JP2006048031A - Photosensitive film, process for producing the same and process for forming permanent pattern - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive film that exhibits higher thermal resistance, higher surface hardness and a lower coefficient of thermal expansion, represents superior conformability to irregularities of substrate surface and less possibility of inferior adhesion of solder resist, is nearly free of lowering of exposure sensitivity, excels in storage stability, and has so satisfactory sensitivity to LDI that it can be suitably used, and to provide a process for producing the photosensitive film and a process for forming a permanent pattern. <P>SOLUTION: The photosensitive film used for forming a permanent pattern comprises a support, a cushion layer, a barrier layer capable of suppressing transfer of substances, and a photosensitive layer, in this order, wherein the photosensitive layer is formed of a photosensitive composition which comprises (A) a binder, (B) a polymerizable compound, (C) a photopolymerization initiator and (D) a filler. It is preferable that interlayer adhesive force between the cushion layer and the barrier layer is smallest among interlayer adhesive forces between layers. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a photosensitive film for forming an insulating film covering a printed wiring board or the like and a solder resist as a protective film, a method for producing the same, and a method for forming a permanent pattern using the photosensitive film.

In general, printed wiring boards to which electronic components such as semiconductors, capacitors, and resistors are soldered are covered with a solder resist that forms an insulating film and a protective film, except for the places where the electronic components are soldered. The adjacent electrodes do not conduct. The solder resist is patterned into a predetermined pattern by exposing and developing the photosensitive resin layer by photolithography.
The solder resist obtained by exposing and developing the photosensitive resin layer is required to have high heat resistance, high surface hardness, and low thermal expansion coefficient.

In recent years, high density printed wiring boards such as build-up wiring boards have been used in portable electronic devices such as mobile phones and digital cameras, and the solder resist has been miniaturized.
Conventionally, the photosensitive resin layer is supplied in the form of a resin solution in which a photosensitive resin material is dissolved in an organic solvent or the like, and is formed by applying the resin solution to the surface of a printed wiring board or the like. (For example, refer to Patent Document 1).
However, in this case, a special coating device such as a roll coater or a spinner is required, and it is difficult to make the thickness of the photosensitive resin layer uniform. There is a problem that waste liquid treatment is difficult.

Conventionally, in order to solve these problems, a photosensitive film in which a photosensitive layer containing a photosensitive resin material and other layers having various functions are laminated on a support to form a dry film is known. (See Patent Documents 2 and 3).
The solder resist is formed by laminating the photosensitive film on the surface of a substrate on which a predetermined wiring pattern is formed by at least one of heating and pressurization, and then peeling off only the support. Obtained by exposure and development.
However, in this case, there is a problem that a solder resist formed using the photosensitive film cannot obtain desired performance with respect to heat resistance, surface hardness, and thermal expansion coefficient. Further, when the photosensitive film is laminated on the surface of the base material on which a predetermined wiring pattern is formed, air bubbles are generated without sufficiently following the unevenness of the surface of the base material, and the solder resist is applied to the base material. There was a problem of causing poor adhesion.
In addition, a substance such as a polymerizable compound contained in the photosensitive layer may move to other adjacent layers, resulting in a problem that exposure sensitivity is lowered.

  On the other hand, conventionally, an exposure apparatus using a photomask is known as an exposure apparatus for performing the photolithography method. However, along with the miniaturization of the solder resist, the expansion and contraction of the substrate during the photolithography process is known. The problem of positional deviation of fine patterns and through-hole land patterns due to expansion / contraction based on temperature / humidity changes of photomask films has become apparent. In order to solve the problem of displacement, a substrate with less deformation or an expensive glass mask has been used.

In recent years, in order to solve these misregistration problems, based on an exposure pattern formed by correcting digital data such as a wiring pattern corresponding to the misregistration information without using a photomask, An exposure apparatus using a laser direct imaging system (hereinafter also referred to as “LDI”) that performs patterning by directly scanning laser light such as a semiconductor laser or a gas laser onto a photosensitive composition has been studied.
However, the conventional solder resist has a problem that it does not have sufficient sensitivity to the laser light of 395 nm to 415 nm used for the LDI.

  Therefore, it has good heat resistance, surface hardness, low thermal expansion coefficient, excellent storage stability, good adhesion to the base material, good workability during solder resist formation, and is sufficient for LDI. A photosensitive film that has sensitivity and can be suitably used, a method for producing the photosensitive film, and a method for forming a permanent pattern using the photosensitive film have not yet been sufficiently satisfactory. Is the current situation.

JP-A 61-243869 JP 2003-162055 A JP-A-9-188745

  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 has high heat resistance, high surface hardness, and low thermal expansion coefficient, excellent storage stability, good followability to the unevenness of the substrate surface, without causing poor adhesion of the solder resist, A photosensitive film used for forming a permanent pattern that is less susceptible to a decrease in exposure sensitivity and can be suitably used with sufficient sensitivity to LDI, a method for manufacturing the same, and formation of a permanent pattern using the photosensitive film It aims to provide a method.

Means for solving the problems are as follows. That is,
<1> A support, a cushion layer, a barrier layer capable of suppressing the movement of a substance, (A) a binder, (B) a polymerizable compound, (C) a photopolymerization initiator, and (D) an extender pigment. A photosensitive film comprising a photosensitive layer made of a photosensitive composition in this order and used for forming a permanent pattern.
<2> The photosensitive film according to <1>, wherein the content of the extender pigment (D) is 10 to 60% by mass.
<3> The photosensitive film according to any one of <1> to <2>, wherein the interlayer adhesive strength between the cushion layer and the barrier layer is the smallest among the interlayer adhesive strengths between the respective layers.
<4> The photosensitive film according to any one of <1> to <3>, wherein the photosensitive layer has a thickness of 10 to 100 μm, and the cushion layer has a thickness of 5 to 100 μm.
<5> The photosensitive film according to any one of <1> to <4>, wherein the cushion layer contains a thermoplastic resin.
<6> The photosensitive film according to <5>, wherein either the glass transition temperature (Tg) or the softening point of the thermoplastic resin is 80 ° C. or lower.
<7> The photosensitive film according to any one of <1> to <6>, wherein the barrier layer includes at least one of a vinyl polymer and a vinyl copolymer.
<8> The glass transition of the binder (A) is (a) maleic anhydride, (b) an aromatic vinyl monomer, and (c) a vinyl monomer, the homopolymer of the vinyl monomer. A copolymer obtained by reacting 0.1 to 1.0 equivalent of a primary amine compound with an anhydride group of a copolymer comprising a vinyl monomer having a temperature (Tg) of less than 80 ° C. It is a photosensitive film in any one of said <1> to <7> containing.
<9> The photosensitive film according to any one of <1> to <8>, wherein the polymerizable compound (B) includes at least one selected from monomers having a (meth) acryl group.
<10> The photopolymerization initiator (C) is selected from halogenated hydrocarbon derivatives, phosphine oxides, hexaarylbiimidazoles, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, and ketoxime ethers. The photosensitive film according to any one of <1> to <9>, including at least one selected from the above.
<11> A cushion layer forming step of applying a water-dispersed emulsion containing a thermoplastic resin on a support and drying to form a cushion layer;
On the cushion layer, a barrier layer forming step in which a barrier layer coating solution in which the composition contained in the barrier layer is dissolved, emulsified or dispersed is applied and dried to form a barrier layer;
On the barrier layer, a solution of a photosensitive composition containing (A) a binder, (B) a polymerizable compound, (C) a photopolymerization initiator and (D) an extender pigment is applied and dried to form a photosensitive layer. And a photosensitive layer forming step of forming a photosensitive film.
<12> A laminating step of laminating the photosensitive film according to any one of <1> to <10> so that the photosensitive layer is on the surface side of the substrate by at least one of heating and pressurization;
An exposure step of exposing the laminated photosensitive layer with light irradiated from a light irradiation means;
And a development step of developing the photosensitive layer exposed in the exposure step.
<13> After the exposure step, the method includes a peeling step of peeling the support and the cushion layer from the barrier layer at the same time between the cushion layer and the barrier layer, and then developing the photosensitive layer by the developing step <12> The method for forming a permanent pattern according to the above.
<14> The above-described <12>, which includes a peeling step of peeling the support and the cushion layer from the barrier layer simultaneously between the cushion layer and the barrier layer after the lamination step, and then exposing the photosensitive layer by the exposure step. The method for forming a permanent pattern according to the above.
<15> The method for forming a permanent pattern according to any one of <12> to <14>, wherein at least one of a protective film and an interlayer insulating film is formed.
<16> After the exposure step modulates the light from the light irradiating means by the light modulating means having n picture elements for receiving and emitting the light from the light irradiating means, the emission surface in the picture element portion The permanent light exposure according to any one of <12> to <15>, wherein the photosensitive layer is exposed with light that has passed through a microlens array in which microlenses having aspherical surfaces capable of correcting aberration due to distortion of the lens are arranged. This is a pattern forming method.
<17> The method for forming a permanent pattern according to <16>, wherein the aspherical surface is a toric surface.
<18> The <16> to <17, wherein the light modulation unit can control any less than n pixel elements arranged continuously from n pixel elements in accordance with pattern information. The permanent pattern forming method according to any one of the above.
<19> The method for forming a permanent pattern according to any one of <16> to <18>, wherein the light modulator is a spatial light modulator.
<20> The method for forming a permanent pattern according to <19>, wherein the spatial light modulation element is a digital micromirror device (DMD).
<21> The method for forming a permanent pattern according to any one of <12> to <20>, wherein the exposure is performed through an aperture array.
<22> The method for forming a permanent pattern according to any one of <12> to <21>, wherein the exposure is performed while relatively moving the exposure light and the photosensitive layer.
<23> The method for forming a permanent pattern according to any one of <12> to <22>, wherein the light irradiation unit can synthesize and irradiate two or more lights.
<24> The light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that collects and couples the laser beams emitted from the plurality of lasers to the multimode optical fiber, respectively. The permanent pattern forming method according to any one of <12> to <23>.
<25> The method for forming a permanent pattern according to <24>, wherein the laser beam has a wavelength of 395 to 415 nm.
<26> The method for forming a permanent pattern according to any one of <12> to <25>, wherein the photosensitive layer is cured after the development step.
<27> The method for forming a permanent pattern according to <26>, wherein the curing treatment is at least one of a whole surface exposure treatment and a whole surface heat treatment performed at 120 to 200 ° C.

  According to the present invention, it is possible to solve conventional problems, high heat resistance, high surface hardness, and low thermal expansion coefficient, excellent storage stability, good followability to unevenness on the substrate surface, and a solder resist. A photosensitive film that does not cause poor adhesion of the film, is unlikely to cause a decrease in exposure sensitivity, has sufficient sensitivity to LDI, and can be suitably used, a method for producing the photosensitive film, and the photosensitive film. A method for forming the permanent pattern used can be provided.

(Photosensitive film)
The photosensitive film of the present invention comprises a support, a cushion layer, a barrier layer, and a photosensitive layer in this order, and further comprises other layers as necessary.

The interlayer adhesive force of each layer is not particularly limited and may be appropriately selected depending on the purpose. Among the interlayer adhesive forces of each layer, the interlayer adhesive force between the cushion layer and the barrier layer (hereinafter, It is preferable that the “interlayer adhesion force A”) is sometimes the smallest.
Further, an interlayer adhesive force between the support and the cushion layer (hereinafter also referred to as “interlayer adhesive force B”) and an interlayer adhesive force between the barrier layer and the photosensitive layer (hereinafter referred to as “interlayer adhesive force”). May be the same as or different from each other, but the interlayer adhesive force C is greater than the interlayer adhesive force B and greater than the interlayer adhesive force A. Moreover, since the number of peeling steps is reduced, it is preferable.
Further, since the interlayer adhesive force A is smaller than the interlayer adhesive force B, the cushion layer peels off together with the support when the support is peeled off, so that the step of peeling only the cushion layer is omitted. Therefore, it is preferable. When the interlayer adhesive force A is greater than the interlayer adhesive force B, it is necessary to peel the cushion layer from the photosensitive layer using an adhesive tape or the like after the support is peeled off.

  The method for minimizing the interlayer adhesive force A is not particularly limited and can be appropriately selected according to the purpose. For example, the interlayer adhesive force A can be reduced by adding a release agent to the cushion layer. And a method of increasing the interlayer adhesive strengths B and C. These methods may be used alone or in combination of two or more.

  There is no restriction | limiting in particular as said mold release agent, It can select suitably from well-known mold release agents, For example, a silicone compound, the compound which has a fluorinated alkyl group, etc. are mentioned.

  Examples of the silicone compound include Daicel UCB, Ebeacryl 1360, 350, Toshiba Silicone dimethyl silicone oil TSF400, methylphenylsilicone oil TSF4300, silicone polyether copolymers TSF4445, TSF4446, TSF4460, TSF4452, and the like. It is done.

