | limiting in particular as content of the said binder in the said photosensitive layer, Although it can select suitably according to the objective, For example, 10-90 mass% is preferable, 20-80 mass% is more preferable, 40- 80% by mass is particularly preferred.
When the content is less than 10% by mass, alkali developability and adhesion to a printed wiring board forming substrate (for example, a copper-clad laminate) may be deteriorated. Stability and strength of the cured film (tent film) may be reduced. The content may be the total content of the binder and the polymer binder used in combination as necessary.

The acid value of the binder is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 70 to 250 (mgKOH / g), more preferably 90 to 200 (mgKOH / g), 100 to 180 (mg KOH / g) is particularly preferable.
When the acid value is less than 70 (mgKOH / g), developability may be insufficient, resolution may be inferior, and permanent patterns such as wiring patterns may not be obtained with high definition. / G), at least one of the developer resistance and adhesion of the pattern deteriorates, and a permanent pattern such as a wiring pattern may not be obtained with high definition.

-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), hexaarylbiimidazoles, oxime derivatives, organic peroxides, thio compounds, Examples include ketone compounds, aromatic onium salts, and metallocenes. Among these, halogenated hydrocarbons having a triazine skeleton, oxime derivatives, ketone compounds, hexaarylbiimidazoles from the viewpoints of sensitivity and storage stability of the photosensitive layer, and adhesion between the photosensitive layer and the printed wiring board forming substrate. System compounds are preferred.

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

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

  Examples of the 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), a compound described in JP-A-62-258241, a compound described in JP-A-5-281728, a compound described in JP-A-5-34920, and U.S. Pat. No. 4,221,976. Examples include compounds described in the specification.

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

  Examples of the compound described in the British Patent 1388492 include 2-styryl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methylstyryl) -4,6- Bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl)- 4-amino-6-trichloromethyl-1,3,5-triazine and the like can be mentioned.

  Examples of the compounds described in JP-A-53-133428 include 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2 -(4-Ethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl]- 4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5- Examples include triazine and 2- (acenaphtho-5-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

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

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

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

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

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

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

  Examples of the oxime derivative suitably used in the present invention include compounds represented by the following structural formulas (28) to (61).

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

  Examples of the metallocenes include bis (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-), JP-A-53-133428, JP-B-57-1819, JP-A-57-6096, and US Pat. Examples thereof include compounds described in the specification of 3615455.

  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-n-propoxycoumarin), 3,3′-carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, JP-A-5-19475, JP-A-7-271028, JP-A-2002-363206 No., JP-A-2002-363207, JP-A-2002-363208, JP-A-2002-363209, etc.), amines (for example, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate) N-butyl acid, 4-dimethylaminobenzoic acid phenethyl, 4-dimethyl 2-phthalimidoethyl tilaminobenzoate, 2-methacryloyloxyethyl 4-dimethylaminobenzoate, pentamethylenebis (4-dimethylaminobenzoate), phenethyl of 3-dimethylaminobenzoic acid, pentamethylene ester, 4-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylaminobenzyl alcohol, ethyl (4-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, tridodecylamine, amino Nofluoranes (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.).

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

  The said photoinitiator may be used individually by 1 type, and may use 2 or more types together. Examples of the combination of two or more include, for example, a combination of hexaarylbiimidazole and 4-aminoketone described in US Pat. No. 3,549,367, a benzothiazole compound described in Japanese Patent Publication No. 51-48516, and trihalomethyl- Combinations of s-triazine compounds, combinations of aromatic ketone compounds (such as thioxanthone) and hydrogen donors (such as dialkylamino-containing compounds and phenol compounds), combinations of hexaarylbiimidazole and titanocene, and coumarins And combinations of titanocene and phenylglycines.

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

-Other ingredients-
In addition to the polymerizable compound having an alkylene oxide group having 3 or more carbon atoms, the binder, and a photopolymerization initiator, the photosensitive layer may contain other components selected as appropriate.
Examples of the other components include polymerization inhibitors, sensitizers, surfactants, plasticizers, color formers, colorants and the like, and adhesion promoters to the substrate surface and other auxiliaries (for example, , Pigments, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, thermal crosslinking agents, surface tension modifiers, chain transfer agents, etc.) . In addition, by appropriately containing these components, properties such as stability, photographic properties, print-out properties, and film properties of the target pattern forming material can be adjusted.

--- Polymerization inhibitor ---
There is no restriction | limiting in particular as said polymerization inhibitor, According to the objective, it can select suitably.
The polymerization inhibitor includes hydrogen donation (or hydrogen donation), energy donation (or energy donation), electron donation (or electron donation) to the polymerization initiation radical component generated from the photopolymerization initiator by the exposure. The polymerization initiation radical is deactivated and the initiation of polymerization is prohibited.

  Examples of the polymerization inhibitor include compounds having a lone electron pair (for example, compounds having oxygen, nitrogen, sulfur, metal, etc.), compounds having pi electrons (for example, aromatic compounds), and the like. A compound having a phenolic hydroxyl group, a compound having an imino group, a compound having a nitro group, a compound having a nitroso group, a compound having an aromatic ring, a compound having a heterocyclic ring, a compound having a metal atom (complex with an organic compound) Including). Among these, a compound having a phenolic hydroxyl group, a compound having an imino group, a compound having an aromatic ring, and a compound having a heterocyclic ring are preferable.

  The compound having a phenolic hydroxyl group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a compound having at least two phenolic hydroxyl groups is preferable. In the compound having at least two phenolic hydroxyl groups, at least two phenolic hydroxyl groups may be substituted with the same aromatic ring or may be substituted with different aromatic rings in the same molecule.

  The compound having at least two phenolic hydroxyl groups is more preferably, for example, a compound represented by the following structural formula (62).

In the structural formula (62), Z represents a substituent, and m represents an integer of 2 or more. n represents an integer of 0 or more. M and n are preferably integers selected so that m + n = 6. Moreover, when n is an integer greater than or equal to 2, said Z may mutually be same or different.
When m is less than 2, the resolution may be deteriorated.

  Examples of the substituent include a carboxyl group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), a hydroxy group, and an alkoxycarbonyl group having 30 or less carbon atoms (for example, a methoxycarbonyl group, Ethoxycarbonyl group, benzyloxycarbonyl group), aryloxycarbonyl group having 30 or less carbon atoms (for example, phenoxycarbonyl group), alkylsulfonylaminocarbonyl group having 30 or less carbon atoms (for example, methylsulfonylaminocarbonyl group, octylsulfonylaminocarbonyl) Group), arylsulfonylaminocarbonyl group (for example, toluenesulfonylaminocarbonyl group), acylaminosulfonyl group having 30 or less carbon atoms (for example, benzoylaminosulfonyl group, acetylaminosulfonyl group, Valoylaminosulfonyl group), an alkoxy group having 30 or less carbon atoms (for example, methoxy group, ethoxy group, benzyloxy group, phenoxyethoxy group, phenethyloxy group, etc.), an arylthio group having 30 or less carbon atoms, or an alkylthio group (for example, Phenylthio group, methylthio group, ethylthio group, dodecylthio group, etc.), aryloxy group having 30 or less carbon atoms (for example, phenoxy group, p-tolyloxy group, 1-naphthoxy group, 2-naphthoxy group, etc.), nitro group, carbon number 30 or less alkyl groups, alkoxycarbonyloxy groups (for example, methoxycarbonyloxy group, stearyloxycarbonyloxy group, phenoxyethoxycarbonyloxy group), aryloxycarbonyloxy groups (for example, phenoxycarbonyloxy group, chlorophenoxycal) Nyloxy group), an acyloxy group having 30 or less carbon atoms (for example, acetyloxy group, propionyloxy group, etc.), an acyl group having 30 or less carbon atoms (for example, acetyl group, propionyl group, benzoyl group, etc.), carbamoyl group (for example, Carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.), sulfamoyl group (for example, sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group) Etc.), an alkylsulfonyl group having 30 or less carbon atoms (for example, methylsulfonyl group, trifluoromethylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, dodecylsulfonyl group), arylsulfonyl group (for example, benzenesulfonyl group, toluenesulfonyl) Group, naphthalenesulfonyl group, pyridinesulfonyl group, quinolinesulfonyl group), aryl group having 30 or less carbon atoms (for example, phenyl group, dichlorophenyl group, toluyl group, methoxyphenyl group, diethylaminophenyl group, acetylaminophenyl group, methoxycarbonylphenyl group) , Hydroxyphenyl group, t-octylphenyl group, naphthyl group, etc.), substituted amino group (for example, amino group, alkylamino group, dialkylamino group, arylamino group, diarylamino group, acylamino group etc.), substituted phosphono group ( For example, phosphono group, diethylphosphono group, diphenylphosphono group), heterocyclic group (for example, pyridyl group, quinolyl group, furyl group, thienyl group, tetrahydrofurfuryl group, pyrazolyl group, isoxazolyl group, isothiazolyl group) Imidazolyl group, oxazolyl group, thiazolyl group, pyridazyl group, pyrimidyl group, pyrazyl group, triazolyl group, tetrazolyl group, benzoxazolyl group, benzimidazolyl group, isoquinolyl group, thiadiazolyl group, morpholino group, piperidino group, piperazino group, indolyl group , Isoindolyl group, thiomorpholino group), ureido group (eg methylureido group, dimethylureido group, phenylureido group etc.), sulfamoylamino group (eg dipropylsulfamoylamino group etc.), alkoxycarbonylamino group (eg For example, ethoxycarbonylamino group and the like), aryloxycarbonylamino group (for example, phenyloxycarbonylamino group), alkylsulfinyl group (for example, methylsulfinyl group and the like), arylsulfy Le group (e.g., such as phenylsulfinyl group), a silyl group (e.g., trimethoxysilyl group, triethoxysilyl group), silyloxy group (e.g., trimethylsilyloxy group) and the like.

