WO2006093040A1 - Pattern forming material, pattern forming apparatus and pattern forming method - Google Patents

Pattern forming material, pattern forming apparatus and pattern forming method Download PDF

Info

Publication number
WO2006093040A1
WO2006093040A1 PCT/JP2006/303404 JP2006303404W WO2006093040A1 WO 2006093040 A1 WO2006093040 A1 WO 2006093040A1 JP 2006303404 W JP2006303404 W JP 2006303404W WO 2006093040 A1 WO2006093040 A1 WO 2006093040A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
pattern forming
photosensitive layer
forming material
pattern
Prior art date
Application number
PCT/JP2006/303404
Other languages
French (fr)
Japanese (ja)
Inventor
Morimasa Sato
Original Assignee
Fujifilm Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujifilm Corporation filed Critical Fujifilm Corporation
Publication of WO2006093040A1 publication Critical patent/WO2006093040A1/en

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers

Definitions

  • the present invention relates to a pattern forming material suitable for dry film resist (DFR), etc., a pattern forming apparatus provided with the pattern forming material, and a pattern forming method using the pattern forming material.
  • DFR dry film resist
  • a pattern forming material in which a photosensitive layer is formed by applying and drying a photosensitive resin composition on a support has been used.
  • a laminate is formed by laminating the pattern forming material on a substrate such as a copper clad laminate on which the permanent pattern is formed, and the photosensitive layer in the laminate is formed on the photosensitive layer.
  • the permanent pattern is formed by exposing to light, developing the light-sensitive layer to form a pattern after the exposure, and then performing an etching process or the like.
  • the surface of a substrate such as PWB (printed wired board) has fine irregularities due to chemical polishing and irregularities caused by uneven thickness of the glass fiber, so that a high-definition permanent pattern is formed.
  • the pattern forming material to be laminated must have an uneven follow-up property.
  • thermoplastic resin layer is provided between the support and the photosensitive layer, and the irregularities on the surface of the substrate are absorbed when transferred under heat and pressure (See Patent Document 1).
  • Patent Document 2 In order to cope with downsizing and high performance of printed wiring boards and the like, a technique for multilayering a photosensitive layer has been developed (see Patent Document 2).
  • pattern forming materials are known in which a plurality of photosensitive layers having different physical properties are laminated in order to improve the coverage of the holes (see Patent Documents 3 and 4).
  • Patent Document 3 a pattern forming material comprising a support on which a first photosensitive layer having low fluidity by heating is provided and a second photosensitive layer having high fluidity by heating is provided thereon.
  • a technique for filling a through-hole with a second photosensitive layer having high fluidity by heating at the time of transfer to a substrate is proposed.
  • the pattern forming material having the multilayer structure has the unevenness following property of the surface of the substrate, but the film thickness is absorbed by absorbing the unevenness.
  • the photosensitive layer in contact with the substrate surface has a softening point lower than that of the outer photosensitive layer or the thermoplastic resin layer
  • the photosensitive layer is softened by heating and pressurizing at the time of lamination.
  • the concave portion on the surface of the base is thick, and the convex portion on the surface of the base is thin.
  • a pattern forming material that is capable of forming a high-definition pattern that is excellent in unevenness followability on the surface of the substrate and that has excellent tent properties and etching uniformity, and a pattern forming apparatus including the pattern forming material, and A pattern forming method using the pattern forming material has not yet been provided, and further improvement and development are desired.
  • Patent Document 1 Japanese Patent Laid-Open No. 5-72724
  • Patent Document 2 Japanese Patent Laid-Open No. 3-17650
  • Patent Document 3 JP-A-8-54732
  • Patent Document 4 Japanese Patent Laid-Open No. 10-111573
  • the present invention has been made in view of the current situation, and it is an object of the present invention to solve the above-described problems and achieve the following objects. That is, the present invention relates to a pattern forming material that is capable of forming a high-definition pattern that is excellent in unevenness followability on the surface of a substrate and that is excellent in tent properties and etching uniformity, and a pattern forming apparatus including the pattern forming material. Another object of the present invention is to provide a pattern forming method using the pattern forming material.
  • the first layer and the second layer are provided in this order, and the glass of the first layer A pattern forming material characterized in that B ⁇ A, where A is the transition temperature (Tg) and B is the glass transition temperature (Tg) of the second layer.
  • A is the transition temperature (Tg)
  • B is the glass transition temperature (Tg) of the second layer.
  • ⁇ 2> The pattern forming material according to ⁇ 1>, wherein the glass transition temperature A of the first layer is -20 to 30 ° C, and the glass transition temperature B of the second layer is 10 to 40 ° C. It is.
  • ⁇ 4> The pattern forming material according to any one of ⁇ 1> to ⁇ 3>, wherein the first layer has a thickness of 5 to 30 ⁇ m, and the second layer has a thickness of 2 to 15 ⁇ m.
  • ⁇ 5> The pattern forming material according to any one of ⁇ 1> to ⁇ 4>, wherein the first layer is a cushion layer and the second layer is a photosensitive layer.
  • thermoplastic resin has a softening point of 80 ° C or lower.
  • the minimum exposure amount capable of pattern formation of the first photosensitive layer is larger than the minimum exposure amount capable of pattern formation of the second photosensitive layer. Pattern forming material.
  • the photosensitive layer contains a binder, a polymerizable compound, and a photopolymerization initiator.
  • ⁇ 14> The pattern forming material according to any one of ⁇ 10> and ⁇ 13>, wherein the polymerizable compound contains a monomer having at least one of a urethane group and an aryl group.
  • Photopolymerization initiators are halogenated hydrocarbon derivatives, hexaryl biimidazoles, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts and
  • ⁇ 17> The pattern forming material according to any one of ⁇ 1> to ⁇ 16>, wherein a barrier layer capable of controlling the movement of a substance is provided between the first layer and the second layer.
  • ⁇ 18> The pattern forming material according to ⁇ 17>, wherein the Noria layer includes at least one of a bull polymer and a bull copolymer.
  • Pattern forming material force The pattern forming material according to any one of ⁇ 1> to ⁇ 20>, which is long and wound in a roll shape.
  • a light irradiating means capable of irradiating light; and a light modulating means for modulating light from the light irradiating means and exposing the photosensitive layer in the pattern forming material.
  • This is a pattern forming apparatus.
  • the light modulation unit further includes a pattern signal generation unit that generates a control signal based on the pattern information to be formed, and the control generated by the pattern signal generation unit generates light emitted from the light irradiation unit.
  • the pattern forming apparatus according to ⁇ 23> wherein the pattern is modulated according to a signal.
  • the light modulation unit since the light modulation unit includes the pattern signal generation unit, the light emitted from the light irradiation unit is converted into a control signal generated by the pattern signal generation unit. Modulated accordingly.
  • the light modulation means has n pixel parts, and forms any less than n of the pixel parts continuously arranged from the n pixel parts. 25.
  • any less than n pixel parts arranged continuously from the n pixel parts in the light modulation unit are controlled according to pattern information. As a result, the light of the light irradiation means power is modulated at high speed.
  • ⁇ 26> The pattern forming apparatus according to any one of ⁇ 23>, ⁇ 25>, wherein the light modulation means is a spatial light modulation element.
  • ⁇ 27> The pattern forming apparatus according to ⁇ 26>, wherein the spatial light modulation element is a digital 'micromirror' device (DMD).
  • DMD digital 'micromirror' device
  • ⁇ 28> The pattern forming apparatus according to any one of the above ⁇ 25>, ⁇ 27>, wherein the pixel part is a micromirror.