  Examples of the compound having a fluorinated alkyl group include a fluorine-based surfactant (for example, perfluoroalkyl group / hydrophilic group-containing oligomer F-171, perfluoroalkyl group / lipophilic group manufactured by Dainippon Ink & Chemicals, Inc. -Containing oligomer F-173, perfluoroalkyl group / hydrophilic group / lipophilic group-containing oligomer F-177, perfluoroalkyl group / lipophilic group-containing urethane F-183, F-184, fluorine-based graft polymer, etc.), fluorine System graft polymers (for example, Aron GF-300, GF-150, etc., manufactured by Toagosei Co., Ltd.).

  The method for increasing the interlayer adhesive force B is not particularly limited and may be appropriately selected depending on the intended purpose. For example, (1) surface treatment is performed on the adhesive surface between the support layer and the cushion layer. A method, (2) a method of adjusting the content of at least one selected from the components contained in at least one of the support and the cushion layer, and (3) containing or applying a component that improves adhesive strength. And (4) a method of containing at least one of a crosslinking agent and a silane coupling agent. These may be used alone or in combination of two or more.

  The method for increasing the interlayer adhesion C is not particularly limited and may be appropriately selected depending on the intended purpose. For example, (5) a method for surface-treating the adhesive surface between the barrier layer and the photosensitive layer (6) The method according to (3) and (4) above, in addition to the method of adjusting the content of at least one selected from components contained in at least one of the barrier layer and the photosensitive layer Etc. These methods may be used alone or in combination of two or more.

  Examples of the surface treatment include plasma treatment, electron beam treatment, glow discharge treatment, corona discharge treatment, and ultraviolet irradiation treatment.

As a method for adjusting the content, for example, when the cushion layer contains a copolymer essential for the ethylene, a method for setting the ethylene copolymerization ratio in the copolymer to less than 60% by mass is mentioned. It is done.
When it exceeds 60 mass%, the interlayer adhesive force C and the interlayer adhesive force B may be smaller than the interlayer adhesive force A.

  Examples of the component for improving the adhesive strength include phenolic substances (for example, cresol novolac resin, phenol resin, etc.), polyvinylidene chloride resin, styrene butadiene rubber, gelatin, polyvinyl alcohol, and celluloses.

Examples of the crosslinking agent include borax, boric acid, borates (for example, orthoborate, InBO ₃ , ScBO ₃ , YBO ₃ , LaBO ₃ , Mg ₃ (BO ₃ ) ₂ , Co ₃ (BO ₃ ) ₂ , two Borate (eg, Mg ₂ B ₂ O ₅ , Co ₂ B ₂ O ₅ ), metaborate (eg, LiBO ₂ , Ca (BO ₂ ) ₂ , NaBO ₂ , KBO ₂ ), tetraborate (eg, Na ₂ B ₄ O ₇ · 10H ₂ O) and boron compounds such as pentaborate (for example, KB ₅ O ₈ · 4H ₂ O, Ca ₂ B ₆ O ₁₁ · 7H ₂ O, CsB ₅ O ₅ ). Among these, borax, boric acid, and borate are preferable, and boric acid is more preferable in that a crosslinking reaction can be rapidly caused, and aldehydes such as formaldehyde, glyoxal, and glutaraldehyde are also preferable. Compounds; ketone compounds such as diacetyl and cyclopentanedione; bis (2-chloroethylurea) -2-hydroxy-4,6-dichloro-1,3,5-triazine, 2,4-dichloro-6-S— Active halogen compounds such as triazine sodium salt; divinylsulfonic acid, 1,3-vinylsulfonyl-2-propanol, N, N′-ethylenebis (vinylsulfonylacetamide), 1,3,5-triacryloyl-hexahydro -Active vinyl compounds such as S-triazine; N-methylol compounds such as dimethylolurea and methyloldimethylhydantoin; melamine resins (for example, methylolmelamine, alkylated methylolmelamine); epoxy resins; 1,6-hexamethylene diisocyanate, etc. Isocyanate compounds; U.S. Pat. No. 301 Aziridine compounds described in US Pat. No. 280, US Pat. No. 2,983,611; Carboximide compounds described in US Pat. No. 3,100,704; Epoxy compounds such as glycerol triglycidyl ether; 1,6-hexamethylene -Ethyleneimino compounds such as -N, N'-bisethyleneurea; halogenated carboxaldehyde compounds such as mucochloric acid and mucophenoxycyclolic acid; 2,3-dihydroxydioxane, 2,3-dihydroxy-1,4-dioxane Dioxane compounds such as: Titanium lactate, aluminum sulfate, chromium alum, potash alum, metal-containing compounds such as zirconyl acetate and chromium acetate, polyamine compounds such as tetraethylenepentamine, hydrazide compounds such as adipic acid dihydrazide, oxazoline groups 2 or more Small molecule or polymer containing, and the like. These may be used alone or in combination of two or more.

  Examples of the silane coupling agent include N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, and N-2 (aminoethyl) 3-amino. Propyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrime Toxylsilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane and the like can be mentioned. Moreover, the silane coupling agent by Shin-Etsu Chemical Co., Ltd. can also be used conveniently.

  The layer containing at least one of the crosslinking agent and the silane coupling agent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the cushion layer and the barrier layer are preferable, and the cushion A layer alone is more preferred.

[Support]
The support is not particularly limited and may be appropriately selected depending on the intended purpose. However, the adhesive force between the support and the cushion layer is larger than the adhesive force between the cushion layer and the barrier layer. In addition, it is preferable that light transmittance is good, and it is more preferable that surface smoothness is good.

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, polytri Various plastic films such as fluoroethylene, cellulose-based film, nylon film and the like can be mentioned, and among these, polyethylene terephthalate is particularly preferable. These may be used alone or in combination of two or more.
As the support, for example, the support described in JP-A-4-208940, JP-A-5-80503, JP-A-5-173320, JP-A-5-72724, or the like is used. You can also.

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

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

[Cushion layer]
The material, physical properties, thickness, structure, etc. of the cushion layer are not particularly limited and may be appropriately selected depending on the intended purpose. However, a layer containing a thermoplastic resin is preferred, and the thermoplastic resin is softened. The point is more preferably 80 ° C. or less, still more preferably 60 ° C. or less, and particularly preferably 50 ° C. or less.
When a cushion layer having a softening point of the thermoplastic resin of 80 ° C. or higher is used, the transfer temperature of the photosensitive film to the substrate surface needs to be high in order to obtain sufficient followability to the unevenness of the substrate surface. In particular, for a film-like base material, it may impair the dimensional stability of the base material, and may be disadvantageous in terms of working time required for heating / cooling, electric power required for heating, etc. is there.
In addition, as a measuring method of the softening point of the said thermoplastic resin, the measuring method based on ASTMD-1235 (Vicker Vicat method) is mentioned.
Further, the cushion layer may be soluble or insoluble in an alkaline liquid. Further, it may be swellable with respect to an alkaline liquid.

Examples of the thermoplastic resin include polyolefin resins such as polyethylene, polypropylene, and polyolefin copolymers, ethylene acetate / vinyl copolymers, ethylene ethyl acrylate copolymers, ethylene acrylate copolymers, and saponified products thereof. Ethylene copolymer resins such as polyvinyl chloride, vinyl chloride copolymers, vinyl chloride copolymer resins such as saponified products thereof, polyvinylidene chloride, vinylidene chloride copolymers, polystyrene, styrene and (meth) acrylic acid Ester copolymers, styrene copolymer resins such as saponified products thereof, polyvinyltoluene, vinyltoluene and (meth) acrylic acid ester copolymers, vinyltoluene copolymer resins such as saponified products thereof, poly (meth) Acrylic acid ester, butyl (meth) acrylate Copolymers of vinyl acetate, vinyl copolymer nylon acetate, copolymer nylon, N- alkoxy-di mesylation nylon, N- dimethylamino nylon or the like of the polyamide resin, etc. These ionomer resins.
Among these, viewpoints such as interlayer adhesive strength at which the interlayer adhesive strength (interlayer adhesive strength A) between the cushion layer and the barrier layer is minimized, and prevention of migration of the polymerization component in the photosensitive layer to the thermoplastic resin during storage, etc. And ethylene vinyl acetate copolymer, polyolefin ionomer, and the like.
Specific examples of the ethylene vinyl acetate copolymer include Chemipearl V type (manufactured by Mitsui Chemicals, Inc.).
Specific examples of the polyolefin ionomer include Chemipearl S type (manufactured by Mitsui Chemicals).
The thermoplastic resin can be used alone or in combination of two or more.
As the thermoplastic resin, an organic high softening point of about 80 ° C. or less according to “Plastic Performance Handbook” (edited by the Japan Plastics Industry Federation, edited by the All Japan Plastics Molding Industry Association, published by the Industrial Research Council, issued on October 25, 1968). It is also possible to use molecules.
Furthermore, it is also possible to add various plasticizers to the thermoplastic resin having a softening point of 80 ° C. or higher so that the substantial softening point is 80 ° C. or lower. The plasticizer is not particularly limited as long as it has a substantial softening point of 80 ° C. or lower, and can be appropriately selected according to the purpose.
As the thermoplastic resin, one that matches the solubility characteristics of the composition constituting the photosensitive layer can be selected, and the thermoplastic resin has solubility characteristics that are soluble in a solvent in which the composition constituting the photosensitive layer does not dissolve at all. It is also possible to choose.
As the cushion layer, various polymers, supercooling substances, adhesion improvers, surfactants, release agents, etc. can be added as long as the softening point of the thermoplastic resin does not exceed 80 ° C. It is.

There is no restriction | limiting in particular as thickness of the said cushion layer, Although it can select suitably according to the objective, For example, 5-100 micrometers is preferable, 10-50 micrometers is more preferable, and 15-40 micrometers is especially preferable.
When the thickness is less than 5 μm, unevenness on the surface of the substrate and unevenness followability to bubbles and the like may be deteriorated, and a high-definition permanent pattern may not be formed. Such a problem may occur.
The method for forming the cushion layer is not particularly limited and may be appropriately selected depending on the purpose. For example, the cushion layer composition may be formed by a method of melt-forming a cushion layer composition containing the thermoplastic resin or the like, or a melt casting method. Examples include a method of forming a film, a method of forming a film of an aqueous dispersion emulsion of a cushion layer composition containing the thermoplastic resin and the like by a casting method, and among these, a method of casting an aqueous dispersion emulsion containing a thermoplastic resin. From the viewpoint of environmental load countermeasures and explosion-proof management, a method of applying a film on the support by the above method is preferable.

[Barrier layer]
The barrier layer is not particularly limited as long as the movement of a substance can be suppressed, and can be appropriately selected according to the purpose. Water-soluble, water-dispersible, soluble in an alkaline liquid, And may be insoluble.
That the movement of the substance can be suppressed means that the increase or decrease in the content of the target substance in the layer adjacent to the barrier layer is suppressed as compared with the case where the barrier layer is not provided.

  There is no restriction | limiting in particular as said substance, Although it can select suitably according to the objective, For example, the substance contained in at least any one of oxygen, water, the said photosensitive layer, and a cushion layer is mentioned.

When the barrier layer is water-soluble, it preferably contains a water-soluble resin. When the barrier layer is water-dispersible, it preferably contains a water-dispersible resin and is soluble in an alkaline liquid. In some cases, it is preferable to include a resin that is soluble in an alkaline liquid. In cases where the resin is insoluble in an alkaline liquid, it is preferable to include a resin that is insoluble in an alkaline liquid.
In addition, as said water solubility degree, what melt | dissolves 0.1 mass% or more with respect to 25 degreeC water, for example, and what melt | dissolves 1 mass% or more is more preferable.

  The resin is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include various alcohol-soluble resins, water-soluble resins, alcohol-dispersible resins, water-dispersible resins, emulsifiable resins, and alkaline liquids. Examples include vinyl polymers (for example, polyvinyl alcohol (including modified polyvinyl alcohols), polyvinylpyrrolidone, etc.), the above-mentioned vinyl copolymers, water-soluble polyamides, and gelatins. , Cellulose, and derivatives thereof. In addition, the thermoplastic resin described in Japanese Patent No. 2794242, the compound used in the intermediate layer, the binder, and the like can also be used. These may be used alone or in combination of two or more.

Examples of the resin insoluble in the alkaline liquid include a copolymer whose main component is ethylene as an essential copolymer component.
The copolymer having ethylene as an essential copolymer component is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethylene-vinyl acetate copolymer (EVA) and ethylene-ethyl acrylate. A copolymer (EEA) etc. are mentioned.