  Examples of the compound represented by the structural formula (74) include alkylcatechol (for example, catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol). 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert -Butyl catechol, 3-tert-butyl catechol, 4-tert-butyl catechol, 3,5-di-tert-butyl catechol, etc.), alkylresorcinol (for example, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol) 4 Ethyl resorcinol, 2-propyl resorcinol, 4-propyl resorcinol, 2-n-butyl resorcinol, 4-n-butyl resorcinol, 2-tert-butyl resorcinol, 4-tert-butyl resorcinol, etc.), alkylhydroquinone (eg, methylhydroquinone) Ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, etc.), pyrogallol, phloroglucin and the like.

The compound having a phenolic hydroxyl group is also preferably a compound in which aromatic rings having at least one phenolic hydroxyl group are linked to each other by a divalent linking group.
Examples of the divalent linking group include groups having 1 to 30 carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, SO, SO _{2 and the} like. The sulfur atom, oxygen atom, SO, and SO ₂ may be directly bonded.
The carbon atom and oxygen atom may have a substituent, and examples of the substituent include Z in the above structural formula (28).
The aromatic ring may have a substituent, and examples of the substituent include Z in the above structural formula (28).

Specific examples of the compound having a phenolic hydroxyl group include bisphenol A, bisphenol S, bisphenol M, a known bisphenol compound used as a color developer for thermal paper, a bisphenol compound described in JP-A-2003-305945, and an oxidation compound. Examples thereof include hindered phenol compounds used as an inhibitor. In addition, monophenol compounds having a substituent such as 4-methoxyphenol, 4-methoxy-2-hydroxybenzophenone, β-naphthol, 2,6-di-t-butyl-4-cresol, methyl salicylate, diethylaminophenol, etc. Can be mentioned.
A commercial product of the compound having a phenolic hydroxyl group includes a bisphenol compound manufactured by Honshu Chemical.

There is no restriction | limiting in particular as a compound which has the said imino group, Although it can select suitably according to the objective, For example, a thing with a molecular weight of 50 or more is preferable, and a thing with a molecular weight of 70 or more is more preferable.
The compound having an imino group preferably has a cyclic structure substituted with an imino group. The cyclic structure is preferably a condensed at least one of an aromatic ring and a heterocyclic ring, and more preferably a condensed aromatic ring. Moreover, in the said cyclic structure, you may have an oxygen atom, a nitrogen atom, and a sulfur atom.

  Specific examples of the compound having an imino group include phenothiazine, phenoxazine, dihydrophenazine, hydroquinoline, or a compound obtained by substituting these compounds with Z in the above structural formula (1).

The compound having a cyclic structure substituted with the imino group is preferably a hindered amine derivative having a hindered amine in part.
Examples of the hindered amine include hindered amines described in JP-A No. 2003-246138.

The compound having the nitro group or the compound having the nitroso group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, those having a molecular weight of 50 or more are preferred, and those having a molecular weight of 70 or more. Is more preferable.
Specific examples of the compound having the nitro group or the compound having the nitroso group include nitrobenzene, a chelate compound of nitroso compound and aluminum, and the like.

The compound having an aromatic ring is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the aromatic ring has a substituent having a lone electron pair (for example, an oxygen atom, a nitrogen atom, a sulfur atom) And the like substituted by a substituent having
Specific examples of the compound having an aromatic ring include, for example, the above-described compound having a phenolic hydroxyl group, the above-mentioned compound having an imino group, and a compound having an aniline skeleton (for example, methylene blue, crystal violet, etc.). It is done.

The compound having a heterocycle is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the heterocycle has an atom having a lone pair of electrons such as nitrogen, oxygen, and sulfur. preferable.
Specific examples of the compound having a heterocyclic ring include pyridine and quinoline.

There is no restriction | limiting in particular as a compound which has the said metal atom, According to the objective, it can select suitably.
The metal atom is not particularly limited as long as it is a metal atom having an affinity for a radical generated from the polymerization initiator, and can be appropriately selected according to the purpose. Examples thereof include copper, aluminum, and titanium. Can be mentioned.

  Among the polymerization inhibitors, a compound having at least two phenolic hydroxyl groups, a compound having an aromatic ring substituted with an imino group, and a compound having a heterocyclic ring substituted with an imino group are preferable, and the imino group has a cyclic structure. Particular preference is given to compounds constituting the part, hindered amine compounds. Specifically, catechol, phenothiazine, phenoxazine, hindered amine, or derivatives thereof are preferable.

  The polymerization inhibitor is generally contained in a trace amount in a commercially available polymerizable compound. From the viewpoint of improving the resolution, the polymerization inhibitor described above is separate from the polymerization inhibitor contained in the commercially available polymerizable compound. Is preferably included. Therefore, the polymerization inhibitor is preferably a compound excluding a monophenol compound such as 4-methoxyphenol contained in the commercially available polymerizable compound for imparting stability.

  The polymerization inhibitor may be added in advance to the photosensitive resin composition solution.

As content of the said polymerization inhibitor, 0.005-0.5 mass% is preferable with respect to the said polymeric compound of the said photosensitive layer, 0.01-0.4 mass% is more preferable, 0.02- 0.2% by mass is particularly preferable.
If the content is less than 0.005% by mass, the resolution may decrease, and if it exceeds 0.5% by mass, the sensitivity to active energy rays may decrease.

  There is no restriction | limiting in particular as the number of lamination | stacking of a photosensitive layer, According to the objective, it can select suitably, For example, one layer may be sufficient and two or more layers may be sufficient.

--- Sensitizer--
The sensitizer is not particularly limited and may be appropriately selected as the light irradiation means by visible light, ultraviolet light, visible light laser, or the like. For example, the sensitizer having a maximum absorption wavelength of 380 to 450 nm. Is preferred.
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, 2-chloro-10-butylacridone, etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylamino Coumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) ) -7-diethylaminocoumarin, 3,3′-carbonylbis (5,7-di-n-propoxycoumarin), 3,3′-carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-Furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinna) Yl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, and the like, and in addition, JP-A-5-19475 and JP-A-7 -2701028, JP-A-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, 0.01-10 mass% is preferable with respect to all the components of the photosensitive resin composition, 0.05-8 mass% is more preferable, 0.1-5 mass% is Particularly preferred.

--Plasticizer--
The plasticizer may be added to control film physical properties (flexibility) of the photosensitive layer.
Examples of the plasticizer include dimethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diheptyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diphenyl phthalate, diallyl phthalate, octyl capryl phthalate, and the like. Phthalic acid esters: Triethylene glycol diacetate, tetraethylene glycol diacetate, dimethylglycol phthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, triethylene glycol dicabrylate, etc. Glycol esters of tricresyl phosphate, triphenyl phosphate, etc. Acid esters; Amides such as 4-toluenesulfonamide, benzenesulfonamide, Nn-butylbenzenesulfonamide, Nn-butylacetamide; diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sepacate, dioctyl Aliphatic dibasic acid esters such as sepacate, dioctyl azelate, dibutyl malate; triethyl citrate, tributyl citrate, glycerin triacetyl ester, butyl laurate, 4,5-diepoxycyclohexane-1,2-dicarboxylic acid Examples include glycols such as dioctyl acid, polyethylene glycol, and polypropylene glycol.

  As content of the said plasticizer, 0.1-50 mass% is preferable with respect to all the components of the said photosensitive layer, 0.5-40 mass% is more preferable, 1-30 mass% is especially preferable.

--Coloring agent--
The color former may be added to give a visible image (printing function) to the photosensitive layer after exposure.
Examples of the color former include tris (4-dimethylaminophenyl) methane (leuco crystal violet), tris (4-diethylaminophenyl) methane, tris (4-dimethylamino-2-methylphenyl) methane, tris (4- Diethylamino-2-methylphenyl) methane, bis (4-dibutylaminophenyl)-[4- (2-cyanoethyl) methylaminophenyl] methane, bis (4-dimethylaminophenyl) -2-quinolylmethane, tris (4-di Aminotriarylmethanes such as propylaminophenyl) methane; 3,6-bis (dimethylamino) -9-phenylxanthine, 3-amino-6-dimethylamino-2-methyl-9- (2-chlorophenyl) xanthine, etc. Aminoxanthines; 3,6-bis (diethyl Aminothioxanthenes such as mino) -9- (2-ethoxycarbonylphenyl) thioxanthene and 3,6-bis (dimethylamino) thioxanthene; 3,6-bis (diethylamino) -9,10-dihydro-9- Amino-9,10-dihydroacridine such as phenylacridine, 3,6-bis (benzylamino) -9,10-dividro-9-methylacridine; aminophenoxazine such as 3,7-bis (diethylamino) phenoxazine Aminophenothiazines such as 3,7-bis (ethylamino) phenothiazone; aminodihydrophenazines such as 3,7-bis (diethylamino) -5-hexyl-5,10-dihydrophenazine; bis (4-dimethylamino) Aminophenylmethanes such as phenyl) anilinomethane; 4-amino-4 ′ Aminohydrocinnamic acids such as dimethylaminodiphenylamine, 4-amino-α, β-dicyanohydrocinnamic acid methyl ester; hydrazines such as 1- (2-naphthyl) -2-phenylhydrazine; 1,4-bis ( Ethylamino) -2,3-dihydroanthraquinones amino-2,3-dihydroanthraquinones; phenethylanilines such as N, N-diethyl-4-phenethylaniline; 10-acetyl-3,7-bis (dimethylamino) ) An acyl derivative of a leuco dye containing basic NH such as phenothiazine; a leuco-like compound which does not have an oxidizable hydrogen such as tris (4-diethylamino-2-tolyl) ethoxycarbonylmentane but can be oxidized to a coloring compound; Leucoin digoid pigment; U.S. Pat. Nos. 3,042,515 and 3,042 Organic amines that can be oxidized to a colored form as described in No. 517 (eg, 4,4′-ethylenediamine, diphenylamine, N, N-dimethylaniline, 4,4′-methylenediamine triphenylamine, N-vinylcarbazole), and among these, triarylmethane compounds such as leuco crystal violet are preferable.