  • ⁇ 29> The pattern forming apparatus according to any one of the above ⁇ 23>, ⁇ 28>, wherein the light irradiation means can synthesize and irradiate two or more lights.
  • the pattern forming apparatus described in 29> above since the light irradiating means can synthesize and irradiate two or more lights, exposure is performed with exposure light having a deep focal depth. As a result, the pattern forming material is exposed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.
  • the light irradiating means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that collects the laser beams irradiated with the plurality of laser forces and couples them to the multimode optical fiber.
  • the putter according to any one of the above Forming device.
  • the light irradiating means may collect the laser light respectively emitted from the plurality of lasers by the collective optical system and be coupled to the multimode optical fiber.
  • exposure is performed with exposure light having a deep focal depth.
  • the exposure to the pattern forming material is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, a very fine pattern is formed.
  • a pattern forming method comprising at least exposing the photosensitive layer in the pattern forming material according to any one of ⁇ 1> to ⁇ 22>.
  • ⁇ 32> The pattern forming method according to ⁇ 31>, wherein the pattern forming material is laminated on the substrate while being heated and pressurized and exposed.
  • ⁇ 33> The pattern forming method according to any one of ⁇ 31>, ⁇ 32>, wherein the exposure is performed imagewise based on pattern information to be formed.
  • ⁇ 34> The pattern forming method according to ⁇ 31>, ⁇ 33>, wherein the exposure is performed using light modulated based on the pattern information to be formed and modulated in accordance with the control signal. It is.
  • the exposure is performed through a microlens array in which microlenses having aspherical surfaces capable of correcting aberrations due to distortion of the exit surface of the picture element portion in the light modulation means are arranged.
  • the pattern forming method according to any one of the above 31> Karaku 35>.
  • ⁇ 38> The pattern forming method according to any one of ⁇ 31>, ⁇ 37>, wherein the exposure is performed through an aperture array.
  • the extinction ratio is improved by performing exposure through the aperture array.
  • the exposure is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.
  • ⁇ 39> The pattern forming method according to any one of ⁇ 31>, ⁇ 38>, wherein the exposure is performed while relatively moving the exposure light and the photosensitive layer.
  • exposure is performed at a high speed by performing exposure while relatively moving the modulated light and the photosensitive layer. For example, when the photosensitive layer is subsequently developed, a high-definition pattern is formed.
  • ⁇ 41> The pattern forming method according to any one of ⁇ 31> to ⁇ 40>, wherein the photosensitive layer is developed after the exposure.
  • ⁇ 43> The pattern formation method according to ⁇ 42>, wherein the permanent pattern is a wiring pattern, and the formation of the permanent pattern is performed by at least one of an etching process and a plating process.
  • a pattern forming material that can solve the conventional problems, can form a high-definition pattern that is excellent in uneven surface followability on the substrate surface, and excellent in tent properties and etching uniformity.
  • a pattern forming apparatus including the pattern forming material and a pattern forming method using the pattern forming material.
  • FIG. 1 is an example of a front view of a microlens constituting a microlens array.
  • FIG. 2 is an example of a side view of a microlens constituting a microlens array.
  • FIG. 3 is an example of a front view of a microlens constituting a microlens array.
  • FIG. 4 is an example of a side view of a microlens constituting a microlens array.
  • FIG. 5 is an example of a schematic diagram showing a condensing state by a microlens in one cross section.
  • FIG. 6 is an example of a schematic view showing a condensing state by a microlens in one cross-section in FIG. 5 and another cross-section.
  • FIG. 7 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.
  • FIG. 8 is an example of a plan view showing an optical image projected on an exposed surface when a microlens array or the like is not used.
  • FIG. 9 is an example of a plan view showing an optical image projected on an exposed surface when a microlens array or the like is used.
  • FIG. 10 is a perspective view showing a configuration of a fiber array light source.
  • FIG. 11 is an example of a front view showing an arrangement of light emitting points in a laser emitting portion of a fiber array light source.
  • FIG. 12 is an example of a diagram showing a configuration of a multimode optical fiber.
  • FIG. 13 is an example of a plan view showing a configuration of a combined laser light source.
  • FIG. 14 is an example of a plan view showing a configuration of a laser module.
  • FIG. 15 is an example of a side view showing the configuration of the laser module shown in FIG.
  • FIG. 16 is a partial side view showing the configuration of the laser module shown in FIG.
  • FIG. 17 is an example of a diagram illustrating an example of a DMD usage area.
  • FIG. 18 is an example of a diagram showing an example of a DMD usage area similar to FIG.
  • FIG. 19 is an example of a schematic perspective view showing an appearance of an example of a pattern forming apparatus.
  • the pattern forming material of the present invention has a first layer and a second layer in this order on a support, the glass transition temperature (Tg) of the first layer is A, and the second layer has a glass transition temperature (Tg).
  • Tg glass transition temperature
  • B glass transition temperature
  • the first layer is a cushion And an embodiment in which the second layer is a photosensitive layer, and (2) an embodiment in which the first layer is a first photosensitive layer and the second layer is a second photosensitive layer.
  • the pattern forming material may have a barrier layer capable of suppressing the movement of a substance between the first layer and the second layer as necessary.
  • the glass transition temperature of the second layer is preferably within the temperature range at the time of lamination, and within the range in which the unevenness followability of the second layer to the substrate can be controlled by controlling the temperature conditions at the time of lamination. I prefer to be there.
  • the glass transition temperature B of the second layer is preferably ⁇ 10 to 40 ° C., more preferably 10 to 40 ° C.
  • the followability to irregularities on the substrate surface may be reduced under general lamination conditions, and is less than ⁇ 10 ° C. Under general lamination conditions, irregularities on the surface of the substrate may be absorbed, resulting in non-uniform film thickness.
  • the glass transition temperature A of the first layer is not particularly limited as long as it is equal to or lower than B of the second layer, but it is preferably 20-30 ° C and 20-20 ° C. Is more preferable.
  • the glass transition temperature A of the first layer exceeds the glass transition temperature B of the second layer, the deformation of the second layer is suppressed and the film thickness may be nonuniform.
  • the measuring method of the glass transition temperature can be appropriately selected according to the purpose without any particular limitation.
  • the TMA method using a thermal analyzer the DSC method using a differential scanning calorimeter, A known method such as a DMA method using a viscosity elasticity measuring apparatus may be used.
  • the measurement sample for example, 10 to 500 mg each of the prepared first layer and the second layer collected using a microtome can be used.
  • the melt viscosity of the second layer is preferably from 500 to 30,000 (Pa 'S), more preferably from 1,000 to 30,000 (Pa ⁇ S) in the range of 40 to 100 ° C! /.
  • the method for measuring the melt viscosity is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include a solid-liquid dynamic viscoelasticity measuring device, a cantilever rheometer, a cone / disk rheometer, Examples thereof include a measurement method using a uniaxial elongation viscosity, a melt indexer and the like.
  • the measurement sample can be appropriately prepared according to the measurement device.
  • the first layer and the second layer force also use a microtome or the like. Can be used.
  • the thickness of the first layer is preferably 5 to 30 ⁇ m, more preferably 10 to 30 ⁇ m. If the thickness of the first layer exceeds 30 m, the resolution may decrease and the load during image formation may increase, and if it is less than 5 m, the transferability to the substrate may deteriorate. .
  • the thickness of the second layer is preferably 2 to 10 m, more preferably 2 to 15 m.
  • the etching property may be deteriorated, and when it is less than 2 m, the cured film may be peeled off during the etching.