There is no restriction | limiting in particular as thickness of the said barrier layer, Although it can select suitably according to the objective, For example, less than 10 micrometers is preferable, 0.1-6 micrometers is more preferable, and 1-5 micrometers is especially preferable.
When the thickness is 10 μm or more, light scattering occurs in the barrier layer during exposure, and at least one of resolution and adhesion may be deteriorated.

  Since the photosensitive film of the present invention has a barrier layer between the cushion layer and the photosensitive layer, substances such as a polymerizable compound contained in the photosensitive layer are prevented from moving to the cushion layer, and at the time of exposure. Sensitivity deterioration of the photosensitive layer can be prevented.

[Photosensitive layer]
The photosensitive layer includes at least (A) a binder, (B) a polymerizable compound, (C) a photopolymerization initiator, and (D) an extender pigment, and further includes other components appropriately selected as necessary. It consists of a photosensitive composition.

<Binder>
There is no restriction | limiting in particular as said (A) binder, According to the objective, it can select suitably, For example, 1 or more types of primary amine compounds are made to react with the anhydride group of a maleic anhydride copolymer. Copolymers obtained, JP-A-51-131706, JP-A-52-94388, JP-A-64-62375, JP-A-2-97513, JP-A-3-289656, JP-A-61-243869 And an epoxy acrylate compound having an acidic group described in JP-A No. 2002-296776.

The binder is preferably swellable in an alkaline aqueous solution, and more preferably soluble in an alkaline aqueous solution.
As the binder exhibiting swellability or solubility with respect to the alkaline aqueous solution, for example, those having an acidic group are preferably exemplified, and 0.1 to 1.2 with respect to the anhydride group of the maleic anhydride copolymer. Particularly preferred is a copolymer obtained by reacting at least one equivalent of a primary amine compound.

Examples of the epoxy acrylate compound having an acidic group include phenol novolac type epoxy acrylate, cresol novolac epoxy acrylate, bisphenol A type epoxy acrylate, and the like, for example, (meth) acrylic acid for epoxy resins and polyfunctional epoxy compounds. And those obtained by reacting a carboxyl group-containing monomer such as phthalic anhydride and further adding a dibasic acid anhydride such as phthalic anhydride.
The molecular weight of the epoxy acrylate compound is preferably 1,000 to 200,000, and more preferably 2,000 to 100,000. When the molecular weight is less than 1,000, the tackiness of the surface of the photosensitive layer may become strong, and after curing of the photosensitive layer described later, the film quality may become brittle or the surface hardness may deteriorate. If it exceeds 1,000, developability may deteriorate.

  An acrylic resin having at least one polymerizable group such as an acidic group and a double bond described in JP-A-6-295060 can also be used. Specifically, at least one polymerizable double bond in the molecule, for example, an acrylic group such as (meth) acrylate group or (meth) acrylamide group, various polymerizations such as carboxylic acid vinyl ester, vinyl ether, allyl ether, etc. Sex double bonds can be used. More specifically, an acrylic resin containing a carboxyl group as an acidic group, glycidyl acrylate, a compound obtained by glycidyl methacrylate, an acrylic resin containing an anhydride group contains a hydroxyl group such as hydroxyalkyl (meth) acrylate And compounds obtained by adding a polymerizable compound to be added. As these commercially available products, for example, “Kaneka Resin AX; manufactured by Kaneka Chemical Industry Co., Ltd.”, “Cyclomer (CYCLOMER) A-200; manufactured by Daicel Chemical Industries, Ltd.”, “Cyclomer (CYCLOMER) M-” 200; Daicel = 112 ° C.) and the like, which may be preferably used alone or in combination of two or more.

The primary amine compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include benzylamine, phenethylamine, 3-phenyl-1-propylamine, 4-phenyl-1-butylamine, 5- Phenyl-1-pentylamine, 6-phenyl-1-hexylamine, α-methylbenzylamine, 2-methylbenzylamine, 3-methylbenzylamine, 4-methylbenzylamine, 2- (p-tolyl) ethylamine, β -Methylphenethylamine, 1-methyl-3-phenylpropylamine, 2-chlorobenzylamine, 3-chlorobenzylamine, 4-chlorobenzylamine, 2-fluorobenzylamine, 3-fluorobenzylamine, 4-fluorobenzylamine, 4 -Bromophenethylamine, 2- (2-chloropheny L) ethylamine, 2- (3-chlorophenyl) ethylamine, 2- (4-chlorophenyl) ethylamine, 2- (2-fluorophenyl) ethylamine, 2- (3-fluorophenyl) ethylamine, 2- (4-fluorophenyl) Ethylamine, 4-fluoro-α, α-dimethylphenethylamine, 2-methoxybenzylamine, 3-methoxybenzylamine, 4-methoxybenzylamine, 2-ethoxybenzylamine, 2-methoxyphenethylamine, 3-methoxyphenethylamine, 4-methoxy Phenethylamine, methylamine, ethylamine, propylamine, 1-propylamine, butylamine, t-butylamine, sec-butylamine, pentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine , Laurylamine, aniline, octylaniline, anisidine, 4-chloroaniline, 1-naphthylamine, methoxymethylamine, 2-methoxyethylamine, 2-ethoxyethylamine, 3-methoxypropylamine, 2-butoxyethylamine, 2-cyclohexyloxyethylamine , 3-ethoxypropylamine, 3-propoxypropylamine, 3-isopropoxypropylamine and the like. Among these, benzylamine and phenethylamine are particularly preferable.
The said primary amine compound may be used individually by 1 type, and may use 2 or more types together.

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

  The binder (A) includes (a) maleic anhydride, (b) an aromatic vinyl monomer, and (c) a vinyl monomer, the glass transition temperature of the homopolymer of the vinyl monomer. A copolymer obtained by reacting 0.1 to 1.0 equivalent of a primary amine compound with an anhydride group of a copolymer comprising a vinyl monomer having a (Tg) of less than 80 ° C. The inclusion is preferred.

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

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

  The molecular weight of the binder is preferably 1,000 to 1,000,000, and more preferably 8,000 to 150,000. When the molecular weight is less than 1,000, the film quality becomes brittle and the surface hardness may deteriorate after curing of the photosensitive layer described later. When the molecular weight exceeds 1,000,000, the photosensitive composition is heated. The fluidity at the time of lamination may be low, and it may be difficult to ensure proper laminating properties, and developability may be deteriorated.

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

<Polymerizable compound>
The (B) polymerizable compound is not particularly limited and may be appropriately selected depending on the intended purpose. The compound which is the above is preferable, for example, at least 1 sort (s) selected from the monomer which has a (meth) acryl group is mentioned suitably.

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

  2-50 mass% is preferable, as for solid content in the said photosensitive composition solid content of the said polymeric compound, 4-40 mass% is more preferable, and 5-30 mass% is especially preferable. If the solid content is less than 5% by mass, problems such as deterioration of developability and reduction in exposure sensitivity may occur, and if it exceeds 50% by mass, the adhesiveness of the photosensitive layer may become too strong. Yes, not preferred.

<Photopolymerization initiator>
The (C) 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. It may be an activator that produces some action with a sensitizer and generates active radicals, or an initiator that initiates cationic polymerization depending on the type of monomer. Among these, those having photosensitivity to visible light from the ultraviolet region are preferable, those having high sensitivity to exposure with laser light having a wavelength of 395 to 415 nm are more preferable, halogenated hydrocarbon derivatives, phosphine It is particularly preferable to include at least one selected from oxides, hexaarylbiimidazoles, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts and ketoxime ethers.
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), phosphine oxide, hexaarylbiimidazole, oxime derivatives, organic peroxides, Preferred examples include thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers and the like.

  Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent No. 1388492, a compound described in JP-A-53-133428, a compound described in German Patent No. 3333724, 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, US Pat. No. 4,221,976 And compounds described in the book.

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

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

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

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

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

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

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

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

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

  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.), metallocenes (for example, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3-) (1H-pyrrol-1-yl) -phenyl) titanium, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), etc.), JP-A-53-133428, Kosho 57-1819, 57-609 JP, and include compounds described in U.S. Patent No. 3,615,455.

  Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzolphenone, benzophenonetetracarboxylic acid or tetramethyl ester thereof, 4,4′-bis (dialkylamino) benzophenone (for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′- Bisdicyclohexylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4′-dimethylamino Nzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-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 hexaarylbiimidazole compound include 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-bisimidazole and 2,2′-bis. (2-Chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′- Bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis (2, , 6-trichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis (2-cyanophenyl) -4,4 ′, 5.5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2-cyanophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis (2-methylphenyl) -4,4 ', 5,5'-tetrakis (4-methoxycarbonylphenyl) biimidazole, 2,2'-bis (2-methylphenyl) -4,4', 5,5'-tetrakis 4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis ( 2-ethylphenyl) -4,4 ′, 5,5′-tetrakis (4-methoxycarbonylphenyl) biimidazole, 2,2′-bis (2-ethylphenyl) -4,4 ′, 5,5′- Tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2-ethylphenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′- Bis (2-phenylphenyl) -4,4 ′, 5,5′-tetrakis (4-methoxycarbonylphenyl) biimidazole, 2,2′-bis (2-phenyl) Enylphenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2-phenylphenyl) -4,4 ′, 5,5′-tetrakis ( 4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-dichlorophenyl)- 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 '-Bis (2-bromophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'- Tetrapheni Biimidazole, 2,2′-bis (2,4,6-tribromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-cyanophenyl) -4 , 4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-dicyanophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4,6-tricyanophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′- Tetraphenylbiimidazole, 2,2′-bis (2,4-dimethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4,6-trimethylphenyl) ) -4,4 ', 5,5'-tetraphenyl Imidazole, 2,2′-bis (2-ethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-diethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4,6-triethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2 -Phenylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-diphenylphenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2′-bis (2,4,6-triphenylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

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

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

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

  The sensitizer is not particularly limited and may be appropriately selected from known sensitizers. For example, known polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, , Fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, indocarbocyanine, thiacarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, Methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squariums (eg, squalium), acridones (eg, acridone, chloroacrine) Don, N-methylacridone, N-butylacridone, N-butyl-chloroacridone, etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl)- 7- (1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3 '-Carbonylbis (5,7-di-n-propoxycoumarin), 3,3'-carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7- Diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin Examples thereof include 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, and others, and JP-A-5-19475, JP-A-7-271028, JP-A-2002-. No. 363206, JP-A No. 2002-363207, JP-A No. 2002-363208, JP-A No. 2002-363209, and the like.

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

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

<External pigment>
The (D) extender pigment is not particularly limited and may be appropriately selected depending on the intended purpose. However, the surface hardness of the formed permanent pattern is improved, the coefficient of thermal expansion is reduced, the dielectric constant and dielectric constant of the cured film itself. In view of the effect of reducing the tangent, inorganic pigments and organic fine particles are preferably used.
The inorganic pigment is not particularly limited and may be appropriately selected from known ones. For example, kaolin, barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, gas phase method silica, amorphous Examples thereof include silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica.
The average particle diameter of the inorganic pigment is preferably less than 10 μm, and more preferably 3 μm or less. When the average particle size is 10 μm or more, resolution may be deteriorated due to light scattering.
There is no restriction | limiting in particular as said organic fine particle, According to the objective, it can select suitably, For example, a melamine resin, a benzoguanamine resin, a crosslinked polystyrene resin etc. are mentioned. Further, silica having an average particle diameter of 1 to 5 μm and an oil absorption of about 100 to 200 m ² / g, spherical porous fine particles made of a crosslinked resin, and the like can be used.

  There is no restriction | limiting in particular as content in the said photosensitive composition of the said extender, Although it can select suitably according to the objective, It is preferable that it is 10-60 mass%. When the addition amount is less than 10% by mass, the surface hardness may not be improved and the thermal expansion coefficient may not be sufficiently reduced. When the addition amount exceeds 60% by mass, when a cured film is formed on the surface of the photosensitive layer, The film quality of the cured film becomes brittle, and when a wiring is formed using a permanent pattern, the function as a protective film for the wiring may be impaired.

<Other ingredients>
The other components are not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a thermal crosslinking agent, a thermal polymerization inhibitor, a plasticizer, and a colorant (color pigment or dye). In addition to these other components, adhesion promoters and other auxiliaries to the substrate surface (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, Perfumes, surface tension modifiers, chain transfer agents, etc.) may be used in combination. By appropriately containing these components, properties such as stability, photographic properties, and film physical properties of the photosensitive film can be adjusted.

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

  Examples of the oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl -3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate or oligomers or copolymers thereof, oxetane groups and novolak resins , Poly (p-hydroxystyrene), cardo-type bisphe And ether compounds with hydroxyl groups, such as siloles, calixarenes, calixresorcinarenes, silsesquioxanes, and the like, as well as unsaturated monomers having an oxetane ring and alkyl (meth) acrylates. And a copolymer thereof.