Furthermore, it is generally known that the color former is combined with a halogen compound for the purpose of coloring the leuco body.
Examples of the halogen compound include halogenated hydrocarbons (for example, carbon tetrabromide, iodoform, ethylene bromide, methylene bromide, amyl bromide, isoamyl bromide, amyl iodide, isobutylene bromide, butyl iodide, Diphenylmethyl bromide, hexachloroethane, 1,2-dibromoethane, 1,1,2,2-tetrabromoethane, 1,2-dibromo-1,1,2-trichloroethane, 1,2,3 tribromopropane, 1-bromo-4-chlorobutane, 1,2,3,4-tetrabromobutane, tetrachlorocyclopropene, hexachlorocyclopentadiene, dibromocyclohexane, 1,1,1-trichloro-2,2-bis (4- Chlorophenyl) ethane and the like; halogenated alcohol compounds (eg, 2,2,2-trichloroethanol, Bromoethanol, 1,3-dichloro-2-propanol, 1,1,1-trichloro-2-propanol, di (iodohexamethylene) aminoisopropanol, tribromo-t-butyl alcohol, 2,2,3-trichlorobutane 1,4-diol and the like; halogenated carbonyl compounds (for example, 1,1-dichloroacetone, 1,3-dichloroacetone, hexachloroacetone, hexabromoacetone, 1,1,3,3-tetrachloroacetone, 1,1 , 1-trichloroacetone, 3,4-dibromo-2-butanone, 1,4-dichloro-2-butanone-dibromocyclohexanone, etc.); halogenated ether compounds (eg 2-bromoethyl methyl ether, 2-bromoethyl ethyl ether) Di (2-bromoethyl) ether, 1,2- Chloroethyl ethyl ether, etc.); halogenated ester compounds (eg, bromoethyl acetate, ethyl trichloroacetate, trichloroethyl trichloroacetate, homopolymers and copolymers of 2,3-dibromopropyl acrylate, trichloroethyl dibromopropionate, α, β Halogenated amide compounds (for example, chloroacetamide, bromoacetamide, dichloroacetamide, trichloroacetamide, tribromoacetamide, trichloroethyltrichloroacetamide, 2-bromoisopropionamide, 2,2,2- Trichloropropionamide, N-chlorosuccinimide, N-bromosuccinimide, etc.); a compound having sulfur or phosphorus (for example, tribromomethylphenylsulfone, 4-nitro) Phenyl tribromomethyl sulfone, 4-chlorophenyl tribromomethyl sulfone, tris (2,3-dibromopropyl) phosphate, etc.), e.g., 2,4-bis (trichloromethyl) 6- phenyltriazole and the like. As the organic halogen compound, a halogen compound having two or more halogen atoms bonded to the same carbon atom is preferable, and a halogen compound having three halogen atoms per carbon atom is more preferable. The said organic halogen compound may be used individually by 1 type, and may use 2 or more types together. Among these, tribromomethylphenyl sulfone and 2,4-bis (trichloromethyl) -6-phenyltriazole are preferable.

  The content of the color former is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, and particularly preferably 0.1 to 5% by mass with respect to all components of the photosensitive layer. Moreover, as content of the said halogen compound, 0.001-5 mass% is preferable with respect to all the components of the said photosensitive layer, and 0.005-1 mass% is more preferable.

--Colorant--
The colorant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a known pigment such as red, green, blue, yellow, purple, magenta, cyan, black, Examples include dyes such as Victoria Pure Blue BO (C.I. 42595), Auramine (C.I. 41000), Fat Black HB (C.I. 26150), Monolite Yellow GT ( CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment)・ Red 146), Hoster Balm Red ESB (CI Pigment Violet 19), Permanent Ruby F H (CI Pigment Red 11), Fastel Pink B Spula (CI Pigment Red 81), Monastral First Blue (CI Pigment Blue 15), Monolite First Black B (CI pigment black 1) and carbon black.

  Examples of the colorant suitable for producing a color filter include C.I. 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, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 83, C.I. I. Pigment violet 23, and those described in JP-A-2002-162752 (0138) to (0141). There is no restriction | limiting in particular as an average particle diameter of the said coloring agent, Although it can select suitably according to the objective, For example, 5 micrometers or less are preferable and 1 micrometer or less is more preferable.

--- Dye--
In the photosensitive layer, a dye can be used for the purpose of coloring the photosensitive resin composition for improving handleability or imparting storage stability.
Examples of the dye include brilliant green (for example, sulfate thereof), eosin, ethyl violet, erythrosine B, methyl green, crystal violet, basic fuchsin, phenolphthalein, 1,3-diphenyltriazine, alizarin red S, thymolphthalein. , Methyl violet 2B, quinaldine red, rose bengal, metanil-yellow, thymol sulfophthalein, xylenol blue, methyl orange, orange IV, diphenyltylocarbazone, 2,7-dichlorofluorescein, paramethyl red, congo red, benzo Purpurin 4B, α-naphthyl-red, Nile blue A, phenacetalin, methyl violet, malachite green, parafuxin, oil blue # 603 (Orien Chemical Co., Ltd.), Rhodamine B, Rhodamine 6G, and the like can be illustrated Victoria Pure Blue BOH, Among these cationic dyes (e.g., Malachite Green oxalate, malachite green sulfates) are preferable. The counter anion of the cationic dye may be a residue of an organic acid or an inorganic acid, for example, a residue such as bromic acid, iodic acid, sulfuric acid, phosphoric acid, oxalic acid, methanesulfonic acid, toluenesulfonic acid ( Anion) and the like.

  As content of the said dye, 0.001-10 mass% is preferable with respect to all the components of the said photosensitive layer, 0.01-5 mass% is more preferable, 0.1-2 mass% is especially preferable.

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

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

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

  The photosensitive layer is, for example, J.I. It may contain organic sulfur compounds, peroxides, redox compounds, azo or diazo compounds, photoreducible dyes, organic halogen compounds, etc. as described in Chapter 5 of “Light Sensitive Systems” Good.

  Examples of the organic sulfur compound include di-n-butyl disulfide, dibenzyl disulfide, 2-mercaptobenzthiazole, 2-mercaptobenzoxazole, thiophenol, ethyltrichloromethane sulfenate, and 2-mercaptobenzimidazole. Is mentioned.

  Examples of the peroxide include di-t-butyl peroxide, benzoyl peroxide, and methyl ethyl ketone peroxide.

  The redox compound is a combination of a peroxide and a reducing agent, and examples thereof include ferrous ions and persulfate ions, ferric ions and peroxides.

  Examples of the azo and diazo compounds include α, α'-azobisiributyronitrile, 2-azobis-2-methylbutyronitrile, and diazonium such as 4-aminodiphenylamine.

  Examples of the photoreducible dye include rose bengal, erythrosine, eosin, acriflavine, lipoflavin, and thionine.

--Surfactant--
In order to improve the surface unevenness generated when the pattern forming material of the present invention is produced, a known surfactant can be added.
The surfactant can be appropriately selected from, for example, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and a fluorine-containing surfactant.

As content of the said surfactant, 0.001-10 mass% is preferable with respect to solid content of the photosensitive resin composition.
When the content is less than 0.001% by mass, the effect of improving the surface shape may not be obtained, and when it exceeds 10% by mass, the adhesion may be deteriorated.

  As the surfactant, in addition to the above-mentioned surfactant, as a fluorine-based surfactant, it contains 40% by mass or more of fluorine atoms in a carbon chain of 3 to 20, and at least 3 counted from the non-bonding terminal A polymer surfactant having, as a copolymerization component, an acrylate or methacrylate having a fluoroaliphatic group in which a hydrogen atom bonded to a carbon atom is fluorine-substituted is also preferred.

  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, 1-100 micrometers is preferable, 2-50 micrometers is more preferable, and 4-30 micrometers is especially preferable.

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

<< Other layers >>
There is no restriction | limiting in particular as said other layer, According to the objective, it can select suitably, For example, layers, such as a cushion layer, a barrier layer, a peeling layer, an adhesive layer, a light absorption layer, a surface protective layer, are mentioned. . The said pattern formation material may have these layers individually by 1 type, and may have 2 or more types. Moreover, you may have 2 or more of the same kind 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 is peelable and has good light transmittance, and further has a smooth surface. Is more preferable.