  • the cushion layer is not particularly limited as long as it satisfies the glass transition temperature, melt viscosity, and thickness ranges of the first layer, and can be appropriately selected according to the purpose. The inclusion is preferred.
  • the thermoplastic resin mainly comprises an alkali-soluble thermoplastic polymer, and other components as necessary. Including, ok.
  • the acid value (mgKOH / g) of the thermoplastic polymer is not particularly limited.
  • a force that can be appropriately selected according to the purpose 50 to 300 force S, preferably 60 to 270 S, more preferably 70 to 250 is particularly preferred.
  • the acid value is within the above range, the developability of the cushion layer can be ensured.
  • the acid value is less than 50, development failure may occur.
  • the acid value exceeds 300, the cushion layer becomes too hard, and uneven followability and laminating properties may be deteriorated.
  • the weight average molecular weight of the thermoplastic polymer is not particularly limited.
  • the force to be selected as appropriate S The force that can be applied S 1,000-300,000 force S is preferable, 3,000-200,000 force is more preferable 5,000-150,000 is particularly preferable.
  • the weight average molecular weight is within the above range, the developability of the cushion layer can be ensured, and the viscosity r? Can be easily adjusted. Further, the effect can be further obtained by the combination with the above acid value range. If the weight average molecular weight is less than 1,000, the membrane may become fragile or the cushion layer may exude during lamination. If it exceeds 300,000, the cushion layer may become too hard, and the unevenness followability and laminating properties may deteriorate.
  • the content of the thermoplastic polymer in the cushion layer is not particularly limited.
  • a force that can be appropriately selected according to the purpose For example, 35 mass% with respect to the total solid content of the cushion layer. It is preferable that the content is 55% by mass or more.
  • the soft soft point (Vicat) of the thermoplastic polymer is not particularly limited.
  • the force can be appropriately selected according to the purpose.
  • the soft soft point of the cushion layer is 80 ° C or lower.
  • those having a substantial soft spot of 80 ° C or less are preferred.
  • alkali-soluble thermoplastic polymers having a softening point of 80 ° C. or lower include ethylene and acrylate copolymer cans, styrene and (meth) acrylate copolymer cans and vinyls.
  • the thermoplastic resin having a softening point of 80 ° C or lower includes, in addition to the above-described thermoplastic resin, “Plastic Performance Handbook” (edited by the Japan Plastics Industry Federation, All Japan Plastics Molding Industry Association, industrial research). Of organic polymers with a soft spot of about 80 ° C or less (published on October 25, 1968) by the Society). In addition, even in an organic polymer material having a soft softening point of 80 ° C or higher, various plasticizers compatible with the organic polymer material are added to the organic polymer material so that a substantial softness can be obtained. It is also possible to lower the point below 80 ° C Noh.
  • the plasticizer is not particularly limited and may be appropriately selected depending on the purpose.
  • polypropylene glycol polyethylene glycol, dioctyl phthalate, diheptino phthalate, dibutino phthalate, tricres Alcohols and esters such as zircphosphate, uddernoresiphosphate and biphenyldiphosphate, amides such as toluenesulfonamide, and the like.
  • the interlayer adhesive force of the pattern forming material is not particularly limited and can be appropriately selected according to the purpose.
  • the interlayer adhesive force between the support and the cushion layer is the smallest among the interlayer adhesive strengths of the respective layers.
  • the interlayer adhesive strength only the support is peeled off from the laminate, the photosensitive layer is exposed through the cushion layer, and then the photosensitive layer is developed using an alkaline developer. be able to.
  • the photosensitive layer can be developed using an alkaline developer.
  • the method for adjusting the interlayer adhesive force is not particularly limited, and can be appropriately selected according to the purpose.
  • a known polymer, supercooling substance, or adhesion improver in the thermoplastic resin can be selected.
  • a method of adding a surfactant, a release agent and the like can be selected.
  • thermoplastic resin examples include a copolymer whose main component is an essential copolymer component of ethylene.
  • the copolymer having ethylene as an essential copolymer component is not particularly limited and can be appropriately selected according to the purpose.
  • ethylene vinyl acetate copolymer (EV A) ethylene-ethyl acrylate. Copolymer (EEA) and the like.
  • the interlayer adhesive force of the pattern forming material can be appropriately selected according to the purpose without any particular limitation.
  • the adhesive strength between the photosensitive layer as the second layer and the cushion layer is preferably the smallest.
  • the method for adjusting the interlayer adhesion can be appropriately selected according to the purpose for which there is no particular limitation.
  • various polymers, supercooled substances, adhesion improvers in the thermoplastic resin can be selected.
  • the ethylene copolymerization ratio in the copolymer having ethylene as an essential copolymerization component is a force that can be appropriately selected according to the purpose without any particular limitation. For example, 60-90% by mass is preferable. 60-80% by mass is more preferred. 65-80% by mass is particularly preferred.
  • the ethylene copolymerization ratio is less than 60% by mass, the interlayer adhesive force between the cushion layer and the photosensitive layer increases, and it becomes difficult to peel off at the interface between the cushion layer and the photosensitive layer. If the amount exceeds 90% by mass, the indirect adhesion between the cushion layer and the photosensitive layer becomes too small, and the cushion layer and the photosensitive layer are very easily peeled off. It may be difficult to produce a pattern forming material containing
  • the interlayer adhesion of each layer is the smallest.
  • the support, the cushion layer, and the barrier layer are peeled from the laminate, and the photosensitive layer is exposed, and then the photosensitive layer is exposed to an alkaline developer.
  • the layer can be developed. Further, the photosensitive layer is exposed through the cushion layer while leaving the support without being peeled, and then the support, the cushion layer, and the barrier layer are peeled from the laminate, and the alkaline layer
  • the photosensitive layer can be developed using a developing solution.
  • the method for adjusting the interlayer adhesive force can be appropriately selected according to the purpose without any particular limitation.
  • a method of containing a release agent in the photosensitive layer, the cushion layer and the barrier A method for surface-treating an adhesive surface with a layer, the support and the cushion layer A method of surface-treating the adhesive surface, a method of adjusting at least one content selected from components contained in at least one of the layers, and a method of containing or applying a component that improves the adhesive force
  • a method of containing a release agent in the photosensitive layer, the cushion layer and the barrier A method for surface-treating an adhesive surface with a layer, the support and the cushion layer
  • a method of surface-treating the adhesive surface a method of adjusting at least one content selected from components contained in at least one of the layers
  • a method of containing or applying a component that improves the adhesive force may be used alone or in combination of two or more.
  • the release agent can be appropriately selected from known release agents with no particular limitations. Examples thereof include silicone compounds and compounds having a fluorinated alkyl group.
  • silicone compound examples include Daicel UCB Co., Ltd., Evecril 1360, 350, Toshiba Silicone Co., Ltd., dimethyl silicone oil TSF400, methylphenol silicone, 1-year-old Inole TSF4300, TSF4446, TSF4460, TSF4452 etc. are listed.
  • Examples of the compound having a fluorinated alkyl group include a fluorine-based surfactant (for example, perfluoroalkyl group 'hydrophilic group-containing oligomer F-171, manufactured by Dainippon Ink & Chemicals, Inc.
  • a fluorine-based surfactant for example, perfluoroalkyl group 'hydrophilic group-containing oligomer F-171, manufactured by Dainippon Ink & Chemicals, Inc.
  • Examples of the surface treatment include plasma treatment, electron beam treatment, glow discharge treatment, corona discharge treatment, and ultraviolet irradiation treatment.