  1-50 mass% is preferable and, as for solid content in the said photosensitive composition solid content of the said epoxy resin compound or oxetane compound, 3-30 mass% is more preferable. When the solid content is less than 1% by mass, the hygroscopicity of the cured film is increased, resulting in deterioration of insulation, or solder heat resistance, electroless plating resistance, and the like may be reduced. If it exceeds 50% by mass, the developability may deteriorate and the exposure sensitivity may decrease, which is not preferable.

Moreover, in order to accelerate the thermosetting of the epoxy resin compound or the oxetane compound, for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethyl Amine compounds such as benzylamine and 4-methyl-N, N-dimethylbenzylamine; quaternary ammonium salt compounds such as triethylbenzylammonium chloride; blocked isocyanate compounds such as dimethylamine; imidazole, 2-methylimidazole and 2-ethylimidazole , 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, etc. Bicyclic amidine compounds and salts thereof; phosphorus compounds such as triphenylphosphine; guanamine compounds such as melamine, guanamine, acetoguanamine, benzoguanamine; 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2 -Vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid S-triazine derivatives such as adducts can be used. These may be used alone or in combination of two or more. The epoxy resin compound or the oxetane compound is a curing catalyst, or any compound that can accelerate the reaction between the epoxy resin compound and the oxetane compound and a carboxyl group. May be.
Solid content in the said photosensitive composition solid content of the said epoxy resin, the said oxetane compound, and the compound which can accelerate | stimulate thermosetting with these and carboxylic acid is 0.01-15 mass% normally.

  Further, as the thermal crosslinking agent, a polyisocyanate compound described in JP-A-5-9407 can be used, and the polyisocyanate compound is aliphatic, cycloaliphatic or aromatic containing at least two isocyanate groups. It may be derived from a group-substituted aliphatic compound. Specifically, a mixture of 1,3-phenylene diisocyanate and 1,4-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate, 1,3- and 1,4-xylylene diisocyanate, bis (4 -Isocyanate-phenyl) methane, bis (4-isocyanatocyclohexyl) methane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, etc .; bifunctional isocyanates, trimethylolpropane, pentalysitol, glycerin, etc. An alkylene oxide adduct of the polyfunctional alcohol and an adduct of the bifunctional isocyanate; hexamethylene diisocyanate, hexamethylene-1,6-diisocyanate Cyclic trimers, such as preparative and derivatives thereof; and the like.

Furthermore, for the purpose of improving the storage stability of the photosensitive film, a compound obtained by reacting a blocking agent with the isocyanate group of the polyisocyanate and its derivative may be used.
Examples of the isocyanate group blocking agent include isopropanol, tert. Alcohols such as butanol; lactams such as ε-caprolactam, phenol, cresol, p-tert. -Butylphenol, p-sec. -Butylphenol, p-sec. -Phenols such as amylphenol, p-octylphenol, p-nonylphenol; heterocyclic hydroxyl compounds such as 3-hydroxypyridine and 8-hydroxyquinoline; dialkylmalonate, methylethylketoxime, acetylacetone, alkylacetoacetate oxime, acetoxime, Active methylene compounds such as cyclohexanone oxime; and the like. In addition to these, compounds having at least one polymerizable double bond and at least one blocked isocyanate group in the molecule described in JP-A-6-295060 can be used.

  Moreover, an aldehyde condensation product, a resin precursor, etc. can be used. Specifically, N, N′-dimethylolurea, N, N′-dimethylolmalonamide, N, N′-dimethylolsuccinimide, trimethylolmelamine, tetramethylolmelamine, hexamethylolmelamine, 1,3-N, N'-dimethylol terephthalamide, 2,4,6-trimethylolphenol, 2,6-dimethylol-4-methyliloanisole, 1,3-dimethylol-4,6-diisopropylbenzene and the like can be mentioned. In place of these methylol compounds, the corresponding ethyl or butyl ether, or acetic acid or propionic acid ester may be used. Moreover, you may use the hexamethoxymethyl melamine which consists of a formaldehyde condensation product of a melamine and urea, the butyl ether of a melamine and a formaldehyde condensation product, etc.

  1-40 mass% is preferable, as for solid content in the said photosensitive composition solid content of the said thermal crosslinking agent, 3-20 mass% is more preferable, and 5-25 mass% is especially preferable. When the solid content is less than 1% by mass, improvement in the film strength of the cured film is not recognized, and when it exceeds 40% by mass, the developability and the exposure sensitivity may be lowered.

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

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

-Color pigment-
There is no restriction | limiting in particular as said coloring pigment, According to the objective, it can select suitably, For example, Victoria pure blue BO (CI. 42595), auramine (CI. 41000), fat black HB (CI. 26150), Monolite Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow HR). Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Hoster Balm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11) Fastel Pink B Supra (CI Pigment Red 81) Monastral Fa Strike Blue (C.I. Pigment Blue 15), mono Light Fast Black B (C.I. Pigment Black 1), carbon, C. I. Pigment red 97, C.I. I. Pigment red 122, C.I. I. Pigment red 149, C.I. I. Pigment red 168, C.I. I. Pigment red 177, C.I. I. Pigment red 180, C.I. I. Pigment red 192, C.I. I. Pigment red 215, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 22, C.I. I. Pigment blue 60, C.I. I. Pigment blue 64 and the like. These may be used alone or in combination of two or more. Moreover, the dye suitably selected from well-known dye can be used as needed.

  The solid content in the photosensitive composition solid content of the color pigment can be determined in consideration of the exposure sensitivity, resolution, etc. of the photosensitive layer at the time of permanent pattern formation, depending on the type of the color pigment. Generally, 0.05 to 10% by mass is preferable, 0.075 to 8% by mass is more preferable, and 0.1 to 5% by mass is particularly preferable.

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

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

As content of the said adhesion promoter, 0.001 mass%-20 mass% are preferable with respect to all the components in the said photosensitive composition, 0.01-10 mass% is more preferable, 0.1 mass% ˜5% by weight is particularly preferred.
When the photosensitive composition contains the adhesion promoter, the adhesion between each layer or the adhesion between the photosensitive layer and the substrate can be improved.

  There is no restriction | limiting in particular as thickness of the said photosensitive layer in the said photosensitive film, Although it can select suitably according to the objective, For example, 3-100 micrometers is preferable and 10-70 micrometers is more preferable.

[Other layers]
There is no restriction | limiting in particular as said other layer, According to the objective, it can select suitably, For example, a peeling layer, a light absorption layer, a surface protective layer, etc. are mentioned.
There is no restriction | limiting in particular in arrangement | positioning, thickness, etc. in the said photosensitive film of the said other layer, According to the objective, it can select suitably.

(Method for producing photosensitive film)
The photosensitive film of the present invention is produced by the following method for producing a photosensitive film.
That is, first, an aqueous dispersion emulsion containing a thermoplastic resin is applied onto the support and dried to form the cushion layer, and then the composition contained in the barrier layer is dissolved on the surface of the cushion layer. It is photosensitive by applying an emulsion or dispersed barrier layer composition coating solution and drying to form a barrier layer, and then applying a solution of the photosensitive composition and drying to form a photosensitive layer. A film is obtained.
The cushion layer is obtained by applying and drying an emulsion in which a thermoplastic resin is dispersed in water as a main component.
It is also possible to add an organic solvent within a range that does not impair the dispersion stability of the emulsion.
In order to improve dispersibility, it is preferable to add an emulsifier to the water-dispersed emulsion containing the thermoplastic resin.
The emulsifier is not particularly limited and may be appropriately selected depending on the intended purpose. And anionic emulsifiers such as polyoxyethylene alkylphenyl ether sulfate ammonium salt, and nonionic emulsifiers such as polyoxyethylene nonylphenyl ether, polyethylene glycol monostearate and sorbitan monostearate.
Since the cushion layer is obtained from a water-dispersed emulsion containing a thermoplastic resin, management of the organic solvent exhaust gas concentration during formation of the photosensitive layer is facilitated, and environmental load countermeasures and explosion-proof management are facilitated.
The barrier layer is obtained by applying the barrier layer composition coating liquid on the surface of the cushion layer and drying it after the cushion layer is formed.
The photosensitive layer can be obtained by applying a solution of the photosensitive composition to the surface of the barrier layer after the formation of the barrier layer and drying it.
There is no restriction | limiting in particular as a solvent of the said barrier layer or a cushion layer, According to the objective, it can select suitably, For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, n- Alcohols such as hexanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone; ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, And esters such as methoxypropyl acetate; aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene; carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, monochloro Halogenated hydrocarbons such as benzene; ethers such as tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane, etc. Is mentioned. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.

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

The photosensitive film is preferably coated with a protective film before the lamination on the substrate, for example. The protective film is attached to the photosensitive layer side during transportation or the like to prevent and protect the photosensitive layer from being stained and damaged, and is peeled off when the photosensitive film is laminated on the substrate.
Examples of the protective film include those similar to the support, silicone paper, polyethylene, polypropylene laminated paper, polyolefin or polytetrafluoroethylene sheet, and among these, polyethylene film, polypropylene A film is preferred.
There is no restriction | limiting in particular as thickness of the said protective film, Although it can select suitably according to the objective, For example, 5-100 micrometers is preferable and 8-30 micrometers is more preferable.
When the protective film is used, it is preferable that the adhesive force X between the photosensitive layer and the support and the adhesive force Y between the photosensitive layer and the protective film satisfy the relationship of adhesive force X> adhesive force Y.
Examples of the combination of the support and the protective film (support / protective film) include polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate, and the like. . Moreover, the relationship of the above adhesive forces can be satisfy | filled by surface-treating at least any one of a support body and a protective film. The surface treatment of the support may be performed in order to increase the adhesive force with the photosensitive layer. For example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow treatment Examples thereof include a discharge irradiation process, an active plasma irradiation process, and a laser beam irradiation process.

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

  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.

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

The photosensitive film of the present invention has a small surface tackiness, good laminating and handling properties, excellent storage stability, and excellent chemical resistance, surface hardness, heat resistance and the like after development. It has the photosensitive layer on which the product is laminated. For this reason, it can be widely used for forming permanent patterns such as column members, rib members, spacers, partition members, display members, holograms, micromachines, proofs, etc., and can be suitably used for the permanent permanent pattern forming method of the present invention. it can.
In particular, since the photosensitive film of the present invention has a uniform thickness, the film is more precisely laminated on the substrate when forming a permanent pattern.

  The permanent pattern formed by the photosensitive film of the present invention is preferably a protective film or an insulating film (interlayer insulating film). The permanent pattern can protect the wiring from external impact and bending, and is suitable as an insulating film for a multilayer wiring board, a build-up wiring board, and the like.

(Permanent pattern forming method)
The permanent pattern forming method of the present invention includes at least a lamination process, an exposure process, and a development process, and further includes other processes that are appropriately selected.
As the permanent pattern forming method of the present invention, specifically, the photosensitive film is laminated so that the photosensitive layer is on the surface side of the substrate by at least one of heating and pressurization, and the lamination An exposure step of exposing the photosensitive layer laminated in the step, and a development step of developing the photosensitive layer exposed in the exposure step, leaving the photosensitive layer in a predetermined pattern on the substrate, And a method of forming a predetermined permanent pattern, that is, a solder resist.
As the permanent pattern forming method of the first aspect, in addition to the above steps, as the other steps, after the exposure step, the support and the cushion layer are simultaneously placed on the barrier layer between the cushion layer and the barrier layer. Preferred examples include a peeling step of peeling off the photosensitive layer, and then developing the photosensitive layer by the developing step.
According to the permanent pattern forming method of the first aspect, at the time of exposure, permeation of oxygen to the photosensitive layer is blocked by the support and the cushion layer, for example, photoradical polymerization as a highly sensitive photosensitive composition. Even when the photosensitive composition of the system is used, the polymerization reaction of the photosensitive composition is not inhibited by the influence of oxygen during exposure, and the sensitivity of the photosensitive layer is prevented from being lowered.
As the permanent pattern forming method of the second aspect, in addition to the above steps, as the other steps, after the lamination step, the support and the cushion layer are simultaneously placed on the barrier layer between the cushion layer and the barrier layer. Preferably, there is a method in which the photosensitive layer is exposed by an exposure step.
According to the permanent pattern forming method of the second aspect, a blurred image is generated in an image formed on the photosensitive layer without being affected by light scattering or refraction by the support and the cushion layer. And high resolution is obtained.

  In the permanent pattern forming method of the present invention, the protective film and the interlayer insulating film formed by the photosensitive film become a permanent pattern.

[Lamination process]
The laminating step is a step of laminating the photosensitive film such that the photosensitive layer is on the surface side of the substrate by at least one of pressurization and heating.