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

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

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

<< Protective film >>
The pattern forming material may form a protective film on the photosensitive layer.
The material contained in the protective film is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include polypropylene resin, polyethylene resin, ethylene-propylene copolymer resin, polyethylene terephthalate resin, and the support. And the like to be used. These may be used alone or in combination of two or more. The protective film may be a laminated film formed by laminating two or more layers. As the laminated film, for example, a laminated film in which a polypropylene resin film and an ethylene-propylene copolymer resin film are laminated is suitable. Listed.

  As a commercial item of the said protective film, for example, Oji Paper Co., Ltd. make, Alphan E-501, MA-410, E-200; Teijin Ltd. make, PS series (PS-25 etc.); GF-1, GF-3, GF-8, etc. are mentioned. In addition, the protective film can be produced by sandblasting a commercially available film.

  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, 8-50 micrometers is more preferable, 10-30 micrometers is especially preferable.

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.
When the protective film is used, for example, the adhesive force A of the layer adjacent to the photosensitive layer and the photosensitive layer and other than the protective film and the adhesive force B of the photosensitive layer and the protective film are the adhesive force A>. The relationship of the adhesive force B is preferable.

  Examples of the combination of the support and the protective film (support / protective film) include polyethylene terephthalate / polypropylene, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate, and the like. Moreover, the relationship of the above adhesive forces can be satisfy | filled by surface-treating at least any one of a support body and a protective film. The surface treatment of the support may be performed in order to increase the adhesive force with the photosensitive layer. For example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow treatment Examples thereof include a discharge irradiation process, an active plasma irradiation process, and a laser beam irradiation process.

Moreover, as a static friction coefficient of the said support body and the said protective film, 0.3-1.4 are preferable and 0.5-1.2 are more preferable.
When the coefficient of static friction is less than 0.3, it slips too much, so when it is made into a roll, winding deviation may occur. When it exceeds 1.4, it becomes difficult to wind into a good roll. Sometimes.

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

[Method for producing pattern forming material]
The pattern forming material can be manufactured, for example, as follows.
First, the material contained in the photosensitive layer is dissolved, emulsified or dispersed in water or a solvent to prepare a photosensitive resin composition solution.

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

  Next, the photosensitive resin composition solution is applied on the support and dried to form a photosensitive layer, whereby a pattern forming material can be produced.

The method for applying the photosensitive resin composition solution is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a spray method, a roll coating method, a spin coating method, a slit coating method, and an extrusion coating method. And various coating methods such as a curtain coating method, a die coating method, a gravure coating method, a wire bar coating method, and a knife coating method.
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.

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

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

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

<Light modulation means>
The light 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.

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

Hereinafter, an example of the light modulation means will be described with reference to the drawings.
As shown in FIG. 1, in the DMD 50, a large number (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 unit is capable of controlling any less than n pixel elements arranged continuously from the n pixel elements according to pattern information. There is a limit to the data processing speed of the light modulation means, and the modulation speed per line is determined in proportion to the number of pixels to be used. By using, the modulation speed per line is increased.

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

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

  For example, 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, and in this case, it is preferable to use the high-speed modulation together. Thereby, high-speed exposure can be performed in a short time.

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

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

Next, an example of a pattern forming apparatus including the light modulation means will be described with reference to the drawings.
As shown in FIG. 7, the pattern forming apparatus including the light modulation means includes a flat plate stage 152 that holds a sheet-like pattern forming material 150 by adsorbing to the surface.
Two guides 158 extending along the stage moving direction are installed on the upper surface of the thick plate-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 pattern forming material 150 are provided on the other side. . The scanner 162 and the detection sensor 164 are respectively attached to the gate 160 and fixedly arranged above the moving path of the stage 152. The scanner 162 and the detection sensor 164 are connected to a controller (not shown) that controls them.

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

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

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

As shown in FIGS. 10 and 11, each of the exposure heads 166 _{11 to} 166 _mn serves as the light modulation means (spatial light modulation element that modulates each pixel) according to the pattern information. A digital micromirror device (DMD) 50 manufactured by Texas Instruments, USA is provided. The DMD 50 is connected to 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.

  An imaging optical system 51 that images the laser beam B reflected by the DMD 50 on the pattern forming material 150 is disposed on the light reflection side of the DMD 50. The imaging optical system 51 is schematically shown in FIG. 10, but as shown in detail in FIG. 11, the imaging optical system 51 includes a first imaging optical system including lens systems 52 and 54 and lens systems 57 and 58. 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 passing through the microlens array 55 by 1.6 times and forms and projects it on the pattern forming material 150. Therefore, as a whole, the image formed by the DMD 50 is enlarged and enlarged by 4.8 times, and is imaged and projected on the pattern forming material 150.

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

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

<Light irradiation means>
The light irradiation means is not particularly limited and may be appropriately selected depending on the purpose. For example, (ultra) high pressure mercury lamp, xenon lamp, carbon arc lamp, halogen lamp, copier, fluorescent tube, LED, etc. , A known light source such as a semiconductor laser, or 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 a laser combining two or more lights (hereinafter, referred to as “combined laser”). More preferred. Even when light irradiation is performed after the support is peeled off, the same light can be used.

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, 400 nm-450 nm is especially preferable.

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

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

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

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

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

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

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

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

  In general, in 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 from an opening formed in the wall surface of the package 40.

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

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

  FIG. 32 shows 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 in the same direction as the arrangement direction of the light emitting points 110a of each chip as shown in FIG. An arrayed multi-cavity laser array can be used as a laser light source.

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

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

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

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

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

  In the above configuration, each of the laser beams B emitted from each of the plurality of light emitting points 110a of the plurality of multi-cavity lasers 110 is collected in a predetermined direction by the rod lens 113, and then each microlens of the lens array 114. It becomes parallel light. The collimated laser beam L is condensed by the 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 beam 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 beam 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 110a of the plurality of multi-cavity lasers 110 arranged on the laser blocks 180 and 182 is collimated by the collimating lens array 184 and condensed. The light is condensed by the lens 120 and enters the core 130 a of the multimode optical fiber 130. The laser light incident on the core 130a propagates in the optical fiber, is combined into one, and is emitted.

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

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

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

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

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

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

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

For example, in a conventional fiber light source in which a semiconductor laser and an optical fiber are coupled on a one-to-one basis, a laser having an output of about 30 mW (milliwatt) is usually used as the semiconductor laser, and the core diameter is 50 μm and the cladding diameter is 125 μm. Since a multimode optical fiber having a numerical aperture (NA) of 0.2 is used, if an output of about 1 W (watt) is to be obtained, 48 multimode optical fibers (8 × 6) must be bundled. 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 a combined laser, an output of about 1 W can be obtained with six multimode optical fibers, and the area of the light emitting region at the laser emitting portion 68 can be obtained. Is 0.0081 mm ² (0.325 mm × 0.025 mm), the luminance at the laser emitting portion 68 is 123 × 10 ⁶ (W / m ² ), which is about 80 times higher than the conventional luminance. be able to. Further, the luminance per optical fiber is 90 × 10 ⁶ (W / m ² ), and the luminance can be increased by about 28 times compared 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 of the present invention, the diameter of the light emitting region of the fiber array light source 66 in the sub-scanning direction is small, so that it passes through the lens system 67 and enters the DMD 50. As a result, the angle of the light beam incident on the scanning surface 56 is reduced. That is, the depth of focus becomes deep. In this example, the diameter of the light emitting region in the sub-scanning direction is about 30 times that of the conventional one, and a depth of focus substantially corresponding to the diffraction limit can be obtained. Therefore, it is suitable for exposure of a minute spot. This effect on the depth of focus is more prominent and effective as the required light quantity of the exposure head is larger. In this example, the size of one pixel projected on the exposure surface is 10 μm × 10 μm. The DMD is a reflective spatial light modulator, but FIGS. 37A and 37B are developed views for explaining the optical relationship.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  In addition, when the magnitude relation of the distortion of the center part in the x direction and the y direction of the micromirror 62 is opposite to the above, the focal length in the cross section parallel to the x direction is in the cross section parallel to the y direction. If the microlens is formed of a toric lens that is smaller than the focal length, similarly, it is possible to expose the pattern forming material 150 with a higher definition image without distortion.

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

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

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

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

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

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

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

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

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

Next, the imaging optical system will be further described.
In the exposure head, when the laser beam is irradiated from the light irradiation 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 a decrease in the image quality. The exposure area 468 is tilted because the DMD 50 is tilted and arranged in order to eliminate the gap between the pixels.

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

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

<Other optical systems>
In the pattern forming method of the present invention, it may be used in combination with other optical systems appropriately selected from known optical systems, for example, a light amount distribution correcting optical system composed of a pair of combination lenses.
The light amount distribution correcting optical system changes the light flux width at each exit position so that the ratio of the light flux width at the peripheral portion to the light flux width at the central portion close to the optical axis is smaller on the exit side than on the incident side. When the DMD is irradiated with the parallel light 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 flux width at each emission position, and the ratio of the light flux width in the peripheral portion to the light flux width in the central portion close to 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 is shown 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. When one semiconductor laser is connected to the incident end of the single mode optical fiber, the light quantity distribution of the emitted light beam from the optical fiber becomes a Gaussian distribution. The pattern forming method of the present invention can be applied to such a case. Further, the present invention can be applied to a case where the light amount in the central portion near the optical axis is larger than the light amount in the peripheral portion, for example, by reducing the core diameter of the multi-mode optical fiber and approaching the configuration of the single mode optical fiber.
Table 1 below shows basic lens data.