  • the ethylene copolymerization ratio in the copolymer is less than 60% by mass. The method of doing is mentioned.
  • Examples of the component for improving the adhesive strength include phenolic substances (for example, cresol monovolac resin, phenol resin, etc.), polysalt-vinylidene resin, styrene butadiene rubber, gelatin, polybulu alcohol, cellulose And the like. These may be included in at least one of the support, the cushion layer, and the barrier layer, if necessary, on the contact surface between the support and the cushion layer, the cushion layer, and the barrier layer. You may apply
  • crosslinking agent examples include borax, boric acid, borates (for example, orthoborate, InBO
  • Aldehyde compounds such as formaldehyde, glyoxal, and glutaraldehyde; ketone compounds such as diacetyl and cyclopentanedione; bis (2-chlorodiethylurea) -2 hydroxy 4, 6 dichloro 1, 3, 5 Active halogen compounds such as triazine, 2, 4 dichloro-6-S-triazine 'sodium salt; divinyl sulfonic acid, 1,3 berylsulfolulu 2-propanol, ⁇ , ⁇ , monoethylenebis (birusulfuluolacetamide) ), 1, 3, 5 Tributyloyl-hexahydro S Triazine and other active bur compounds; dimethylol urea, methylol dimethylhydantoin and other ⁇ -methylol compounds; Epoxy resin; 1, 6-hexamethylene diis
  • silane coupling agent examples include: ⁇ -2 (aminoethyl) 3aminopropyl methyldimethoxysilane, ⁇ -2 (aminoethyl) 3aminopropyltrimethoxysilane, ⁇ - 2 (Aminoethyl) 3 Aminopropyltriethoxysilane, 3 Aminopropyltrimethoxysilane, 3 Aminopropyltriethoxysilane, 3 Triethoxysilyl mono N— (1, 3 Dimethyl
  • a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be suitably used.
  • the layer containing at least one of the cross-linking agent and the silane coupling agent can be appropriately selected depending on the purpose without any particular limitation.
  • the cushion layer and the noria layer are preferable. More preferably, the cushion layer alone is more preferable.
  • At least one of the components included in the support at least one selected from the component force included in the cushion layer, and the components included in the noria layer.
  • the component force contained in the cushion layer is selected from the components contained in the photosensitive layer, wherein at least one selected from the component force and at least one selected from the components contained in the barrier layer are made into a hydrophobic substance.
  • the component is polybulal alcohol
  • the polybulal alcohol having a saponification degree of 85% or less or a modified polybulal alcohol can be appropriately selected and used.
  • the polybulal alcohol may be used in combination with the crosslinking agent, the silane coupling agent, or the like.
  • modified polybulal alcohol examples include cation-modified polybulal alcohol (for example, carboxy-modified polybulal alcohol), cation-modified polybulal alcohol, acetoacetylated polybulal alcohol, silanol-modified polybulal alcohol, hydrophobic group-modified polybutyl alcohol.
  • examples include polybulal alcohol (for example, terminal alkylpolybulal alcohol), hydrophilic group-modified polyvinyl alcohol (for example, ethylene oxide-modified polybulal alcohol), terminal thiol polybulal alcohol, exeval (manufactured by KURARENE), and the like.
  • the cushion layer is prepared by dissolving the thermoplastic resin and, if necessary, other components in an organic solvent to prepare a coating solution (a coating solution for a thermoplastic resin layer). It can be formed by coating on the support.
  • a coating solution a coating solution for a thermoplastic resin layer.
  • the organic solvent include methyl ethyl ketone and 1-methoxy-2-propanol.
  • the photosensitive layer contains a binder, a polymerizable compound, and a photopolymerization initiator, and appropriately contains other components as necessary.
  • the photosensitive layer has a glass transition temperature, a melt viscosity, and a thickness range of the second layer. As long as it is satisfied, it can be appropriately selected according to the purpose for which there is no restriction.
  • the first photosensitive layer has a glass transition temperature of the first layer, The range of melt viscosity and thickness is satisfied, and the second photosensitive layer satisfies the range of glass transition temperature, melt viscosity, and thickness of the second layer.
  • the photosensitivity of the second photosensitive layer is higher than the photosensitivity of the first photosensitive layer.
  • the first photosensitive layer is irradiated with light having a wavelength of 405 nm. It is preferable that the minimum exposure amount that can be patterned on the photosensitive layer is larger than the minimum exposure amount that can be patterned on the second photosensitive layer.
  • the light irradiated from the support side during exposure proceeds in the order of the support, the first photosensitive layer, and the second photosensitive layer when the support is provided, and the curing of the second photosensitive layer is Before the first photosensitive layer, the process starts with a small amount of light energy.
  • the amount of light energy is increased after the entire second photosensitive layer is cured, curing of the first photosensitive layer starts, and when the amount of light energy is further increased, the entire first photosensitive layer is cured.
  • the amount of light energy at which the second photosensitive layer begins to cure is preferably in the range of 0.05-: LOmjZcm 2 , more preferably in the range of 0.1-5 mjZcm 2 0 A range of 15 to 2.5 mjZcm 2 is particularly preferred.
  • the amount of light energy required of the second photosensitive layer in order to cure in the range of preferably tool 0. 2 ⁇ 15mj / cm 2 in the range of 0. l ⁇ 20mj / cm 2 More preferably 0.4 to: LOmj / cm 2 is particularly preferable.
  • the ratio (AZB) of the amount of light energy A required to cure the second photosensitive layer to the amount of light energy B necessary to cure the first photosensitive layer is 0.005-0.
  • a force S in the range of 5 is preferable, a force in the range of 0.01 to 0.4 is more preferable than a force S, and a range of 0.02 to 0.35 is particularly preferable.
  • the ratio (CZA) between the amount of light energy A required to cure the second photosensitive layer and the amount of light energy C required until the first photosensitive layer begins to cure (CZA) is in the range of 1-10. It is particularly preferable that it is in the range of 1.1-9, and it is particularly preferable that it is in the range of 1.3-8.
  • the light energy C is particularly preferably in the range of 0.1 ⁇ 200MjZcm 2 is in the range of more preferably tool 2 ⁇ 50MiZcm 2 in the range of good Mashigu l ⁇ 100mjZcm 2.
  • the noinder is more preferably soluble in an alkaline liquid, preferably swellable in an alkaline liquid.
  • Suitable examples of the binder exhibiting swellability or solubility with respect to the alkaline liquid include those having an acidic group.
  • the acidic group is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a carboxyl group, a sulfonic acid group, and a phosphoric acid group, and among these, a carboxyxenore group is preferable. .
  • binder having a carboxyl group examples include a vinyl copolymer having a carboxyl group, polyurethane resin, polyamic acid resin, and modified epoxy resin.
  • solubility in a coating solvent Viewpoints such as solubility in alkaline developer, suitability for synthesis, and ease of adjustment of film properties.
  • Vinyl copolymers having a carboxyl group are preferred.
  • the vinyl copolymer having a carboxyl group can be obtained by copolymerization with at least (1) a vinyl monomer having a carboxyl group, and (2) a monomer copolymerizable therewith. Examples thereof include compounds described in paragraphs 0164 to 0205 of 2005-258431.
  • the binder content in the photosensitive layer is not particularly limited. For example, 10 to 90% by mass is preferable, and 20 to 80% by mass is more preferable, and 40 to 80% by mass is particularly preferable.
  • the content is less than 10% by mass, the alkali developability and the adhesion to a printed wiring board forming substrate (for example, a copper-clad laminate) may be deteriorated. The stability against image time and the strength of the cured film (tent film) may be reduced.