In the lamination step, the heating temperature is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 70 to 130 ° C, more preferably 80 to 110 ° C.
There is no restriction | limiting in particular as a pressure of the said pressurization, Although it can select suitably according to the objective, For example, 0.01-1.0 MPa is preferable and 0.05-1.0 MPa is more preferable.

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

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

[Exposure process]
There is no restriction | limiting in particular as said exposure process, According to the objective, it can select suitably, An analog exposure process, a digital exposure process, etc. are mentioned.
The analog exposure step is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the surface of the photosensitive layer is irradiated with light from a light irradiation means via a photomask. And a step of forming an image of the photomask and exposing.
The digital exposure process is not particularly limited and may be appropriately selected depending on the purpose. For example, a control signal is generated based on pattern information to be formed, and light modulation means is used in accordance with the control signal. The step of irradiating and exposing the modulated light onto the photosensitive layer is exemplified, and specifically, the light modulating means having at least n pixel parts for receiving and emitting the light from the light irradiating means. After the light from the light irradiating means is modulated, the photosensitive layer is subjected to light that has passed through a microlens array in which microlenses having aspherical surfaces capable of correcting aberrations due to distortion of the exit surface in the picture element portion are arranged. A step of exposing the photosensitive layer formed by the forming step is preferably exemplified.

In the exposure step, the light emitted from the light irradiation means is not particularly limited and can be appropriately selected according to the purpose. For example, an electromagnetic wave that activates a photopolymerization initiator and a sensitizer, Examples include ultraviolet to visible light, electron beams, X-rays, and laser beams. Among these, laser beams that can perform on / off control of light in a short time and easily control light interference are preferable.
There is no restriction | limiting in particular as a wavelength of the light of the said ultraviolet to visible light, Although it can select suitably according to the objective, 330-650 nm is preferable and the objective of shortening the exposure time of a photosensitive composition is 395. ˜415 nm is more preferable, and 405 nm is particularly preferable.
The light irradiation method by the light irradiation means is not particularly limited and can be appropriately selected according to the purpose. For example, a high pressure mercury lamp, a xenon lamp, a carbon arc lamp, a halogen lamp, a cold cathode tube for a copying machine, The method of irradiating with well-known light sources, such as LED and a semiconductor laser, is mentioned. In addition, it is preferable to synthesize and irradiate two or more light beams from these light sources, and to irradiate a laser beam (hereinafter sometimes referred to as “combined laser beam”) composed of two or more light beams. Is particularly preferred.
There is no restriction | limiting in particular as the irradiation method of the said combined laser beam, Although it can select suitably according to the objective, A laser irradiated from a several laser light source, a multimode optical fiber, and this several laser light source There is a method of forming and irradiating a combined laser beam with a collective optical system that collects light and couples it to the multimode optical fiber.

In the exposure step, the method for modulating light is not particularly limited as long as it is a method for modulating light by means of light modulation means having n number of pixel parts for receiving and emitting light from the light irradiation means. Although it can select suitably according to this, The method of controlling the arbitrary less than n image-element parts arrange | positioned continuously from n image element parts according to pattern information is mentioned suitably.
There is no restriction | limiting in particular as the number (n) of said picture element parts, According to the objective, it can select suitably.
The arrangement of the picture element portions in the light modulation means is not particularly limited and may be appropriately selected according to the purpose. For example, it is preferably arranged two-dimensionally and arranged in a lattice pattern. Is more preferable.
The light modulation method is not particularly limited and may be appropriately selected depending on the intended purpose. A preferable example is a method using a spatial light modulation element as the light modulation means.
The spatial light modulation element is not particularly limited and may be appropriately selected depending on the intended purpose. However, a digital micromirror device (DMD) or a MEMS (Micro Electro Mechanical Systems) type spatial light modulation element (SLM) may be used. A Special Light Modulator), an optical element that modulates transmitted light by an electro-optic effect (PLZT element), a liquid crystal light shutter (FLC), and the like. Among these, a DMD is particularly preferable.

In the exposure step, the light modulated by the modulation means is allowed to pass through a microlens array in which microlenses having aspherical surfaces capable of correcting aberrations due to distortion of the exit surface in the picture element portion are arranged.
The microlens arranged in the microlens array is not particularly limited as long as it has an aspheric surface, and can be appropriately selected according to the purpose. However, the microlens is a microlens having a toric surface. Preferably there is.
Furthermore, in the exposure step, it is preferable that the light modulated by the modulation means is allowed to pass through an aperture array, a coupling optical system, other optical systems selected as appropriate.

In the exposure step, the method for exposing the photosensitive layer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include digital exposure and analog exposure, but digital exposure is preferred. .
The digital exposure method is not particularly limited and may be appropriately selected depending on the purpose. For example, the digital exposure method is performed using laser light modulated according to a control signal generated based on predetermined pattern information. Is preferred.
Further, in the exposure step, the method for exposing the photosensitive layer is not particularly limited and can be appropriately selected according to the purpose. From the viewpoint of enabling high-speed exposure in a short time, It is preferably carried out while relatively moving the photosensitive layer, and particularly preferably used in combination with the digital micromirror device (DMD).

  Hereinafter, a pattern forming apparatus suitably used in the permanent pattern forming method of the present invention will be described with reference to the drawings.

FIG. 7 is a schematic perspective view showing the appearance of a pattern forming apparatus suitably used in the permanent pattern forming method of the present invention.
As shown in FIG. 7, the pattern forming apparatus including the light modulation means adsorbs the sheet-like pattern forming material 150 on the upper surface of a thick plate-like installation table 156 supported by four legs 154. A flat plate-like stage 152 is provided.
The stage 152 is arranged so that the longitudinal direction thereof faces the stage moving direction, and is supported by a guide 158 formed on the upper surface of the installation table 156 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 downward C-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 end portion of the gate 160 is fixed to both side surfaces in the longitudinal center portion 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 that detect the front and rear ends of the pattern forming material 150 are provided on the other side. ing. 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.

FIG. 8 is a schematic perspective view showing the configuration of the scanner. FIG. 9A is a plan view showing an exposed region formed on the photosensitive layer, and FIG. 9B is a diagram showing an arrangement of exposure areas by the exposure head.
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.

FIG. 10 is a perspective view showing a schematic configuration of the exposure head.
As shown in FIG. 10, each of the exposure heads 166 _{11 to} 166 _mn serves as the light modulation means (spatial light modulation element for modulating each pixel) that modulates a light beam according to pattern information. A digital micromirror device (hereinafter also referred to as “DMD”) 50 manufactured by Instruments Co., Ltd. A fiber array light source 66 as a light irradiating means 66 provided with laser emitting portions 68 arranged in a line along a direction corresponding to the side direction, and a laser beam emitted from the fiber array light source 66 are corrected and placed on the DMD. A condensing lens system 67, a mirror 69 that reflects laser light transmitted through the lens system 67 toward the DMD 50, and a laser reflected by the DMD 50 The B, and an image forming optical system 51 forms an image on the pattern forming material 150. In FIG. 10, the lens system 67 is schematically shown.

FIG. 12 shows a controller that controls the DMD based on the pattern information.
As shown in FIG. 12, the DMD 50 is connected to a controller 302 having a data processing unit, a mirror drive control unit, and the like. 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.

FIG. 1 is a partially enlarged view showing a configuration of a digital micromirror device (DMD) as the light modulation means.
As shown in FIG. 1, in the DMD 50, a large number (for example, 1024 × 768) of micromirrors (micromirrors) 62 each constituting a pixel (pixel) are arranged on a SRAM cell (memory cell) 60 in a lattice shape. This is a mirror device arranged in a row. 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. The entire structure is monolithically configured. ing.

2A and 2B are diagrams for explaining the operation of the DMD.
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 in which the micromirror 62 is tilted to + α degrees when the micromirror 62 is in an on state, and FIG. 2B shows a state in which the micromirror 62 is tilted to −α degrees that is in an off state.
Therefore, by controlling the tilt of the micromirror 62 in each pixel of the DMD 50 according to the pattern information, the laser light incident on the DMD 50 is reflected in the tilt direction of each micromirror 62.
FIG. 1 shows an example of a state in which the micromirror 62 is controlled to + α degrees or −α degrees. On / off control of each micromirror 62 is performed by the controller 302 connected to the DMD 50. A light absorber (not shown) is arranged in the direction in which the laser beam B reflected by the micromirror 62 in the off state travels.

The DMD 50 is preferably 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.
As shown in FIG. 3B, the DMD 50 has a plurality of micromirror arrays (for example, 756 pairs) arranged in the short direction, in which a large number (for example, 1024) of micromirrors are arranged in the longitudinal direction. and which is, by inclining the DMD 50, the pitch P ₂ of the scanning locus of the exposure beams 53 from each micromirror (scan line), it becomes narrower than the pitch P ₁ of the scanning line in the case of not tilting the DMD 50, 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.
When the laser light B is irradiated from the fiber array light source 66 to the DMD 50, the laser light emitted from the fiber array light source 66 is turned on and off for each pixel, and the pattern forming material 150 has approximately the same number of pixels as the DMD 50 used. Exposure is performed in elementary units (exposure area 168). 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.
Here, the data processing speed of the entire DMD 50 is limited, and the modulation speed per line is determined in proportion to the number of pixels to be used. Therefore, one line can be obtained by using only a part of the micromirror array. The modulation speed per hit is increased. 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.
In the DMD 50, 768 micromirror rows in which 1024 micromirrors are arranged in the main scanning direction are arranged in the subscanning direction, but a part of micromirror rows (eg, 1024 × 256 rows) is arranged by the controller 302. Only is controlled to drive.
4 (A) and 4 (B) are diagrams showing areas where DMD is used.
As shown in FIG. 4 (A), the DMD use area may be a micromirror array arranged at the center of the DMD 50. As shown in FIG. 4 (B), the end of the DMD 50 may be used. Arranged micromirror rows 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.
For example, in the case of using only 384 sets out of 768 sets of micromirror arrays, the modulation can be performed twice as fast per line as compared with the case of using all 768 sets. Also, when only 256 pairs are used in the 768 sets of micromirror arrays, modulation can be performed three times faster per line than when all 768 sets are used.

  As described above, according to the permanent 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 speed 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.

As the exposure method, 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 a scanner 162.
Further, as the exposure method, as shown in FIGS. 6A and 6B, after the pattern forming material 150 is scanned in the X direction by the scanner 162, the scanner 162 is moved by one step in the Y direction. The entire surface of the pattern forming material 150 may be exposed by a plurality of scans by repeating scanning and movement, such as scanning in the direction.

  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, the lens system 67 and the imaging optical system 51 will be described.
FIG. 11 is a cross-sectional view in the multiple scanning direction along the optical axis showing the details of the configuration of the exposure head in FIG.
As shown in FIG. 11, the lens system 67 includes a condensing lens 71 that condenses the laser light B as illumination light emitted from the fiber array light source 66, and a rod that is inserted in the optical path of the light that has passed through the condensing lens 71. 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 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.

  As shown in FIG. 11, the imaging optical system 51 includes a first imaging optical system including lens systems 52 and 54, a second imaging optical system including lens systems 57 and 58, and these imaging optical systems. And an aperture array 59. The microlens array 55 is inserted between the microlens array 55 and the aperture array 59.

The microlens array 55 is formed by two-dimensionally arranging a large number of microlenses 55a corresponding to the pixels of the DMD 50. In this example, as will be described later, only 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 direction and the horizontal direction. The focal length of the micro lens 55a is 0.19 mm, and the NA (numerical aperture) is 0.11.
Further, the microlens 55a is formed from the optical glass BK7.
The beam diameter of the laser beam B at the position of each microlens 55a is 41 μm.

  In the aperture array 59, a large number of apertures (openings) 59a corresponding to the respective microlenses 55a of the microlens array 55 are formed. The diameter of each aperture 59a is 10 μm.

The first imaging optical system forms an image on the microlens array 55 by enlarging the image by the DMD 50 three times.
The second imaging optical system enlarges the image that has passed through the microlens array 55 by 1.6 times, and forms and projects the image on the pattern forming material 150.
Accordingly, in the entire optical system, an image formed by the DMD 50 is magnified 4.8 times and formed 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.

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

FIG. 13A is a cross-sectional view along the optical axis showing the configuration of the exposure head.
As shown in FIG. 13A, the exposure head includes a light irradiating means 144 for irradiating the DMD 50 with laser light, and a lens system (imaging optical system) 454 for enlarging the laser light reflected by the DMD 50 to form an image. 458, a microlens array 472 in which a large number of microlenses 474 are arranged corresponding to each pixel portion of the DMD 50, and an aperture array 476 in which a large number of apertures 478 are provided corresponding to each microlens of the microlens array 472. , And lens systems (imaging optical systems) 480 and 482 for forming an image of the laser beam that has passed through the aperture on the exposed surface 56.