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

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

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

In the above formula (A), each coefficient is defined as follows.
Z: Length of a perpendicular line (mm) drawn from a point on the aspheric surface at a height ρ from the optical axis to the tangent plane (plane perpendicular to the optical axis) of the apex of the aspheric surface
ρ: Distance from optical axis (mm)
K: Conic coefficient C: Paraxial curvature (1 / r, r: Paraxial radius of curvature)
ai: i-th order (i = 3 to 10) aspheric coefficient In the numerical values shown in Table 2, the symbol “E” indicates that the subsequent numerical value is a “power 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 exposing the photosensitive layer in the pattern forming material by the exposing step, curing the exposed region of the photosensitive layer, and developing by removing an uncured region to form a resist pattern. It is.

  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. Resist residues may be generated during the removal of the uncured region. However, since the residues are removed by a resist pattern shaping process described later, it is not necessary to strictly remove the development process. Therefore, for example, the immersion time in the developing solution can be minimized, and problems such as chipping and swelling of the cross-linked portion and peeling from the substrate can be prevented satisfactorily.

  There is no restriction | limiting in particular as said developing solution, Although it can select suitably according to the objective, For example, alkaline aqueous solution, an aqueous developing solution, an organic solvent etc. are mentioned, Among these, weakly alkaline aqueous solution is preferable. Examples of the basic component of the weak alkaline aqueous solution include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, phosphorus Examples include potassium acid, sodium pyrophosphate, potassium pyrophosphate, and borax.

The pH of the weak alkaline aqueous solution is, for example, preferably about 8 to 12, and more preferably about 9 to 11. Examples of the weak alkaline aqueous solution include a 0.1 to 5% by mass aqueous sodium carbonate solution or an aqueous potassium carbonate solution.
The temperature of the developer can be appropriately selected according to the developability of the photosensitive layer, and is preferably about 25 ° C. to 40 ° C., for example.

  The developer includes a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.) and accelerates development. Therefore, it 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.

[Resist pattern shaping process]
The resist pattern shaping step is a step of shaping a cured film of the resist pattern by a dry process on the resist pattern formed by the developing step, and further removing a residue remaining when the uncured region is removed. is there. By this step, the resist pattern having the inverted trapezoidal cross-sectional shape is shaped into a rectangular shape, and the residue remaining on the surface of the substrate can be satisfactorily removed. If a high temperature is applied to the resist pattern, the polymerization reaction of the resin proceeds more than immediately after the exposure, and as a result, the cured film becomes too hard and is likely to be chipped or cracked. Then, since the cured film is carbonized, the resist pattern shaping step is preferably performed at a temperature lower than the melting temperature of the pattern forming material, specifically 150 ° C. or less.
Further, the specific processing means in the pattern shaping step is not particularly limited as long as it is a dry process, and can be appropriately selected according to the purpose. For example, plasma etching treatment, atmospheric pressure ozone surface treatment, etc. Can be mentioned.

In the resist pattern after development, curing is more likely to proceed at a portion closer to the light source, and curing is less likely to proceed at a portion closer to the base. Therefore, as shown in FIG. It has an inverted trapezoidal shape in which the surface side close to is wide. In addition, in the gap between the inverted trapezoidal cured films 506, a residue 508 that cannot be removed at the time of removing the uncured region in the development process remains.
With the inverted trapezoidal shape, the gap between the cured films becomes narrow, and when the etchant is poured in a direction perpendicular to the substrate, that is, from the upper surface of the cured layer, the etchant can enter the gaps due to surface tension. Therefore, the etching may not be performed well. Also, the presence of the residue obstructs the contact between the etching site and the etchant and causes the etching property to deteriorate.

In the resist pattern shaping step, as shown in FIG. 40 (B), the excess portion of the inverted trapezoidal cured film is trimmed into a rectangular shape, and at the same time, the residue remaining in the gap between the cured films is removed.
Therefore, the etching solution or the like can surely enter the gap between the cured films, and the etching solution and the etching site can be reliably brought into contact with each other. In addition, since the treatment is performed in a dry process, the occurrence of swelling or chipping of the cured film due to the treatment liquid can be prevented. As a result, the etchant can easily enter the gaps between the cured films, the etching process can be performed satisfactorily and the quality of the pattern product can be improved.

<Plasma etching process>
The plasma etching process is preferably performed under reduced pressure, and after evacuating the chamber in which the substrate is placed, a processing gas such as ozone gas, Ar gas, active gas O ₂ gas, or CF ₄ gas is introduced into the chamber. By introducing and applying a voltage, a plasma state is generated, the process gas is ionized, the ionized process gas is physically collided, and in the case of an active gas, a chemical reaction is performed on the substrate. Etching is performed on the resist pattern. As described above, since the dry process is performed, the cured film can be prevented from swelling and chipping and can be shaped with high accuracy. In addition, by performing under reduced pressure, high-density plasma can be efficiently generated, and the etching process can be performed with high accuracy and efficiency.

<Atmospheric pressure ozone surface treatment>
The atmospheric ozone surface treatment is preferably carried out under atmospheric pressure, in a chamber in which the substrate is placed, O ₂ gas is compressed by introducing ionized ozone gas (O 3 ^_2), the cured film and chemistry of the substrate Surface treatment is performed by reacting, and resist pattern shaping is performed. In the atmospheric pressure ozone surface treatment, it is only necessary to always introduce the treatment gas into the chamber under atmospheric pressure, so there is no need to evacuate the chamber, saving time for evacuation and improving work efficiency. Can be improved. Also in this case, since it is performed by a dry process, the cured film can be prevented from swelling and chipping, and high-precision shaping is possible.

[Other processes]
There is no restriction | limiting in particular as said other process, Although selecting suitably from the process in well-known pattern formation is mentioned, For example, an etching process, a plating process, etc. are mentioned. These may be used alone or in combination of two or more.
When the printed wiring board is manufactured by the subtractive method shown in FIG. 38, the etching process is performed after the resist pattern shaping step. When the semi-additive method shown in FIG. 39 is used, the etching process is performed after the resist pattern shaping step. A plating process and an etching process are performed.

<Etching process>
The etching step can be performed by a method appropriately selected from known etching methods.
There is no restriction | limiting in particular as an etching liquid used for the said etching process, Although it can select suitably according to the objective, For example, when the said metal layer is formed with copper, a cupric chloride solution, Examples thereof include a ferric chloride solution, an alkali etching solution, and a hydrogen peroxide-based etching solution. Among these, a ferric chloride solution is preferable from the viewpoint of an etching factor.
A permanent pattern can be formed on the surface of the substrate by removing the pattern after performing the etching process in the etching step.
There is no restriction | limiting in particular as said permanent pattern, According to the objective, it can select suitably, For example, a wiring pattern etc. are mentioned suitably.
<Plating process>
The plating step can be performed by a method appropriately selected from known plating processes.
Examples of the plating treatment include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high flow solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfamate, and hard gold. Examples of the treatment include gold plating such as plating and soft gold plating.
A permanent pattern can be formed on the surface of the substrate by removing the pattern after plating by the plating step, and further removing unnecessary portions by etching or the like as necessary.

[Method of manufacturing printed wiring board]
The pattern formation method of this invention can be used suitably for manufacture of a printed wiring board. Hereinafter, an example of the manufacturing method of the printed wiring board using the pattern formation method of this invention is demonstrated.

(1) Lamination process First, a printed wiring board forming substrate having through holes and having a surface covered with a metal plating layer is prepared. As the printed wiring board forming substrate, for example, a copper-clad laminated substrate and a substrate in which a copper plating layer is formed on an insulating base material such as glass-epoxy, or an interlayer insulating film is laminated on these substrates to form a copper plating layer A substrate (laminated substrate) on which is formed can be used.

Next, when a protective film is provided on the pattern forming material, the protective film is peeled off so that the photosensitive layer in the pattern forming material is in contact with the surface of the printed wiring board forming substrate. Crimp using the. Thereby, the laminated body which has the said board | substrate for printed wiring board formation and the said laminated body in this order is obtained.
There is no restriction | limiting in particular as lamination | stacking temperature of the said pattern formation material, For example, room temperature (15-30 degreeC) or under heating (30-180 degreeC) is mentioned, Among these, under heating (60-140 degreeC) ) Is preferred.
There is no restriction | limiting in particular as roll pressure of the said crimping | compression-bonding roll, For example, 0.1-1 Mpa is preferable.
There is no restriction | limiting in particular as the speed | rate of the said crimping | compression-bonding, and 1-3 m / min is preferable.
Further, the printed wiring board forming substrate may be preheated to 30 to 60 ° C., or may be laminated under reduced pressure.

(2) Exposure process Next, the photosensitive layer is cured by irradiating light from the surface of the laminate opposite to the substrate.
At this time, exposure may be performed after peeling the support as necessary (for example, when the light transmittance of the support is insufficient).
The removal of the support may be performed after the exposure process or after the (1) lamination process.