  • the above content may be the total content of the binder and the polymer binder used in combination as necessary.
  • the binder content in the second photosensitive layer is included in the second photosensitive layer within the above range for sensitivity adjustment. If it is contained in the first photosensitive layer !, make adjustments such as lowering the binder content (higher content of the polymerizable compound).
  • the acid value of the binder can be appropriately selected depending on the purpose for which there is no particular limitation. For example, 100 to 250 (mgKOH / g) is preferable, and 120 to 220 (mgKOHZ g) is more preferable. The preferred range is 150 to 220 (mgKOH / g).
  • the acid value is less than lOO (mgKOHZg)
  • developability may be insufficient
  • resolution may be inferior
  • permanent patterns such as wiring patterns may not be obtained with high definition.
  • the amount exceeds / g
  • at least one of the developer resistance and adhesion of the pattern deteriorates, and a permanent pattern such as a wiring pattern may not be obtained with high definition.
  • the polymerizable compound can be appropriately selected according to the purpose without any particular limitation.
  • a monomer or oligomer having at least one of a urethane group and an aryl group is preferably exemplified. These preferably have two or more polymerizable groups.
  • Examples of the polymerizable group include an ethylenically unsaturated bond (for example, a (meth) atalyl group, a (meth) acrylamide group, a styryl group, a beryl group such as a butyl ester or a butyl ether, a allylic ether or the like.
  • Aryl groups such as aryl esters
  • polymerizable cyclic ether groups for example, epoxy groups, oxetane groups, etc.
  • the monomer having a urethane group is not particularly limited as long as it has a urethane group, and can be appropriately selected according to the purpose. For example, it is described in paragraphs 0210 to 0262 of JP 2005-258431 A. And the like.
  • the monomer having an aryl group is not particularly limited as long as it has an aryl group, and can be appropriately selected according to the purpose. For example, it is described in paragraphs 0263 to 0271 of JP 2005-258431 A. And the like.
  • a polymerizable monomer other than the monomer having a urethane group and the monomer having an aryl group may be used.
  • Examples of the polymerizable monomer other than the monomer containing a urethane group and the monomer containing an aromatic ring include the compounds described in paragraphs 0272 to 0284 of JP-A-2005-258431. It is done.
  • the content of the polymerizable compound in the photosensitive layer is, for example, preferably 5 to 90% by mass, more preferably 15 to 60% by mass, and particularly preferably 20 to 50% by mass.
  • the strength of the tent film may be reduced, and if it exceeds 90% by mass, edge fusion during storage (extruding failure of the roll end force) may be deteriorated. is there.
  • the monomer content of the second photosensitive layer is adjusted within the above range to adjust the sensitivity. Adjustment, such as making it higher than a content rate, may be performed.
  • the content of the polyfunctional monomer having two or more of the polymerizable groups in the polymerizable compound is preferably 5 to: L00 mass% is preferable 20 to: L00 mass% is more preferable 40 to 40 : L00% by mass is particularly preferable.
  • the photopolymerization initiator can be appropriately selected from known photopolymerization initiators that are not particularly limited as long as they have the ability to initiate polymerization of the polymerizable compound.
  • known photopolymerization initiators that are not particularly limited as long as they have the ability to initiate polymerization of the polymerizable compound.
  • the compound described in paragraphs 0286 to 0310 of JP-A-2005-258431 can be mentioned.
  • the content of the photopolymerization initiator in the photosensitive layer is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and particularly preferably 0.5 to 15% by mass.
  • the amount of the photopolymerization initiator contained in the photosensitive layer may be larger than the amount of the photopolymerization initiator contained in the first photosensitive layer.
  • the photopolymerization initiator content of the second photosensitive layer is preferably 1.5 to L00 times the content of the photopolymerization initiator of the first photosensitive layer, and more preferably 1.8 times to A 50-fold amount is preferable, and a 2 to 20-fold amount is particularly preferable.
  • Examples of the other components include sensitizers, thermal polymerization inhibitors, plasticizers, color formers, colorants, and the like, and adhesion promoters to the substrate surface and other auxiliary agents (for example, pigments). , Conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, release accelerators, antioxidants, fragrances, thermal crosslinking agents, surface tension modifiers, chain transfer agents, etc.) .
  • Examples of these compounds include, for example, compounds described in JP-A-2005-258431, paragraphs 0312 and 0336, and the like. Properties such as stability, photographic properties, print-out properties, film properties, etc. can be adjusted.
  • the barrier layer can be appropriately selected according to the purpose without particular limitation as long as the movement of the substance can be suppressed, and is soluble in an alkaline liquid which may be water-soluble or water-dispersible. It may be insoluble.
  • the ability to suppress the movement of the substance means that the content of the target substance in the first layer and the second layer adjacent to the barrier layer is increased compared to the case where the barrier layer is not provided. Or it means that the decrease is suppressed.
  • the substance can be appropriately selected depending on the purpose for which there is no particular limitation.
  • the substance is included in at least one of oxygen, water, the first layer, and the second layer. Substances.
  • the barrier layer is water-soluble or water-dispersible
  • the barrier layer when the barrier layer is soluble in an alkaline liquid that preferably contains a water-soluble or water-dispersible resin, the alkaline liquid It is preferable to contain soluble greaves.
  • the water solubility is preferably, for example, preferably 0.1% by mass or more, and more preferably 1% by mass or more, with respect to 25 ° C. water.
  • the resin can be appropriately selected according to the purpose for which there is no particular limitation.
  • various alcohol-soluble resins, water-soluble resins, alcohol-dispersible resins, water-dispersible resins examples include fats, emulsifiable fats, and fats that are soluble in alkaline liquids.
  • specific examples include bulle polymers (for example, polybulal alcohol (including modified polybulal alcohols), polyvinylpyrrolidone, etc.), Examples thereof include the above-mentioned vinyl copolymers, water-soluble polyamides, gelatin, cellulose, and derivatives thereof.
  • the thermoplastic resin described in Japanese Patent No. 2794242 and the compounds 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.
  • the barrier layer is insoluble in the alkaline liquid
  • Examples of the resin insoluble in the alkaline liquid include a copolymer whose main component is ethylene as a necessary copolymer component.
  • the copolymer having ethylene as an essential copolymer component is a force that can be appropriately selected according to the purpose without any particular limitation.
  • ethylene vinyl acetate copolymer (EV A) ethylene-ethyl acrylate. Copolymer (EEA) and the like.
  • the thickness of the barrier layer can be appropriately selected according to the purpose for which there is no particular limitation. For example, it is preferably less than 10 ⁇ m, more preferably 0.1 to 6 ⁇ m 1 ⁇ 5 ⁇ m is particularly preferred.
  • the thickness is 10 / z m or more, light scattering occurs in the barrier layer during exposure, and at least one of resolution and adhesion may be deteriorated.
  • the support can be appropriately selected according to the purpose without particular limitation, Those having good light transmittance are preferred, and the surface smoothness is more preferred.
  • the support is preferably made of a synthetic resin and transparent, for example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic.
  • plastic films such as butyl acetate copolymer, polytetrafluoroethylene, polytrifluoroethylene, 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.
  • the thickness of the support is not particularly limited, and can be appropriately selected according to the purpose.
  • F column; t is 2-150 ⁇ m force S girlish, 5-: LOO ⁇ m force SJ-like girls, 8-50 ⁇ m force S Particularly preferred.
  • the shape of the support is not particularly limited and may be appropriately selected depending on the purpose, but is preferably long.