FIG. 14 is a diagram showing a result of measuring the flatness of the reflecting surface of the micromirror 62 constituting the DMD 50.
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. In the drawing, the x direction and the y direction 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.
FIGS. 15A and 15B show the height position displacement of the reflecting surface of the micromirror 62 along the x direction and the y direction in FIG. 14, respectively.
As shown in FIGS. 14 and 15, there is distortion on the reflection surface of the micromirror 62, and when attention is particularly paid to the center of the mirror, distortion in one diagonal direction (y direction) is different from that in the other diagonal line. It 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.

FIGS. 16A and 16B are views showing the front and side shapes of the entire microlens array 55, respectively.
As shown in FIG. 16A, the microlens array 55 is configured by arranging microlenses 55a in parallel in the horizontal direction and 1024 rows and in the vertical direction corresponding to the micromirrors 62 of the DMD 50, respectively.
The long side dimension of the microlens array 55 is 50 mm, and the short side dimension is 20 mm.
In FIG. 9A, the arrangement order of the micro lenses 55a is indicated by j for the horizontal direction and k for the vertical direction.

FIGS. 17A and 17B are views showing a front shape and a side shape of the microlens constituting the microlens array. Note that FIG. 17A also shows the contour lines of the microlens 55a.
As shown in FIGS. 17A and 17B, the end surface of the microlens 55a on the light emission side has an aspherical shape that corrects aberration due to distortion of the reflection surface of the micromirror 62.
Specifically, the aspherical microlens 55a is a toric lens having a radius of curvature Rx in the x direction of −0.125 mm and a radius of curvature Ry in the y direction of −0.1 mm.
FIG. 18 is a schematic diagram showing a condensing state by the microlens in one cross section (A) and another cross section (B).
As shown in FIG. 18, since a toric lens having an aspherical end surface on the light emission side is used as the microlens 55a constituting the microlens array, laser light in a cross section parallel to the x direction and the y direction is used. When the B condensing state is compared between the cross section parallel to the x direction and the cross section parallel to the y direction, the radius of curvature of the microlens 55a is smaller in the latter cross section, and the focal length is smaller. Shorter.

The shape of the microlens 55a may be a secondary aspherical shape or a higher order (4th order, 6th order,...) Aspherical shape. By adopting the higher order aspherical shape, the beam shape can be further refined.
In addition to making the end surface shape of the light exit side of the microlens 55a a toric surface, it is also possible to form a microlens array from microlenses having one of two light passing end surfaces as a spherical surface and the other as a cylindrical surface. It is.

19A, 19B, 19C, and 19D are diagrams showing the results of simulating the beam diameter in the vicinity of the condensing position (focal position) of the microlens 55a by a computer.
For comparison, FIGS. 20a, 20b, 20c, and 20d show the results of a similar simulation performed when the microlens 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 is the curvature in the x direction (= 1 / Rx), Cy is the curvature in the y direction (= 1 / Ry), X is the distance from the lens optical axis O in the x direction, Y Indicates the distance from the lens optical axis O in the y direction, respectively.

  19A to 19D and FIG. 20A to FIG. 20D, in the permanent pattern forming method of the present invention, the microlens 55a has a focal length in the cross section parallel to the y direction in the cross section parallel to the x direction. By using a toric lens that is smaller than the focal length, distortion of the beam shape in the vicinity of the condensing position is suppressed. Therefore, it is possible to expose the pattern forming material 150 with a higher definition image without distortion.

  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.

The aperture array 59 is disposed in the vicinity of the light collection position of the microlens array 55. Only the light that has passed through the corresponding microlens 55 a is incident on each aperture 59 a provided in the aperture array 59. Therefore, it is possible to prevent light from the adjacent micro lens 55a not corresponding to one aperture 59a corresponding to the one micro lens 55a from entering, and to increase the extinction ratio.
If the diameter of the aperture 59a is reduced to some extent, an effect of suppressing distortion of the beam shape at the condensing position of the microlens 55a can be obtained, but the amount of light blocked by the aperture array 59 is increased, and the light utilization efficiency is reduced. . In this case, the microlens 55a having the aspherical shape prevents light from being blocked and keeps light use efficiency high.

  In addition, although the aberration due to the distortion of the reflection surface of the micromirror 62 constituting the DMD 50 is corrected by the microlens array 55 and the aperture array 59, the permanent pattern forming method of the present invention using a spatial light modulation element other than the DMD. However, if there is distortion on the surface of the picture element portion of the spatial light modulator, the present invention can be applied to correct the aberration caused by the distortion and prevent the beam shape from being distorted.

  As shown in FIG. 13A, the imaging optical system includes lenses 480 and 482, and the light that has passed through the aperture array 476 is imaged on the exposed surface 56 by the imaging optical system.

As described above, in the pattern forming apparatus, the laser light reflected by the DMD 50 is magnified several times by the magnifying lenses 454 and 458 of the lens system and projected onto the exposed surface 56, so that the entire image area is Become wider. 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, since the pattern forming apparatus includes the micro lens array 472 and the aperture array 476, the laser light reflected by the DMD 50 corresponds to each pixel part of the DMD 50 by each micro lens of the micro lens array 472. Focused. As a result, 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). It is possible to perform high-definition exposure while preventing deterioration of characteristics.
Note that the exposure area 468 is inclined because the DMD 50 is inclined and disposed 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 for the light irradiating means 144, the angle of the light beam incident from the lens 458 to each microlens of the microlens array 472 is reduced, so that a part of the light flux of the adjacent pixel enters. Can be prevented. That is, a high extinction ratio can be realized.

FIGS. 22A and 22B are views showing the front shape and side shape of another microlens array.
As shown in FIG. 22, as another microlens array, each microlens has a refractive index distribution for correcting aberration due to distortion of the reflection surface of the micromirror 62.
As illustrated, the external shape of the other microlens 155a is a parallel plate. The x and y directions in the figure are as described above.
FIG. 23 is a schematic view showing a condensing state of the laser beam B in the cross section parallel to the x direction and the y direction by the microlens 155a of FIG.
As shown in FIG. 23, the micro lens 155a has a refractive index distribution that gradually increases outward from the optical axis O. In FIG. 23, the broken line shown in the micro lens 155a indicates that the refractive index is light. A position changed from the axis O at a predetermined equal pitch is shown. As shown in the drawing, when comparing the cross section parallel to the x direction and the cross section parallel to the y direction, 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 55a shown in FIGS. 17 and 18, the refractive index distribution is given together, and the aberration due to the distortion of the reflecting surface of the micromirror 62 can be corrected by both the surface shape and the refractive index distribution. Is possible.

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

FIG. 24 is an explanatory diagram showing the concept of correction by the light quantity distribution correction optical system.
As shown in FIG. 24A, the case where the entire luminous flux width (total luminous flux width) H0 and H1 is 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 amount distribution correcting 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 beam 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 beam in the central portion with respect to the light having the same light flux widths h0 and h1 on the incident side, and conversely changes the incident light flux in 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 on the incident side (h1 / h0 = 1) ( (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 a width Η3 and emitted (H0 <H3). Even in such a case, the light quantity distribution correcting optical system has the same light beam width h0, h1 on the incident side, and the light beam width h10 in the central part is larger than that in the peripheral part on the emission side. Conversely, the luminous flux width h11 at the peripheral part is made smaller than that at the central part. Considering the expansion rate of the light beam, the expansion rate for the incident light beam in the central portion is made larger than that in the peripheral portion, and the expansion rate for the incident light beam in the peripheral portion is made smaller than that in the central portion. Also in this case, the ratio “h11 / h10” of the light flux width in the peripheral portion to the light flux width in the central portion is smaller than the ratio (h1 / h0 = 1) on the incident side ((h11 / h10) <1). .

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

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

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

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

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

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

FIG. 26 shows a light amount distribution of illumination light obtained by the pair of combination lenses shown in Tables 1 and 2. Here, the horizontal axis represents coordinates from the optical axis, and the vertical axis represents the light amount ratio (%). For comparison, FIG. 25 shows a light amount distribution (Gaussian distribution) of illumination light when correction is not performed.
As shown in FIGS. 25 and 26, the light amount distribution correction optical system performs a correction to obtain a substantially uniform light amount distribution 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.

Next, the fiber array light source 66 as a light irradiation means will be described.
27A (A) is a perspective view showing a configuration of a fiber array light source, FIG. 27A (B) is a partially enlarged view of (A), and FIGS. 27A (C) and (D) are laser emitting portions. It is a top view which shows the arrangement | sequence of the light emission point in. FIG. 27 b is a front view showing the arrangement of the light emitting points in the laser emission part of the fiber array light source.

  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 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.

  Further, in order to arrange the emission ends of the optical fibers 31 having a small cladding diameter in a row without any gaps, the multi-mode optical fibers 30 are stacked between two adjacent multi-mode optical fibers 30 in a portion having a large cladding diameter, The exit end of the optical fiber 31 coupled to the stacked multi-mode optical fiber 30 is between the two exit ends of the optical fiber 31 coupled to the two adjacent multi-mode optical fibers 30 at a portion where the cladding diameter is large. It is arranged to be sandwiched between.

  In such an optical fiber, 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 provided at the tip of the multimode optical fiber 30 having a large cladding diameter on the laser light emission side. It can be obtained by bonding. In the two optical fibers, the incident end face of the optical fiber 31 is fused and joined to the outgoing end face of the multimode optical fiber 30 so that the central axes of both optical fibers coincide. As described above, the diameter of the core 31 a of the optical fiber 31 is the same as the diameter of the core 30 a of the multimode optical fiber 30.

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

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

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

  However, the cladding diameter of the optical fiber 31 is not limited to 60 μm. The clad diameter of the optical fiber used in the conventional fiber array light source is 125 μm, but the depth of focus becomes deeper as the clad diameter becomes smaller. Therefore, the clad diameter of the multimode optical fiber is preferably 80 μm or less, preferably 60 μm or less. More preferably, it is 40 μm or less. On the other hand, since the core diameter needs to be at least 3 to 4 μm, the cladding diameter of the optical fiber 31 is preferably 10 μm or more.

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

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

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

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

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

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

  FIG. 32 shows 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 parallel to the active layer and a divergence angle in a direction perpendicular to the active layer, respectively, 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.

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 direction in which 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 that coincides with the width direction (direction orthogonal 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 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.

Since the fiber array light source uses a high-intensity fiber array light source in which the emission ends of the optical fibers of the combined laser light source are arranged in an array as the light irradiating means for illuminating the DMD, it has a high output and a deep focus. A pattern forming apparatus having a depth 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. For example, a single laser beam that emits laser light incident from a single semiconductor laser having one light emitting point is emitted. A fiber array light source obtained by arraying fiber light sources including optical fibers can be used.

  As the light irradiation means having a plurality of light emitting points, for example, as shown in FIG. 33, a laser array in which a plurality of (for example, seven) chip-shaped semiconductor lasers LD1 to LD7 are arranged on the heat block 100 is used. 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 are arranged in a predetermined direction can also be used. Since the multicavity laser 110 can arrange the light emitting points with higher positional accuracy than the case where the chip-shaped semiconductor lasers are arranged, it is easy to multiplex 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 multicavity laser 110 only in a plane perpendicular to the active layer, the coupling efficiency of the laser beam B to the multimode 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 condensed in a predetermined direction by the rod lens 113, and then each microlens of the lens array 114. It becomes parallel light. The collimated laser beam L is condensed by the condenser lens 120 and enters the core 130a of the multimode optical fiber 130. The laser light incident on the core 130a propagates in the optical fiber, is combined into one, and is emitted.

  Furthermore, as another 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 heat block 180 having a substantially rectangular shape. A storage space is formed between the two heat 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 combines the laser beam at 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 multicavity lasers 110 arranged on the heat 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.

  In each exposure head 166 of the scanner 162, laser beams B1, B2, B3, B4, B5, and 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.

The condensing optical system includes collimator lenses 11 to 17 and a condensing lens 20. Also, the converging optical system and the multimode optical fiber 30 constitute a multiplexing optical system.
The laser beams B1 to B7 condensed as described above by the condenser lens 20 are incident on the core 30a of the multimode optical fiber 30, propagate through the optical fiber, and are combined into one laser beam B. The light exits from the optical fiber 31 coupled to the exit 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 section 68 of the fiber array light source 66, high-luminance light emitting points are arranged in a line along the main scanning direction. 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.