(3) Development step The uncured region of the photosensitive layer on the printed wiring board forming substrate is removed by dissolution with an appropriate developer, and the pattern of the cured layer in the wiring pattern formation region and the cured layer in the tent formation region And a metal layer is exposed on the surface of the printed wiring board forming substrate.
Moreover, you may perform the process which further accelerates | stimulates the hardening reaction of a hardening part by post-heat processing or post-exposure processing as needed after image development. The development may be a wet development method as described above or a dry development method.

(4) Resist Pattern Shaping Step The resist pattern formed in the developing step has an inverted trapezoidal cross section as shown in FIG. 40A, and residues are attached to the surface of the metal layer. In the resist pattern shaping step, the excess portion of the trapezoidal cured film is cut and shaped into a rectangular shape, and at the same time, the residue attached to the surface of the metal layer is removed (FIG. 40B).
(5) Wiring portion forming step A method of peeling the cured photosensitive layer after etching the printed wiring board forming substrate using the resist pattern shaped in the resist pattern shaping step (for example, as shown in FIG. 38) Subtractive method), or the photosensitive layer cured after plating is peeled off, and an unnecessary copper foil layer is processed by etching (for example, the semi-additive method shown in FIG. 39) to form a wiring portion. can do.
Among these, the subtractive method is preferable from the viewpoint of easy management and high technical level, capable of producing the wiring part with a high yield, and producing a circuit board with a very small wiring part at low cost. The semi-additive method is preferred when forming a pattern with finer portions and higher resolution.

  There is no restriction | limiting in particular as etching liquid which performs the said etching process, Although it can select suitably according to the objective, For example, when the said metal layer is formed with copper, a cupric chloride solution, chloride, A ferric chloride solution, an alkaline etching solution, a hydrogen peroxide-based etching solution, and the like can be given. Among these, a ferric chloride solution is preferable from the viewpoint of an etching factor.

In order to peel off the cured photosensitive layer, it is treated with a strong alkaline aqueous solution or the like and removed as a peeled piece from the printed wiring board.
There is no restriction | limiting in particular as a base component in the said strong alkali aqueous solution, For example, sodium hydroxide, potassium hydroxide, etc. are mentioned.
As pH of the said strong alkali aqueous solution, about 12-14 are preferable, for example, and about 13-14 are more preferable.
There is no restriction | limiting in particular as said strong alkali aqueous solution, For example, 1-10 mass% sodium hydroxide aqueous solution or potassium hydroxide aqueous solution etc. are mentioned.

The printed wiring board may be a multilayer printed wiring board.
In addition, you may use the said pattern formation material not only for said etching process but for a plating process. Examples of the plating method include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high flow solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfamate, and hard gold. Examples thereof include gold plating such as plating and soft gold plating.

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

Example 1
Using the pattern forming method of the present invention, a printed circuit board was manufactured by a subtractive method, and its performance was evaluated.
<Manufacture of laminates>
-Production of pattern forming material-
A photosensitive resin composition solution having the following composition is applied onto a 16 μm-thick polyethylene terephthalate film (manufactured by Toray Industries, Inc., 16QS52) as the support, and dried to form a 15 μm-thick photosensitive layer on the support. Then, the pattern forming material was manufactured.

[Composition of photosensitive resin composition solution]
-Phenothiazine 0.0049 part by mass-Methacrylic acid / methyl methacrylate / styrene copolymer (copolymer composition (mass ratio): 29/19/52, mass average molecular weight: 60,000, acid value 189) 11.8 mass Part, polymerizable monomer represented by the following structural formula (78) 5.6 parts by mass, ½ molar ratio adduct of hexamethylene diisocyanate and tetraethylene oxide monomethacrylate 5.0 parts by mass, dodecapropylene glycol diacrylate 56 parts by weight, 2,2-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole 1.7 parts by mass, 10-butyl-2-chloroacridone 0.09 parts by mass, Malachite green oxalate 0.016 parts by mass, leuco crystal violet 0.1 parts by mass, methyl ethyl ketone 0 parts by mass, 1-methoxy-2-propanol 20 parts by mass, fluorine-based surfactant (F780F, manufactured by Dainippon Ink Co., Ltd.) 0.021 parts by mass In addition, the phenothiazine is the polymerization inhibitor and is contained in the molecule. A compound having an aromatic ring, a heterocyclic ring, and an imino group.

However, m + n represents 10 in Structural Formula (78).

  A 12 μm-thick polypropylene film (manufactured by Oji Paper Co., Ltd., Alphan-501) was laminated as the protective film on the photosensitive layer of the pattern forming material. Next, a laminator (MODEL8B-720-PH) was used as the substrate while peeling the protective film of the pattern forming material on the surface of a copper clad laminate (no through-hole, copper thickness 12 μm) polished, washed with water and dried. , Manufactured by Taisei Laminator Co., Ltd.) to prepare a laminate in which the copper-clad laminate, the photosensitive layer, and the support were laminated in this order. The pressure bonding conditions were a pressure roll temperature of 105 ° C., a pressure roll pressure of 0.3 MPa, and a laminating speed of 1 m / min.

  With respect to the photosensitive layer of the laminate, the shortest development time and sensitivity (the amount of light energy necessary for curing the photosensitive layer) were measured by the following methods. The results are shown in Table 3.

(1) Measuring method of the shortest development time About the said laminated body, the shortest development time of the photosensitive layer was measured.
The support is peeled off from the laminate of 510 mm × 610 mm, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. is sprayed on the entire surface of the photosensitive layer at a pressure of 0.15 MPa. The time required until the photosensitive layer on the stretched laminate was dissolved and removed was measured, and this was taken as the shortest development time. As a result of this measurement, the minimum development time of the photosensitive layer was 7 seconds. The results are shown in Table 3.

(2) Measurement of sensitivity With respect to the photosensitive layer of the pattern forming material in the prepared laminate, from the support side, a pattern forming apparatus described below is used, with an interval of 0.1 mJ / cm ² to 2 ^1/2 times. Exposure was performed by irradiating with light having different light energy amounts up to 100 mJ / cm ^2, and a part of the photosensitive layer was cured. After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) is peeled off from the laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. is sprayed on the entire surface of the photosensitive layer on the copper clad laminate. Spraying was performed at a time of .15 MPa twice as long as the shortest development time determined in (1) above, the uncured area was dissolved and removed, and the thickness of the remaining cured area was measured. Subsequently, the relationship between the light irradiation amount and the thickness of the cured layer was plotted to obtain a sensitivity curve. From the sensitivity curve thus obtained, the amount of light energy when the thickness of the cured region was 15 μm was determined as the amount of light energy necessary for curing the photosensitive layer.
As a result, the amount of light energy (sensitivity) necessary for curing the photosensitive layer was 12 mJ / cm ² . The results are shown in Table 3.

<Pattern formation>
About the laminate, using the following pattern forming apparatus, pattern formation by the following method, after performing the resist pattern shaping for the obtained resist pattern, for the shaped resist pattern, shaping, resolution, And the adhesion was evaluated. The results are shown in Table 3.
-Pattern forming device-
27 to 32 as the light irradiating means, and 768 pairs of micromirror arrays in which 1024 micromirrors are arranged in the main scanning direction shown in FIG. 4 as the light modulating means are arranged in the sub-scanning direction. The microlens array 472 in which the DMD 50 controlled to drive only 1024 × 256 rows and the microlenses 474 whose one surface is a toric surface shown in FIG. A pattern forming apparatus having optical systems 480 and 482 for imaging light passing through the array onto the pattern forming material was used.

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

  As shown in FIGS. 14 and 15, there is distortion on the reflection surface of the micromirror 62, and when attention is paid particularly to the center of the mirror, distortion in one diagonal direction (y direction) is different from that in the other diagonal line. It was found that the strain was larger than the distortion in the direction (x direction). For this reason, it has been found 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 clear from a comparison between 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, the distortion of the beam shape in the vicinity of the condensing position was suppressed. As a result, the pattern forming material 150 can be exposed to a higher definition pattern without distortion. Moreover, it turns out that the area | region where a beam diameter is small is wider, ie, the depth of focus is larger in this embodiment shown to FIG.

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

―Pattern formation―
The laminate was manufactured and allowed to stand at room temperature (23 ° C., 55% RH) for 10 minutes. From the support of the obtained laminate, exposure was performed for each line width in increments of 5 μm from 10 μm to 50 μm in line width / space = 1/1 using the pattern forming apparatus. The amount of exposure at this time was the amount of light energy necessary for curing the photosensitive layer of the pattern forming material measured in (2). After leaving still at room temperature for 10 minutes, the support body was peeled off from the said laminated body. A 1 mass% sodium carbonate aqueous solution at 30 ° C. is sprayed over the entire surface of the photosensitive layer on the copper clad laminate at a spray pressure of 0.15 MPa for twice the shortest development time determined in (1) above, and the uncured area is Dissolved and removed.

<Resist pattern shaping process>
The resist pattern after the development was subjected to a resist pattern shaping process using a plasma etching process by a dry process. As the processing conditions, after evacuating the inside of the chamber in which the substrate is placed, applying a voltage while introducing ozone gas into the chamber to generate a plasma state, thereby processing the resist pattern on the substrate. went.