  • the length of the long support is not particularly limited, and examples thereof include a length of 10 m to 20000 m.
  • the pattern forming material may form a protective film on the second layer (photosensitive layer).
  • Examples of the protective film include those used for the support, paper, polyethylene, paper laminated with polypropylene, and the like. Among these, a polyethylene film and a polypropylene film are preferable.
  • the thickness of the protective film is not particularly limited and can be appropriately selected according to the purpose. For example, 5 to: LOO / zm force is preferable, 8 to 50 111 is preferable, and 10 to 30 / zm is preferable. Particularly preferred.
  • the interlayer adhesive force between the protective film and the second layer (photosensitive layer) is preferably the smallest among the interlayer adhesive forces of the other layers.
  • the support and the protective film examples include polyethylene terephthalate z polypropylene, polyethylene terephthalate z polyethylene, polychlorinated bur Z cellophane, polyimide Z polypropylene, polyethylene terephthalate z polyethylene terephthalate, and the like.
  • the above-described adhesive force relationship can be satisfied by surface-treating at least one of the support and the protective film.
  • the surface treatment of the support may be performed in order to increase the adhesive force with the first layer (cushion layer or first photosensitive layer).
  • coating of an undercoat layer corona discharge treatment
  • examples thereof include flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow discharge irradiation treatment, active plasma irradiation treatment, and laser beam irradiation treatment.
  • the coefficient of static friction between the support and the protective film is preferably 0.3 to 1.4, more preferably 0.5 to 1.2 force! / !.
  • the pattern forming material is preferably stored, for example, wound around a cylindrical core and wound into a long roll.
  • the length of the long pattern forming material is not particularly limited, and can be appropriately selected, for example, a range force of 10 m to 20, OOOm.
  • slitting may be performed so that it is easy for the user to use, and a long body in the range of 100 m to l, OOOm may be rolled.
  • the support is wound up so as to be the outermost side.
  • the roll-shaped pattern forming material may be slit into a sheet shape.
  • a separator especially moisture-proof and desiccant-containing
  • the protective film may be surface-treated in order to adjust the adhesion between the protective film and the second layer (photosensitive layer).
  • an undercoat layer having a polymer strength such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, polyvinyl alcohol or the like 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. it can.
  • the photosensitive layer, the barrier layer, the support, and the protective film in addition to the cushion layer, the photosensitive layer, the barrier layer, the support, and the protective film, as long as the glass transition point of the layer that contacts the substrate is the highest.
  • You may have layers, such as a layer and a surface protective layer. Each of the layers may have one layer or two or more layers.
  • the pattern forming material can be manufactured, for example, as follows. First, the materials contained in the first layer, the second layer, and the barrier layer are dissolved, emulsified or dispersed in water or a solvent to prepare a coating solution.
  • the solvent of the coating solution can be appropriately selected according to the purpose without any particular limitation.
  • 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, diisoptyl ketone; Ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl ethyl propionate, phthalic acid Esters such as dimethyl, ethyl benzoate, and methoxypropyl acetate; aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene; tetrasalt carbon, trichloroethylene, chloroform, 1, 1, 1-
  • Hydrogen fluorides such as tetrahydrofuran, jetyl ether, ethylenic glycolenomonoethylenoateol, ethyleneglycolenomonoethylenotenole, 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide , Dimethyl sulfoxide, sulfolane and the like. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.
  • the first layer coating solution (cushion layer coating solution or first photosensitive layer coating solution) is applied onto the support and dried to form the first layer.
  • the noria layer coating solution is applied and dried to form a noria layer
  • the second layer coating solution (photosensitive layer coating solution) is formed on the barrier layer.
  • a coating solution for the second photosensitive layer and dried to form the second layer, whereby a pattern forming material can be produced.
  • the method of applying the coating solution is appropriately selected according to the purpose for which there is no particular limitation. For example, spray coating, roll coating, spin coating, slit coating, etching coating, curtain coating, die coating, gravure coating, wire bar coating, knife coating, etc. A method is mentioned.
  • the drying conditions vary depending on each component, the type of solvent, the ratio of use, etc., but are usually 60 to 110 ° C. for 30 seconds to 15 minutes.
  • the pattern forming material of the present invention is capable of forming a high-definition pattern excellent in uneven surface followability on the substrate surface and excellent in tent property and etching uniformity, various pattern formations are possible.
  • Suitable for forming permanent patterns such as wiring patterns, color filters, column materials, rib materials, spacers, liquid crystal structural members such as partition walls, and forming patterns for holograms, micromachines, proofs, etc.
  • it can be suitably used in the pattern forming method and pattern forming apparatus of the present invention.
  • the pattern forming apparatus of the present invention includes the pattern forming material of the present invention, and has at least light irradiation means and light modulation means.
  • the pattern forming method of the present invention includes at least an exposure step, and includes other steps appropriately selected.
  • the said exposure process is a process of exposing with respect to the photosensitive layer in the pattern formation material of this invention.
  • the pattern forming material of the present invention is as described above.
  • the exposure target is not particularly limited as long as it is a photosensitive layer in the pattern forming material, and can be appropriately selected according to the purpose.
  • the pattern forming material is formed on a substrate. It is preferable to be performed on the laminated body.
  • the substrate may be appropriately selected from known materials having no particular limitation, medium strength, high surface smoothness, force, and a surface having an uneven surface, but a plate-shaped substrate (substrate) may be used.
  • a plate-shaped substrate for example, copper-clad laminate
  • glass plate for example, soda glass plate
  • synthetic resin film for example, paper, metal plate, etc.
  • the layer structure of the laminate includes at least the second layer and the first layer in this order on a substrate, for example, (1) the substrate, the photosensitive layer, the cushion layer, And (2) a layer configuration having the substrate, the second photosensitive layer, the first photosensitive layer, and the support in this order, and (3) the substrate, the photosensitive layer.
  • a layer structure having and in this order is preferred.
  • the method of forming the laminate can be appropriately selected according to the purpose without any particular limitation, but at least one of heating and pressurizing the pattern forming material on the substrate is performed! While preferred, laminating.
  • the heating temperature can be appropriately selected without particular limitation as long as the temperature exceeds the glass transition temperature of the second layer, and is preferably 40 to 150 ° C., for example.
  • the pressure of the pressurization is a force that can be appropriately selected according to the purpose for which there is no particular limitation.
  • F column; t is preferably 0.1 to 1. OMPa force, 0.2 to 0.8 MPa force ⁇ More preferred! / ⁇ .
  • the apparatus for performing at least one of heating and pressurization can be appropriately selected according to the purpose of restriction, and examples thereof include a laminator and a vacuum laminator.
  • the apparatus for performing at least one of the heating and pressurization can be appropriately selected according to the purpose of restriction, such as a laminator (for example, VP-— manufactured by Taisei Laminator Co., Ltd.) Are preferable.
  • a laminator for example, VP-— manufactured by Taisei Laminator Co., Ltd.
  • the exposure of the laminate can be appropriately selected according to the purpose without any particular limitation.
  • the photosensitive layer may be exposed through the support, the cushion layer, and the barrier layer. After the support, cushion layer and barrier layer are peeled off, the photosensitive layer may be exposed.
  • the exposure can be appropriately selected according to the purpose for which there is no particular limitation, and powers such as digital exposure, analog exposure, etc. Among these, digital exposure is preferable.
  • the digital exposure can be appropriately selected according to the purpose without particular limitation. For example, it is preferable to generate a control signal based on the pattern formation information to be formed, and to use light modulated in accordance with the control signal.