Next, the permanent pattern forming method of the present invention using the pattern forming apparatus will be described.
First, 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).
Next, 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 when the stage 152 passes under the gate 160, the pattern information stored in the frame memory is sequentially read out for a plurality of lines. 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 on / off controlled for each exposure head 166 based on the generated control signal by the mirror drive control unit.
Next, when the DMD 50 is irradiated with laser light from the fiber array light source 66, the laser light reflected when the micromirrors of the DMD 50 are turned on is exposed to the exposed surface 56 of the pattern forming material 150 by the lens systems 54 and 58. Imaged on top.
In this way, the laser light emitted from the fiber array light source 66 is turned on / off for each pixel, and the pattern forming material 150 is exposed in approximately the same number of pixel units (exposure area 168) as the number of used pixel elements of the DMD 50. The
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.

[Development process]
The developing step includes a step of developing the photosensitive layer by exposing the photosensitive layer by the exposing step and removing an unexposed portion.
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.

  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.

[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, a peeling process, a hardening process process, a plating process, etc. are mentioned. These may be used alone or in combination of two or more.
-Peeling process-
As said peeling process, the peeling process in the permanent pattern formation method of a 1st aspect and the peeling process in the permanent pattern formation method of a said 2nd aspect are mentioned, for example.
-Curing process-
When the permanent pattern forming method of the present invention is a permanent pattern forming method for forming a permanent pattern such as a protective film or an interlayer insulating film, a curing process for curing the photosensitive layer after the developing step It is preferable to provide a process.
There is no restriction | limiting in particular as said hardening process, Although it can select suitably according to the objective, For example, a whole surface exposure process, a whole surface heat processing, etc. are mentioned suitably.

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

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

-Plating process-
The plating step can be performed by an appropriately selected method 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 plating. And gold plating such as soft gold plating.
A permanent pattern can be formed on the surface of the substrate by removing the pattern after the plating process in the plating process, and further removing unnecessary portions by an etching process or the like as necessary.

  Since the permanent pattern forming method of the present invention can form a permanent pattern with high definition and efficiency by suppressing distortion of an image formed on the pattern forming material, high-definition exposure is required. It can be suitably used for forming various patterns and the like, and can be particularly suitably used for forming high-definition wiring patterns.

-Method for forming protective film and interlayer insulating film-
When the permanent pattern forming method of the present invention is a permanent pattern forming method of forming at least one of a protective film and an interlayer insulating film using a so-called solder resist, the permanent pattern forming method of the present invention on a printed wiring board Thus, a permanent pattern can be formed, and soldering can be performed as follows.
That is, the development step forms a hardened layer that is the permanent pattern, and the metal layer is exposed on the surface of the printed wiring board. Gold plating is performed on the portion of the metal layer exposed on the surface of the printed wiring board, and then soldering is performed. Then, a semiconductor or a component is mounted on the soldered portion. At this time, the permanent pattern by the hardened layer exhibits a function as a protective film or an insulating film (interlayer insulating film), and prevents external impact and conduction between adjacent electrodes.

  In the permanent pattern forming method of the present invention, if the permanent pattern formed by the permanent pattern forming method is the protective film or the interlayer insulating film, the wiring can be protected from external impact and bending, In particular, the interlayer insulating film is useful for high-density mounting of semiconductors and components on, for example, a multilayer wiring board or a build-up wiring board.

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

Example 1
[Production of photosensitive film for permanent pattern formation]
As a support, an olefin / acrylic acid emulsion (trade name: Chemipearl S-100, manufactured by Mitsui Chemicals, Inc., solid content concentration: 27 mass%) on a polyethylene terephthalate (PET) film having a thickness of 20 μm, a wire bar It was applied and dried to form a cushion layer having a thickness of 20 μm.

Next, a barrier layer composition solution having the following composition was applied onto the cushion layer and dried to form a 1.5 μm thick barrier layer.
[Barrier layer composition solution]
-PVA205 (trade name: manufactured by Kuraray Co., Ltd., polyvinyl alcohol, saponification rate = 80%) ... 130 parts by mass-PVP K-90 (trade name: manufactured by GAF Corporation, polyvinylpyrrolidone) ... 60 parts by mass Surflon S-131 (trade name: manufactured by Asahi Glass Co., Ltd., fluorinated surfactant) ... 10 parts by mass · Methanol ... 1675 parts by mass · Distilled water ... 1675 parts by mass

  Next, a photosensitive composition solution having the following composition was applied onto the barrier layer formed on the support and dried to form a photosensitive layer having a thickness of 10 μm on the barrier layer. On the photosensitive layer, 12 μm thick polypropylene was laminated as a protective film to form a permanent pattern forming photosensitive film.

[Composition of photosensitive composition solution]
Barium sulfate dispersion: 24.75 parts by mass Styrene / maleic anhydride / butyl acrylate copolymer (molar ratio 40/32/28) and benzylamine (1 relative to the anhydride group of the copolymer) 0.035 equivalent) and 35 mass% methyl ethyl ketone solution of addition reaction product ... 13.36 parts by mass R712 (manufactured by Nippon Kayaku Co., Ltd., bifunctional acrylic monomer) ... 3.06 parts by mass dipentaerythritol hexa Acrylate: 4.59 parts by mass IRGACURE 819 (Ciba Specialty Chemicals Co., Ltd.) 1.98 parts by mass A 30% by mass methyl ethyl ketone solution of F780F (Dainippon Ink Co., Ltd.) 0.066 Part by mass-Hydroquinone monomethyl ether-0.024 part by mass-Methyl ethyl ketone-8.60 parts by weight The barium sulfate dispersion was composed of 30 parts by weight of barium sulfate (manufactured by Sakai Chemical Co., Ltd., B30), 34.29 parts by weight of a 35% by weight methyl ethyl ketone solution of the styrene / maleic anhydride / butyl acrylate copolymer, and 1-methoxy- After mixing in advance with 35.71 parts by mass of 2-propyl acetate, the motor mill M-200 (manufactured by Eiger) was used for 3.5 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 1.0 mm. Prepared by dispersing.

<Lamination process>
The surface of the laminated substrate having a copper thickness of 12 μm is subjected to a chemical polishing treatment, and the permanent pattern forming photosensitive film is superposed on the laminated substrate after the protective film is peeled off, and then a vacuum laminator (MVLP500, Laminate was made under the conditions of 0.4 MPa and 90 ° C. using a machine manufactured by Meiki Seisakusho.
There was no tackiness on the surface of the photosensitive layer, and the peelability of the protective film was good.
Next, after the laminate was cooled to room temperature, the support and the cushion layer were peeled off from the barrier layer. The peelability at this time was good.

<Exposure process>
The photosensitive layer in the laminate from which the support and the cushion layer have been peeled is exposed in a pattern with a laser beam of 405 to 415 nm from above the barrier layer using the following pattern forming apparatus, The area of the part was cured.

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

  As the microlens, a toric lens 55a is used as shown in FIGS. 17 and 18, and a curvature radius Rx = −0.125 mm in a direction optically corresponding to the x direction, corresponding to the y direction. The radius of curvature Ry in the direction to travel is −0.1 mm.

  In addition, the aperture array 59 disposed in the vicinity of the condensing position of the microlens array 55 is disposed so that only light that has passed through the corresponding microlens 55a is incident on each aperture 59a.

<Development process>
The laminated body after exposure was allowed to stand at room temperature for 10 minutes, and then an aqueous solution of sodium carbonate (30 ° C., 1% by mass) was sprayed on the entire surface of the photosensitive layer for 60 seconds at a spray pressure of 0.15 MPa, and uncured. After dissolving and removing the region, the substrate was washed with water and dried.
Further, a heat treatment was performed at 160 ° C. for 30 minutes to form a solder resist film. When the obtained solder resist film was visually observed, peeling, blistering, and discoloration were not recognized.

[Evaluation]
About the photosensitive film for permanent pattern formation of Example 1, and a laminated body, lamination property, sensitivity, resolution, storage stability, heat resistance, and surface hardness were evaluated on condition of the following. The results are shown in Table 3.

<Evaluation of laminating properties>
About the said laminated body manufactured in Example 1, the presence or absence of the bubble between the said photosensitive layer and the said wiring-laminated laminated board was observed visually, and the following evaluation criteria evaluated. The results are shown in Table 3.
-Evaluation criteria-
○: Air bubbles do not exist ×: Air bubbles exist

<Resolution>
(1) Method for measuring the shortest development time The support and the cushion layer are peeled off from the laminate produced in the same manner as in Example 1, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. is added to the entire surface of the photosensitive layer by 0. Spraying was performed at a pressure of 15 MPa, and the time required from the start of spraying of the aqueous sodium carbonate solution until the photosensitive layer was dissolved and removed was measured, and this was taken as the shortest development time.
As a result, the shortest development time was 40 seconds.

(2) Measurement of sensitivity The support and the cushion layer are peeled off from the laminate produced in the same manner as in Example 1, and a 405 nm laser as the light irradiation means is applied to the photosensitive layer from above the barrier layer. a patterning device having a light source, and exposure by irradiating light with different light energy amount from 0.1 mJ / cm ² to 100 mJ / cm ² at ^{2 1/2} times the interval, the portion of the photosensitive layer The area was cured. After standing at room temperature for 10 minutes, an aqueous solution of sodium carbonate (30 ° C., 1% by mass) is sprayed over the entire surface of the photosensitive layer at a spray pressure of 0.15 MPa, twice the shortest development time determined in (1) above. Spraying was performed to dissolve and remove the uncured region, and the thickness of the remaining cured region was measured. Next, a sensitivity curve is obtained by plotting the relationship between the light irradiation amount and the thickness of the cured layer. From the sensitivity curve thus obtained, the amount of light energy when the thickness of the cured region was 4 μm was determined as the amount of light energy necessary for curing the photosensitive layer, and this was taken as the sensitivity. The results are shown in Table 3. The pattern forming apparatus includes a light modulating unit made of the DMD and includes the pattern forming material.

(3) Measurement of resolution A laminate produced in the same manner as in Example 1 was allowed to stand at room temperature (23 ° C., 55% RH) for 10 minutes, and then the support and the cushion layer were peeled off to form the pattern. Using the forming apparatus, each line width was exposed in 1 μm increments from 5 μm to 20 μm in line width / space = 1/1, and each line width was exposed in 5 μm increments from 20 μm to 50 μm in line width. The exposure amount at this time is the amount of light energy necessary for curing the photosensitive layer of the pattern forming material measured in (2). After standing at room temperature for 10 minutes, the shortest development time determined in (1) above with a sodium carbonate aqueous solution (30 ° C., 1% by mass) as the developer on the entire surface of the photosensitive layer at a spray pressure of 0.15 MPa. Spraying for 2 times the time, the uncured area was dissolved and removed. The surface of the copper-clad laminate with the cured resin pattern thus obtained was observed with an optical microscope, and the minimum line width without any abnormalities such as tsumari and twisting was measured on the cured resin pattern line. did. The smaller the numerical value, the better the resolution. The results are shown in Table 3.

<Storage stability>
About the laminated body manufactured like Example 1, and the sample for the thermo compulsory test which left the said laminated body for 3 days at 40 degreeC and 65% RH, it was carried out similarly to the measurement of said (2) sensitivity, respectively. The amount of light energy required to cure 7 steps of 15 steps was measured. Table 3 shows the amount of light energy of the thermo test sample.
Moreover, the sensitivity change of the sample for the thermo forced test was evaluated by the change in the number of steps. If the change is within −2 steps to +2 steps, there is no problem as a practical change in exposure sensitivity. The results are shown in Table 3.

<Heat resistance>
The substrate on which the solder resist film was formed was pickled, then treated with a water-soluble flux, immersed in a solder bath at 260 ° C. for 5 seconds three times, and then the water-soluble flux was washed with water and removed. The solder resist film was visually observed and evaluated according to the following evaluation criteria. The results are shown in Table 3.
-Evaluation criteria-
○: No peeling, blistering, or discoloration is observed.
X: Any of peeling, blistering, and discoloration is recognized.

<Surface hardness>
About the soldering resist film which performed the process similar to the said heat resistance evaluation, the surface hardness was measured based on JISK5400. The results are shown in Table 3.

<Delamination between barrier layer and cushion layer>
An attempt was made to peel the support and the cushion layer from the barrier layer from the prepared laminate, and the peelability at that time was evaluated according to the following evaluation criteria.
〔Evaluation criteria〕
○: Peeling between the barrier layer and the cushion layer, and no change on the surface of the barrier layer Δ: Part of the cushion layer remaining on the surface of the barrier layer ×: No peeling between the barrier layer and the cushion layer Status

(Example 2)
In Example 1, the photosensitive film and the laminated body were produced like Example 1 except having added 5 mass parts of methoxymethylol melamine as a thermal crosslinking agent to the photosensitive composition.
About the obtained permanent pattern-forming photosensitive film and the laminate, laminating property, sensitivity, resolution, storage stability, heat resistance, delamination between the barrier layer and the cushion layer, and The surface hardness was evaluated. The results are shown in Table 3.