(3) Evaluation of formability The shape of the resist pattern after the resist pattern shaping step was observed, and the shapeability was evaluated based on the following criteria. In addition, when the resist pattern before the resist pattern shaping step and the resist pattern after the resist pattern shaping step were compared with each other with an SEM photograph or the like, in Example 1, before the resist pattern shaping, as shown in FIG. The cross-sectional shape of the resist pattern was an inverted trapezoidal shape, and residues were attached to the gaps. By performing the resist pattern shaping process, the cross-sectional shape of the resist pattern was shaped into a rectangle as shown in FIG. In addition, the residue was removed well.
-Evaluation criteria-
◎ ・ ・ ・ Resist is rectangular and there is no resist residue between patterns ○ ・ ・ ・ Resist is inverted trapezoid, but there is no resist residue between patterns △ ・ ・ ・ Resist Although it is rectangular, there is resist residue between the patterns. × ・ ・ ・ The resist is inverted trapezoid and there is resist residue between the patterns.

(4) Resolution measurement The surface of the copper-clad laminate with a cured resin pattern obtained as described above is observed with an optical microscope, and the cured resin pattern line has a minimum line width free from abnormalities such as tsumari and twist. Measurement was made and this was taken as the resolution. The smaller the numerical value, the better the resolution. The results are shown in Table 3.

(5) Evaluation of adhesion The laminate was prepared in the same manner as described above, and was allowed to stand for 10 minutes at room temperature (23 ° C., 55% RH). From the support side of the obtained laminate, using the pattern forming apparatus, L (line): S (space) = 1: 5, line width 5 μm to 50 μm, each line width is exposed in 5 μm increments, Ten lines were prepared for each. The exposure amount at this time is the amount of light energy necessary for curing the photosensitive layer of the pattern forming material measured above. After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) was peeled off from the laminate. On the entire surface of the photosensitive layer on the copper-clad laminate, a 1% by mass sodium carbonate aqueous solution at 30 ° C. is sprayed at a spray pressure of 0.15 MPa for twice the shortest development time as described above to dissolve uncured regions. After removing, development processing was performed. Next, the resist pattern after the development was subjected to a resist pattern shaping process using a plasma etching process by a dry process as described above.
Apply the JIS-standardized cello tape (registered trademark) to the obtained line pattern, press the cello tape strongly with your finger to bring it into close contact with the line pattern, and then pull and pull the cello tape in the direction perpendicular to the copper-clad laminate. I peeled it off. At this time, if even one of the ten lines is peeled off, it is determined as NG. In particular, since the tip of the line pattern was easily peeled off, the evaluation was performed mainly on the tip. The smallest line width that does not become NG is shown in Table 3 as an evaluation result. For example, when two 20 μm line patterns were peeled off and none of the 25 μm line patterns were peeled off, the adhesion was expressed as 25 μm. The smaller this value, the better the adhesion.

(6) Evaluation of etching property A laminate was prepared in the same manner as described above, and was allowed to stand for 10 minutes at room temperature (23 ° C, 55% RH). From the support side of the obtained laminate, using the pattern forming apparatus, the line width is exposed in increments of 5 μm from 5 μm to 50 μm with a line width of 5 μm to 50 μm, and 10 lines each. Produced. Thereafter, in the same manner as in the evaluation of adhesion, development processing was performed to obtain a resist pattern. Next, the resist pattern after the development was subjected to a resist pattern shaping process using a plasma etching process by a dry process as described above.
The laminated body having the resist pattern subjected to the resist pattern shaping step is subjected to an etching process as described below to form a wiring pattern, and the etching property is evaluated based on the resolution of the wiring pattern. It was.
An iron chloride etchant (ferric chloride-containing etching solution, 40 ° Baume, liquid temperature 40 ° C.) is sprayed at 0.25 MPa for 36 seconds on the surface of the exposed copper-clad laminate in the laminate. Etching was performed by dissolving and removing the uncovered exposed copper layer. Next, the formed pattern was removed by spraying a 2% by mass aqueous sodium hydroxide solution to prepare a printed wiring board having a copper layer wiring pattern on the surface as the permanent pattern. The wiring pattern on the printed wiring board was observed with an optical microscope, the minimum line width of the wiring pattern was measured, and the etching property was evaluated. A smaller minimum line width means that a finer wiring pattern can be obtained and the etching property is better. In Example 1, the minimum line width of the resolvable wiring pattern was 20 μm, and the etching property was extremely excellent. The results are shown in Table 3.

(Example 2)
A printed circuit board was manufactured by a semi-additive method using the pattern forming method of the present invention, and its performance was evaluated.
<Manufacture of laminates>
A pattern-forming material formed in the same manner as in Example 1 was laminated on the surface of a copper-clad laminate in which a sputter foil was laminated as a substrate to prepare a laminate. The sputter foil has a two-layer structure comprising a Ni layer laminated on the surface of a copper clad laminate and a Cu layer having a thickness of 0.2 μm laminated on the surface.

Using the laminate produced in the same manner as described above, a resist pattern shaping step is performed by plasma etching in the same manner as in Example 1 on the resist pattern obtained by exposing and developing in the same manner as in Example 1. It was. About the resist pattern after a resist pattern shaping process, it carried out similarly to Example 1, and evaluated the shaping property, the resolution, and adhesiveness. The results are shown in Table 3.
Moreover, with respect to the laminated body which has the resist pattern which performed the resist pattern shaping process, the plating process in a semi-additive method was performed as follows, and plating property was evaluated.
(7) Evaluation of plating properties-Pretreatment-
A laminate was prepared in the same manner as described above and allowed to stand for 10 minutes at room temperature (23 ° C., 55% RH). From the support side of the obtained laminate, using the pattern forming apparatus, the line width is exposed in increments of 5 μm from 5 μm to 50 μm with a line width of 5 μm to 50 μm, and 10 lines each. Produced. Thereafter, development processing was performed in the same manner as described above to obtain a resist pattern. Next, the resist pattern after the development was subjected to a resist pattern shaping process using a plasma etching process by a dry process as described above.
The resist pattern subjected to the resist pattern shaping step was washed with pure water, and then degreased with Melplate PC-316 (acid immersion degreasing agent, manufactured by Meltex). Next, after washing with hot water and water, pickling was performed with a cleaning solution of sulfuric acid: pure water = 1: 9. This pickling serves not only to remove the oxide film, but also to co-wash the copper sulfate plating bath in the next step.
-Plating treatment-
The resist pattern was plated with a copper sulfate plating bath using a plating solution having the following composition.
Plating solution composition CuSO ₄ · _5H 2 O (copper sulfate pentahydrate, powder) 75 g / l
H ₂ SO ₄ (sulfuric acid) 190 g / l
Cl ⁻ (HCl aqueous solution) 50 mg / l
Cover Grime CLX-A (Meltex, additive) 5 ml / l
Cover Grime CLX-C (Meltex, additive) 5ml / l
After the plating treatment, primary cleaning and secondary cleaning were performed. Thereafter, the formed pattern is removed by spraying a 2% by mass aqueous sodium hydroxide solution, and the etching process is performed to prepare a printed wiring board having a copper layer wiring pattern on the surface as the permanent pattern. did. The wiring pattern on the printed wiring board was observed with an optical microscope, the minimum line width of the wiring pattern was measured, and the plating property was evaluated. A smaller line width means that a higher-definition plating pattern is obtained and the plating property is excellent. In Example 2, the minimum line width of the resolvable wiring pattern was 15 μm, and the plating property was extremely excellent. The results are shown in Table 3.

(Example 3)
In Example 1, except that the resist pattern shaping step was performed by the atmospheric pressure ozone surface treatment described below, a pattern forming material and a laminate were produced in the same manner as in Example 1, and this laminate was exposed and developed. Thus, a resist pattern was obtained. The resist pattern obtained by the atmospheric pressure ozone surface treatment was evaluated for formability, resolution and adhesion.
<Atmospheric pressure ozone surface treatment>
An ozone gas (O ₃ ² ) obtained by compressing and ionizing O ₂ gas is introduced into the chamber in which the substrate is placed, under atmospheric pressure, and chemically reacted with the cured film of the substrate with respect to the resist pattern after development. Then, the surface treatment was performed and the resist pattern was shaped.
Next, in the same manner as in Example 1, the laminated body having the resist pattern subjected to the resist pattern shaping process is etched by the subtractive method to obtain the minimum line width of the formed wiring pattern. In addition, the etching property was evaluated. The results are shown in Table 3.

Example 4
In Example 2, except that the resist pattern shaping step was performed by the atmospheric pressure ozone surface treatment shown in Example 3, a pattern forming material and a laminate were produced in the same manner as in Example 2, and this laminate was exposed. Development was performed to obtain a resist pattern. With respect to the resist pattern obtained by the atmospheric pressure ozone surface treatment, the resolution, adhesion and shaping were evaluated.
Next, in the same manner as in Example 2, the laminated body having the resist pattern subjected to the resist pattern shaping process is plated by the semi-additive method, and the minimum line width of the formed wiring pattern is determined. Then, the plating property was evaluated. The results are shown in Table 3.

(Comparative Example 1)
In Example 1, except that the resist pattern shaping step was not performed, a pattern forming material and a laminate were produced in the same manner as in Example 1, and this laminate was exposed and developed to obtain a resist pattern. About the obtained resist pattern, the formability, the resolution, and the adhesiveness were evaluated. Further, the formability in the comparative example was evaluated by the shape of the resist pattern that was not subjected to resist pattern shaping.
Next, the resist pattern obtained in the same manner as in Example 1 is etched by the subtractive method in the same manner as in Example 1, and based on the minimum line width of the formed wiring pattern, The etching property was evaluated. The results are shown in Table 3.