  • the digital exposure means can be appropriately selected according to the purpose without any particular limitation.
  • Examples thereof include a light modulation unit that modulates the irradiated light.
  • the light modulating means can be appropriately selected according to the purpose without any limitation as long as light can be modulated.
  • the light modulating means preferably has n pixel portions.
  • the light modulation means having the n picture elements can be appropriately selected according to the purpose without any particular limitation, and for example, a spatial light modulation element is preferable.
  • Examples of the spatial light modulator include a digital micromirror device (DMD), a MEMS (Micro Electro Mechanical Systems) type spatial light modulator (SLM; Special Light Modulator), and transmission by an electro-optic effect.
  • Examples include optical elements that modulate light (PLZT elements) and liquid crystal light shirts (FLC). Among these, DMD is preferred.
  • the light modulation means includes pattern signal generation means for generating a control signal based on pattern information to be formed.
  • the light modulating means modulates light according to the control signal generated by the pattern signal generating means.
  • control signal can be appropriately selected according to the purpose for which there is no particular limitation.
  • a digital signal is preferably used.
  • Examples of the light modulation means include those described in paragraphs 0016 to 0047 of JP-A-2005-258431.
  • the light irradiation means can be appropriately selected according to the purpose without any particular limitation.
  • a known light source such as a semiconductor laser or means capable of combining and irradiating two or more lights can be mentioned. Among these, means capable of combining and irradiating two or more lights are preferable.
  • the light emitted from the light irradiation means is, for example, an electromagnetic wave that passes through the support and activates the photopolymerization initiator and sensitizer used when the light is irradiated through the support. In particular, ultraviolet to visible light, electron beams, X-rays, laser light, etc.
  • laser light is preferred.
  • Laser that combines two or more lights (hereinafter sometimes referred to as “combined laser”) ) Is more preferable. Even when the support is peeled off and the light is irradiated with light, the same light can be used.
  • the ultraviolet power is preferably 300 to 1500 nm, more preferably 320 to 800 mn, and 330 ⁇ ! ⁇ 650mn force ⁇ especially preferred!
  • the wavelength of the laser beam is, for example, preferably 200 to 1500 nm force S, more preferably 300 to 800 nm force S, and 330 mm! ⁇ 500mn force more preferred, 400 ⁇ ! ⁇ 450mn power ⁇ especially preferred! /,
  • a plurality of lasers, a multimode optical fiber, and a laser beam irradiated with each of the plurality of laser forces are condensed and coupled to the multimode optical fiber.
  • Means having a collective optical system to be used is preferable.
  • Examples of means (fiber array light source) that can irradiate the combined laser include means described in paragraphs 0110 to 0146 of JP-A No. 2005-258431.
  • the exposure is preferably performed using the modulated light through a microlens array, and may be performed through an aperture array, an imaging optical system, or the like.
  • the microlens array is a force that can be appropriately selected according to the purpose without any particular limitation.
  • a microlens having an aspherical surface capable of correcting aberration due to distortion of the exit surface in the pixel portion Preferred are those arranged.
  • the aspherical surface can be appropriately selected according to the purpose for which there is no particular limitation.
  • a toric surface is preferable.
  • Examples of the means such as the microlens array, the aperture array, and the imaging optical system include the means described in Paragraph 0050 Force et al. .
  • the light of the microlens 55a is used.
  • the end surface on the emission side is an aspheric surface (toric surface)
  • a microlens array is configured by using microlenses in which one of the two light passing end surfaces is a spherical surface and the other is a cylindrical surface. Similar effects can be obtained.
  • the microlens force of the microlens array is an aspherical shape that corrects aberration due to distortion of the reflecting surface of the micromirror, but such an aspherical shape is adopted.
  • the same effect can be obtained by providing each microphone lens constituting the microlens array with a refractive index distribution that corrects aberration due to distortion of the reflection surface of the micromirror.
  • FIG. 1 and FIG. 2 respectively show the front shape and the side shape of the micro lens 155a.
  • the external shape of the micro lens 155a is a parallel plate shape.
  • the x and y directions in the figure are as described above.
  • FIG. 1 and 2 schematically show the condensing state of the laser beam B in the cross section parallel to the X direction and the y direction by the microlens 155a.
  • the microlens 155a has a refractive index distribution that gradually increases toward the outside of the optical axis O force.
  • the broken line shown in the microlens 155a in FIG. The position changed with the pitch is shown.
  • the ratio of the refractive index change of the microlens 155a is larger in the latter cross section, and the focal length Is getting shorter. Even when a microlens array composed of such a refractive index distribution type lens is used, the same effect as in the case of using the microlens array 55 can be obtained.
  • microlens having the aspherical surface shape like the microlens 55a shown in Figs. 3 to 6 the above refractive index distribution is given together, and both the surface shape and the refractive index distribution are provided. However, it is possible to correct the aberration caused by distortion of the reflecting surface of the micromirror 62.
  • the aberration due to the distortion of the reflection surface of the micromirror 62 constituting the DMD 50 is corrected.
  • the pattern forming method of the present invention using a spatial light modulation element other than the DMD.
  • the present invention is applied to correct the aberration caused by the distortion, and the beam shape may be distorted. Can be prevented.
  • the cross-sectional area force of the light beam reflected by the DMD 50 in the ON direction is several times by the lens systems 454 and 458 (for example, 2x).
  • the expanded laser light is condensed by each microlens of the microlens array 472 so as to correspond to each pixel part of the DMD 50 and passes through a corresponding aperture of the aperture array 476.
  • the laser beam that has passed through the aperture is imaged on the lens system 480, 482 [exposed surface 56].
  • the laser beam reflected by the DMD 50 is magnified several times by the magnifying lenses 454 and 458 and projected onto the exposed surface 56, so that the entire image area is widened. .
  • the microlens array 472 and the aperture array 476 are not arranged, one pixel size (spot size) of each beam spot BS projected onto the exposure surface 56 is exposed as shown in FIG.
  • the size increases according to the size of area 468, and the MTF (Modulation Transfer Function) characteristic representing the sharpness of exposure area 468 is degraded.
  • the laser light reflected by the DMD50 corresponds to each pixel part of the DMD50 by each microlens of the microlens array 472. Focused. As a result, as shown in FIG. 9, even when the exposure area is enlarged, the spot size of each beam spot BS can be reduced to a desired size (for example, lO ⁇ mX lO ⁇ m). It is possible to perform high-precision exposure by preventing a decrease in the exposure time.
  • the exposure area 468 is inclined because the DMD 50 is inclined to eliminate the gap between the pixels.
  • the aperture array can shape the beam so that the spot size on the exposed surface 56 is constant. At the same time, by passing through an aperture array provided corresponding to each pixel, crosstalk between adjacent pixels can be prevented.
  • the angle of the light beam incident on each microlens of the microlens array 472 from the lens 458 becomes small. It is possible to prevent a part of the light beam from entering. That is, high quenching Ratio can be realized.
  • the pattern forming method of the present invention 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 quantity distribution correcting optical system changes the light flux width at each exit position so that the ratio of the light flux width in the peripheral portion to the light flux width in the central portion close to the optical axis is smaller on the exit side than on the entrance side.
  • Examples of the light quantity distribution correcting optical system include means described in paragraphs 0090 to 0105 of JP-A-2005-258431.
  • the developing step exposes the photosensitive layer in the pattern forming material in the exposing step, cures the exposed region of the photosensitive layer, and then removes the uncured region to form an image, thereby forming a no-turn. It is a process.
  • the development step can be preferably carried out, for example, by a developing means.