(Example 3)
In Example 1, the photosensitive film and the laminated body were produced like Example 1 except having formed the photosensitive layer using the photosensitive composition solution which consists of the following compositions.
About the obtained photosensitive film and the said laminated body, it carries out similarly to Example 1, and evaluates laminating property, sensitivity, resolution, storage stability, heat resistance, delamination property of a barrier layer and a cushion layer, and surface hardness. Went. The results are shown in Table 3.

[Composition of photosensitive composition solution]
・ ZFR resin (manufactured by Nippon Kayaku Co., Ltd .: product obtained by reacting a reaction product of an epoxy compound and an ester compound of an unsaturated monocarboxylic acid with a saturated or unsaturated polybasic acid anhydride) 35 parts by mass ESLV-80XY (manufactured by Nippon Steel Chemical Co., Ltd .: epoxy resin having two or more epoxy groups in the molecule) 8 parts by mass 2-methyl-1- [4- (methylthio) phenyl] -2- Morpholinopropan-1-one: 4.5 parts by mass 2,4-diethylxanthone: 0.5 parts by mass Silicone elastomer (SY series, manufactured by Wacker) ... 5 parts by mass Dipenta Erythritol hexaacrylate: 3 parts by mass Melamine: 4 parts by mass Phthalocyanine blue: 1 part by mass Silica: 20 parts by mass Precipitated barium sulfate: 15 parts by mass

Example 4
In Example 1, the photosensitive film and the laminated body were produced like Example 1 except having formed the photosensitive layer using the photosensitive composition solution which consists of the following compositions.
About the obtained permanent pattern-forming photosensitive film and the laminate, as in Example 1, laminating properties, sensitivity, resolution, storage stability, heat resistance, delamination between the barrier layer and the cushion layer, The surface hardness was evaluated. The results are shown in Table 3.

-Photosensitive composition solution-
85 parts by mass of (a) having the following composition was kneaded by a roll mill and mixed with 15 parts by mass of trimethylolpropane triglycidyl ether to prepare a photosensitive composition solution.
[Composition of Compounding Component (a)]
Resin A (*) 40 parts by mass 2-hydroxyethyl acrylate 15 parts by mass benzyl diethyl ketal 2.5 parts by mass 1-benzyl-2-methylimidazole 1. 0 parts by mass-Leveling agent (trade name: Modaflow, manufactured by Monsanto)-1.0 part by mass-Barium sulfate-25 parts by mass-Phthalocyanine green-0.5 parts by mass * The resin A is 1 equivalent of a cresol novolac type epoxy resin having an epoxy equivalent of 217 and having an average of 7 phenol nucleus residues and epoxy groups in one molecule and 1.05 equivalent of acrylic acid are reacted. From the viscous liquid obtained by reacting the resulting reaction product with 0.67 equivalents of tetrahydrophthalic anhydride in a conventional manner using phenoxyethyl acrylate as a solvent. Resin. The resin A is a viscous liquid containing 35 parts by mass of phenoxyethyl acrylate, and exhibits an acid value of 63.4 mgKOH / g as a mixture.

(Example 5)
In Example 1, 17 parts by mass of an ethylene / vinyl acetate copolymer solution (Evaflex 45X (manufactured by Mitsui Dupont Polychemical Co., Ltd., vinyl acetate content: 46% by mass)) on a support, 83 parts by mass of toluene, A photosensitive film and a laminate were produced in the same manner as in Example 1 except that a cushion layer was formed by applying and drying the mixed solution.
About the obtained photosensitive film and the said laminated body, it is the same as that of Example 1, lamination property, sensitivity, resolution, storage stability, heat resistance, delamination property between the barrier layer and the cushion layer, and surface hardness. Evaluation was performed. The results are shown in Table 3.

(Example 6)
In Example 1, a photosensitive film and a laminate were produced in the same manner as in Example 1 except that a cushion layer-forming coating solution having the following composition was applied onto a support and dried to form a cushion layer. Was made.
About the obtained photosensitive film and the said laminated body, it is the same as that of Example 1, lamination property, sensitivity, resolution, storage stability, heat resistance, delamination property between the barrier layer and the cushion layer, and surface hardness. Evaluation was performed. The results are shown in Table 3.

[Cushion layer forming coating solution]
Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio): 55 / 11.7 / 4.5 / 28.8, mass average molecular weight: 80000) 15.0 parts by mass -2,2-bis (4- (methacryloyloxypentaethoxy) phenyl) propane (trade name: BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.)-7.0 parts by mass -Fluorine-based surface activity Agent (trade name: F177P, manufactured by Dainippon Ink & Chemicals, Inc.) 0.3 parts by mass Methanol 30.0 parts by mass Methyl ethyl ketone 19.0 parts by mass 1-methoxy-2 -Propanol ... 10.0 parts by mass

(Comparative Example 1)
In Example 1, a photosensitive film and a laminate were produced in the same manner as in Example 1 except that the cushion layer was not formed on the support.
About the obtained photosensitive film and the said laminated body, it is the same as that of Example 1, lamination property, sensitivity, resolution, storage stability, heat resistance, delamination property between the barrier layer and the cushion layer, and surface hardness. Evaluation was performed. The results are shown in Table 3.

(Comparative Example 2)
In Example 3, a photosensitive film and a laminate were produced in the same manner as in Example 3 except that no barrier layer was formed on the cushion layer.
About the obtained photosensitive film and the said laminated body, it is the same as that of Example 1, lamination property, sensitivity, resolution, storage stability, heat resistance, delamination property between the barrier layer and the cushion layer, and surface hardness. Evaluation was performed. The results are shown in Table 3.

(Comparative Example 3)
In Example 4, a photosensitive film and a laminate were produced in the same manner as in Example 4 except that no barrier layer was formed on the cushion layer.
About the obtained permanent pattern-forming photosensitive film and the laminate, as in Example 1, laminating properties, sensitivity, resolution, storage stability, heat resistance, delamination between the barrier layer and the cushion layer, The surface hardness was evaluated. The results are shown in Table 3.

(Comparative Example 4)
In Example 1, a photosensitive film and a laminate were produced in the same manner as in Example 1 except that the barium sulfate dispersion was not added to the photosensitive composition solution.
About the obtained photosensitive film and the said laminated body, it is the same as that of Example 1, lamination property, sensitivity, resolution, storage stability, heat resistance, delamination property between the barrier layer and the cushion layer, and surface hardness. Evaluation was performed. The results are shown in Table 3.

From the results of Table 3, compared with Comparative Examples 1 to 4, the permanent patterns of Examples 1 to 2 and 5 have high sensitivity, high resolution, excellent storage stability, and formed solder. It was found that the resist film was excellent in heat resistance and hardness. Moreover, since the permanent pattern of Examples 3-4 used epoxy acrylate-type resin as a binder of a photosensitive layer, although it is somewhat inferior to a sensitivity, resolution, and storage stability, it is in heat resistance and hardness of the formed solder resist film. It turned out to be excellent. Moreover, since the permanent pattern and laminate of Example 6 include an alkali-soluble thermoplastic resin having high adhesion to the barrier layer in the cushion layer coating solution, it has high sensitivity, high resolution, and storage stability. It was found that the peelability between the barrier layer and the cushion layer was inferior although it was excellent in heat resistance and heat resistance and hardness.

  The method for forming a permanent pattern according to the present invention suppresses distortion of an image formed on a photosensitive layer, thereby providing a permanent pattern (a protective film such as an interlayer insulating film or a solder resist pattern) in the printed wiring board field including a package substrate. Since it can be formed with high definition and efficiency, it can be suitably used for forming various patterns that require high-definition exposure, and particularly suitable for forming high-definition permanent patterns. be able to.

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 permanent 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 permanent pattern forming method (pattern forming apparatus) of the present invention. .

Explanation of symbols

LD1-LD7 GaN-based semiconductor laser 10 Heat block 11-17 Collimator lens 20 Condensing lens 30-31 Multimode optical fiber 44 Collimator lens holder 45 Condensing lens holder 46 Fiber holder 50 Digital micromirror device (DMD)
52 Lens system 53 Reflected light image (exposure beam)
54 Lens of second imaging optical system 55 Micro lens array 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

Claims (23)

  Photosensitive material comprising a support, a cushion layer, a barrier layer capable of suppressing the movement of a substance, (A) a binder, (B) a polymerizable compound, (C) a photopolymerization initiator, and (D) an extender pigment. A photosensitive film comprising a photosensitive layer made of a composition in this order and used for forming a permanent pattern.   The photosensitive film according to claim 1, wherein the content of the extender pigment (D) is 10 to 60% by mass.   The photosensitive film according to claim 1, wherein the interlayer adhesive strength between the cushion layer and the barrier layer is the smallest among the interlayer adhesive strengths between the respective layers.   The photosensitive film according to claim 1, wherein the photosensitive layer has a thickness of 10 to 100 μm, and the cushion layer has a thickness of 5 to 100 μm.   The photosensitive film in any one of Claim 1 to 4 in which a cushion layer contains a thermoplastic resin.   The photosensitive film according to claim 5, wherein either the glass transition temperature (Tg) or the softening point of the thermoplastic resin is 80 ° C. or less.   The photosensitive film according to claim 1, wherein the barrier layer contains at least one of a vinyl polymer and a vinyl copolymer.   The binder (A) is (a) maleic anhydride, (b) an aromatic vinyl monomer, and (c) a vinyl monomer, the glass transition temperature (Tg) of the homopolymer of the vinyl monomer. And a copolymer obtained by reacting 0.1 to 1.0 equivalent of a primary amine compound to the anhydride group of the copolymer consisting of a vinyl monomer having a temperature of less than 80 ° C. Item 8. The photosensitive film according to any one of Items 1 to 7.   The photosensitive film in any one of Claim 1 to 8 in which the polymeric compound (B) contains at least 1 sort (s) selected from the monomer which has a (meth) acryl group.   The photopolymerization initiator (C) is at least selected from halogenated hydrocarbon derivatives, phosphine oxides, hexaarylbiimidazoles, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts and ketoxime ethers. The photosensitive film in any one of Claim 1 to 9 containing 1 type. A cushion layer forming step of applying a water-dispersed emulsion containing a thermoplastic resin on a support and drying to form a cushion layer; and
On the cushion layer, a barrier layer forming step in which a barrier layer coating solution in which the composition contained in the barrier layer is dissolved, emulsified or dispersed is applied and dried to form a barrier layer;
On the barrier layer, a solution of a photosensitive composition containing (A) a binder, (B) a polymerizable compound, (C) a photopolymerization initiator and (D) an extender pigment is applied and dried to form a photosensitive layer. And a photosensitive layer forming step for forming the photosensitive film. A lamination step of laminating the photosensitive film according to any one of claims 1 to 10 so that the photosensitive layer is on the surface side of the substrate by at least one of heating and pressurization,
An exposure step of exposing the laminated photosensitive layer with light irradiated from a light irradiation means;
A development step of developing the photosensitive layer exposed in the exposure step.   The permanent removal according to claim 12, further comprising a peeling step of peeling the support and the cushion layer from the barrier layer simultaneously between the cushion layer and the barrier layer after the exposure step, and then developing the photosensitive layer by the developing step. Pattern forming method.   The permanent layer according to claim 12, further comprising a peeling step of peeling the support and the cushion layer from the barrier layer simultaneously between the cushion layer and the barrier layer after the lamination step, and then exposing the photosensitive layer by the exposure step. Pattern forming method.   The permanent pattern formation method according to claim 12, wherein at least one of a protective film and an interlayer insulating film is formed.   After the exposure process modulates the light from the light irradiating means by the light modulating means having n picture elements for receiving and emitting the light from the light irradiating means, the exposure process is caused by the distortion of the emission surface in the picture element. The method for forming a permanent pattern according to claim 12, wherein the photosensitive layer is exposed with light that has passed through a microlens array in which microlenses having aspherical surfaces capable of correcting aberrations are arranged.   The permanent pattern forming method according to claim 16, wherein the aspherical surface is a toric surface.   18. The light modulation means can control any less than n number of image elements arranged continuously from n image elements in accordance with pattern information. 18. A permanent pattern forming method.   The permanent pattern forming method according to claim 16, wherein the light modulation means is a spatial light modulation element.   The permanent pattern formation method according to claim 19, wherein the spatial light modulation element is a digital micromirror device (DMD).   21. The permanent pattern forming method according to claim 12, wherein the exposure is performed through an aperture array.   The permanent pattern forming method according to claim 12, wherein the photosensitive layer is cured after the development step. The permanent pattern forming method according to claim 22, wherein the curing process is at least one of a whole surface exposure process and a whole surface heat treatment performed at 120 to 200 ° C.