(Comparative Example 2)
In Example 2, a pattern forming material and a laminate were produced in the same manner as in Example 2 except that the resist pattern shaping step was not performed, and this laminate was exposed and developed to obtain a resist pattern. The obtained resist pattern was evaluated for resolution, adhesion, and shaping (resist pattern shape before shaping).
Next, the resist pattern obtained in the same manner as in Example 2 is subjected to a plating process by a semi-additive method in the same manner as in Example 2, and based on the minimum line width of the formed wiring pattern, The plating property was evaluated. The results are shown in Table 3.

(Comparative Example 3)
In Example 3, a pattern forming material and a laminate were produced in the same manner as in Example 3 except that the resist pattern shaping step was not performed, and this laminate was exposed and developed to obtain a resist pattern. The obtained resist pattern was evaluated for resolution, adhesion, and shaping (resist pattern shape before shaping).
Next, the laminated body having a resist pattern not subjected to resist pattern shaping is subjected to an etching process by a subtractive method in the same manner as in Example 1, and based on the minimum line width of the formed wiring pattern, The etching property was evaluated. The results are shown in Table 3.

(Comparative Example 4)
In Example 4, a pattern forming material and a laminate were produced in the same manner as in Example 4 except that the resist pattern shaping step was not performed, and this laminate was exposed and developed to obtain a resist pattern. The obtained resist pattern was evaluated for resolution, adhesion, and shaping (resist pattern shape before shaping).
Next, for a laminate having a resist pattern that is not subjected to resist pattern shaping, a plating process is performed by a semi-additive method in the same manner as in Example 2, and based on the minimum line width of the formed wiring pattern, The plating property was evaluated. The results are shown in Table 3.

From the results of Table 3, the resist pattern after shaping the resist pattern of Examples 1 and 2 is excellent in formability because of its excellent pattern shape, compared to the resist pattern shaping of Comparative Examples 1 and 2, Moreover, the high resolution and adhesiveness of the resist pattern were obtained. Further, it has been found that a wiring pattern formed by performing an etching process or a plating process using a resist pattern having excellent formability, resolution and adhesion is high-definition and excellent in etching property or plating property.
Further, in Examples 1 and 2 where the resist pattern shaping was performed by plasma etching, it was found that an extremely high-definition wiring pattern was obtained that was particularly excellent in etching property and plating property.

  The pattern forming method of the present invention can form a permanent pattern such as a wiring pattern with high definition and efficiency, and can achieve both high resolution and high adhesion between the substrate and the photosensitive layer. Therefore, it can be preferably used for forming a high-definition wiring pattern.

FIG. 1 is an example of a partially enlarged view showing a configuration of a digital micromirror device (DMD). 2A and 2B are examples of explanatory diagrams for explaining the operation of the DMD. FIGS. 3A and 3B are examples of plan views showing the arrangement of the exposure beam and the scanning line in a case where the DMD is not inclined and in a case where the DMD is inclined. 4A and 4B are examples of diagrams illustrating examples of DMD usage areas. FIG. 5 is an example of a plan view for explaining an exposure method in which the pattern forming material is exposed by one scanning by the scanner. 6A and 6B are examples of plan views for explaining an exposure method for exposing a pattern forming material by a plurality of scans by a scanner. FIG. 7 is an example of a schematic perspective view illustrating an appearance of an example of the pattern forming apparatus. FIG. 8 is an example of a schematic perspective view illustrating the configuration of the scanner of the pattern forming apparatus. FIG. 9A is an example of a plan view showing an exposed region formed in the pattern forming material, and FIG. 9B is an example of a diagram showing an array of exposure areas by each exposure head. FIG. 10 is an example of a perspective view showing a schematic configuration of an exposure head including light modulation means. FIG. 11 is an example of a sectional view in the sub-scanning direction along the optical axis showing the configuration of the exposure head shown in FIG. FIG. 12 is an example of a controller that controls DMD based on pattern information. FIG. 13A is an example of a cross-sectional view along the optical axis showing the configuration of another exposure head having a different coupling optical system, and FIG. 13B shows the exposure when a microlens array or the like is not used. FIG. 13C is an example of a plan view showing a light image projected on 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. FIGS. 15A and 15B are examples of graphs showing the distortion of the reflection surface of the micromirror in the two diagonal directions of the mirror. FIG. 16 is an example of a front view (A) and a side view (B) of a microlens array used in the pattern forming apparatus. FIG. 17 is an example of a front view (A) and a side view (B) of 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 the result of simulating the beam diameter in the vicinity of the condensing position of the microlens of the present invention. FIG. 19B is an example of a diagram showing the same simulation result as that in FIG. 19A at another position. FIG. 19c is an example of a diagram showing the same simulation result as in FIG. 19a at another position. FIG. 19d is an example of a diagram showing the same simulation result as in FIG. 19a at another position. FIG. 20a is an example of a diagram showing the result of simulating the beam diameter in the vicinity of the condensing position of the microlens in the conventional pattern forming method. FIG. 20b is an example of a diagram showing the same simulation result as in FIG. 20a at another position. FIG. 20c is an example of a diagram showing the same simulation result as in FIG. 20a for another position. FIG. 20d is an example of a diagram illustrating simulation results similar to those in FIG. 20a at different positions. FIG. 21 is an example of a plan view showing another configuration of the combined laser light source. FIG. 22 shows an example of a front view (A) and an example of a side view (B) of the microlens constituting the microlens array. FIG. 23 is an example of a schematic diagram illustrating a light condensing state by the microlens of FIG. 22 in one cross section (A) and another cross section (B). FIGS. 24A, 24B, and 24C are examples of explanatory diagrams about the concept of correction by the light amount distribution correction optical system. FIG. 25 is an example of a graph showing the light amount distribution when the light irradiation means has a Gaussian distribution and the light amount distribution is not corrected. FIG. 26 is an example of a graph showing the light amount distribution after correction by the light amount distribution correcting optical system. 27A (A) is a perspective view showing the configuration of the fiber array light source, FIG. 27A (B) is an example of a partially enlarged view of (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 pattern forming method (pattern forming apparatus) of the present invention. FIG. 38 is an example of a process chart for explaining the pattern forming method of the present invention in the subtractive method. FIG. 39 is an example of a process chart for explaining the pattern forming method of the present invention in the semi-additive method. FIG. 40A is a cross-sectional view of a resist pattern formed by development, and shows a state where a residue is generated in a gap between resist patterns having a reverse trapezoidal cross-sectional shape. FIG. 40B is a cross-sectional view of the resist pattern showing a state in which the resist pattern is shaped into a rectangle by the resist pattern shaping step and residues on the substrate surface are removed.

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 55a Micro lens 56 Surface to be exposed (scanning surface)
57 Lens of second imaging optical system 58 Lens of second imaging optical system 59 Aperture array 64 Laser module 66 Fiber array light source 67 Lens system 68 Laser emitting unit 69 Mirror 70 Prism 71 Condensing lens 72 Rod integrator 73 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 Pattern forming material 152 Stage 155a Micro lens 156 Installation table 158 Guide 160 Gate 162 Scanner 164 Sensor 166 Exposure head 168 Exposure area 170 Exposed area 180 Heat block 184 Collimating lens Ray 302 controller 304 stage driver 454 lens system 468 exposure area 472 microlens array 474 microlens 476 aperture array 478 aperture 480 lens system 501a underlayer (Cu foil)
501b Underlayer (Ni, Cr foil)
502 Insulating Layer 503 Support 504 Photosensitive Layer 505 Pressing Roll 506 Cured Film 507 Electrolytic Copper Plating 508 Residue

Claims (12)

  The photosensitive layer in a pattern forming material having at least a photosensitive layer on a support is laminated on a substrate to be processed, the photosensitive layer is exposed and developed to form a resist pattern, and then dried on the resist pattern. A pattern forming method, wherein a resist pattern shaping step is performed by a process.   The pattern formation method according to claim 1, wherein the resist pattern shaping step is performed by a plasma etching process.   The pattern formation method according to claim 2, wherein the plasma etching process is performed under reduced pressure.   The pattern formation method according to claim 1, wherein the resist pattern shaping step is performed by atmospheric pressure ozone surface treatment.   The pattern formation method according to claim 4, wherein the atmospheric pressure ozone surface treatment is performed in the atmosphere.   The pattern forming method according to claim 1, wherein the substrate is a printed wiring board manufacturing substrate.   The pattern forming method according to claim 1, wherein a permanent pattern is formed after the resist pattern shaping step is performed.   The pattern forming method according to claim 7, wherein the permanent pattern is a wiring pattern, and the permanent pattern is formed by at least one of an etching process and a plating process.   The pattern formation method according to claim 8, wherein the wiring pattern is formed by one of a subtractive method and a semi-additive method.   The pattern formation method in any one of Claim 1 to 9 in which a photosensitive layer contains a polymeric compound, a binder, and a photoinitiator.   The exposure is performed by modulating light from the light irradiating means by light modulating means having n picture elements for receiving and emitting light from the light irradiating means, and then aberration due to distortion of the exit surface in the picture element. The pattern forming method according to claim 1, wherein the pattern forming method includes at least a microlens array in which microlenses having aspherical surfaces capable of correcting the above are arranged. The pattern forming method according to claim 11, wherein the aspherical surface is a toric surface.