  • the developing means is not particularly limited as long as it can be developed using a developer, and can be appropriately selected according to the purpose.
  • the means for spraying the developer, and applying the developer And means for immersing in the developer may be used alone or in combination of two or more.
  • the developing unit may include a developing solution replacing unit that replaces the developing solution, a developing solution supply unit that supplies the developing solution, and the like.
  • the developer can be appropriately selected depending on the purpose without any particular limitation, and examples thereof include alkaline solutions, aqueous developers, organic solvents, and the like. Alkaline aqueous solutions are preferred.
  • the basic component of the weak alkaline liquid 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 weakly alkaline aqueous solution is more preferably about 9 to 11 force, for example, preferably about 8 to 12.
  • Examples of the weak alkaline aqueous solution include 0.1 to 5% by mass of sodium carbonate aqueous solution or potassium carbonate aqueous solution.
  • the temperature of the developer can be appropriately selected according to the developability of the photosensitive layer, and for example, about 25 ° C. to 40 ° C. is preferable.
  • the developer is a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.)
  • an organic solvent for example, alcohols, ketones, esters, ethers, amides, latatones, etc.
  • the developer may be an aqueous developer obtained by mixing water or an alkaline aqueous solution and an organic solvent, or may be an organic solvent alone.
  • the etching step can be performed by a method appropriately selected from among known etching methods.
  • the etching solution used for the etching treatment can be appropriately selected according to the purpose without any particular limitation.
  • a cupric chloride solution examples thereof include a ferric solution, an alkaline etching solution, and a hydrogen peroxide-based etching solution.
  • a point strength of etching factor—a salty ferric solution is preferable.
  • a permanent pattern can be formed on the surface of the substrate by removing the pattern after performing the etching process in the etching step.
  • the permanent pattern is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include a wiring pattern.
  • the plating step can be performed by an appropriately selected method selected from known plating processes.
  • the plating treatment include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-flow solder plating, nickel plating such as watt bath (nickel sulfate-salt nickel nickel) plating, and nickel sulfamate.
  • gold plating such as hard gold plating and soft gold plating.
  • a permanent pattern can be formed on the surface of the substrate by removing the pattern after performing a plating process in the plating process, and further removing unnecessary portions by an etching process or the like as necessary.
  • the pattern forming method of the present invention can be suitably used for the production of a printed wiring board, particularly for the production of a printed wiring board having a hole portion such as a through hole or a via hole.
  • a hole portion such as a through hole or a via hole.
  • the second pattern forming material is placed on the printed wiring board forming substrate having the hole portion as the base.
  • Layers photosensitive layer or second photosensitive layer
  • the photosensitive layer is cured by irradiation, (3) the support in the pattern forming material and the cushion layer are removed from the laminate when the cushion layer is provided, and (4) the photosensitive layer in the laminate is developed.
  • the pattern can be formed by removing the uncured portion in the laminate.
  • the removal of the cushion layer is not particularly limited, and may be performed anywhere after (2).
  • the cushion layer is insoluble in the alkaline liquid, it is preferably removed before (4).
  • the removal of the support in (3) may be performed between (1) and (2) instead of between (2) and (4).
  • the barrier layer May be removed together with the support in (3) or may be removed during development in (4).
  • a method of etching or plating the printed wiring board forming substrate using the formed pattern for example, a known subtractive method or additive method (for example, Semi-additive method and full additive method)).
  • the subtractive method is preferable in order to form a printed wiring board with industrially advantageous tenting.
  • the cured resin remaining on the printed wiring board forming substrate is peeled off.
  • the copper thin film portion is further etched after the peeling to produce a desired printed wiring board. can do.
  • a multilayer printed wiring board can also be manufactured in the same manner as the printed wiring board manufacturing method.
  • a printed wiring board forming substrate having through holes and having a surface covered with a metal plating layer is prepared.
  • the printed wiring board forming substrate for example, a copper clad laminated substrate and a substrate in which a copper plating layer is formed on an insulating base material such as glass-epoxy, or an interlayer insulating film is laminated on these substrates, and a copper plating layer is formed.
  • a formed substrate (laminated substrate) can be used.
  • the protective film is peeled off, and the second layer (photosensitive layer or second photosensitive layer) in the pattern forming material becomes the print Pressure is applied using a pressure roller so as to be in contact with the surface of the wiring board forming substrate (lamination process).
  • the laminated body which has the said board
  • the lamination temperature of the pattern forming material is preferably a force that can be appropriately selected as long as it exceeds the glass transition temperature of the second layer. For example, 40 to 150 ° C. is preferable.
  • the roll pressure of the pressure-bonding roll is not particularly limited and can be appropriately selected. For example, 0.1 to LMPa is preferable.
  • the speed of the crimping can be selected as appropriate without any particular limitation. z minutes are preferred.
  • the printed wiring board forming substrate may be preheated or laminated under reduced pressure.
  • the photosensitive layer is cured by irradiating light from the surface of the laminate opposite to the substrate.
  • the support may be peeled off and the force may be exposed.
  • the barrier layer may be peeled off and the force may be exposed.
  • the uncured region of the photosensitive layer on the printed wiring board forming substrate is dissolved and removed with an appropriate developer, and the cured layer for forming the wiring pattern and the curing for protecting the metal layer of the through hole are performed.
  • a layer pattern is formed to expose the metal layer on the surface of the printed wiring board forming substrate (development process).
  • a post-heating treatment or a post-exposure treatment may be performed to further accelerate the curing reaction of the cured portion.
  • the development may be a wet development method as described above or a dry development method.
  • etching step the metal layer exposed on the surface of the printed wiring board forming substrate is dissolved and removed with an etching solution (etching step). Since the opening of the through hole is covered with a cured resin composition (tent film), the metal coating of the through hole prevents the etching solution from entering the through hole and corroding the metal plating in the through hole. Will remain in the prescribed shape. Thereby, a wiring pattern is formed on the printed wiring board forming substrate.
  • the etching solution is not particularly limited and can be appropriately selected depending on the purpose.
  • a cupric chloride solution examples thereof include a ferric solution, an alkaline etching solution, a hydrogen peroxide-based etching solution, and the like.
  • a salty ferric solution is preferable from the viewpoint of an etching factor.
  • the printed wiring board is formed by using the hardened layer as a release piece with a strong alkaline aqueous solution or the like. Remove from the forming substrate (cured product removal step).
  • the base component in the strong alkaline aqueous solution is not particularly limited, and examples thereof include sodium hydroxide and potassium hydroxide.
  • the pH of the strong alkaline aqueous solution is, for example, preferably about 13-14, more preferably about 12-14.
  • the strong alkaline aqueous solution is not particularly limited, and examples thereof include 1 to 10% by mass of sodium hydroxide aqueous solution or potassium hydroxide aqueous solution.
  • the printed wiring board may be a multilayer printed wiring board.
  • the pattern forming material may be used in a Meki process that is performed only by the etching process.
  • the plating method include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-throw solder plating, watt bath (nickel sulfate-salt nickel) plating, nickel plating such as nickel sulfamate, Examples include hard gold plating and gold plating such as soft gold plating.
  • the pattern forming method of the present invention uses the pattern forming material of the present invention, formation of various patterns, formation of permanent patterns such as wiring patterns, color filters, pillar materials, rib materials, spacers, etc. It can be suitably used for the production of liquid crystal structural members such as partition walls, holograms, micromachines, proofs, etc., and can be particularly suitably used for the formation of high-definition wiring patterns.
  • the pattern forming apparatus of the present invention includes the pattern forming material of the present invention, it forms various patterns, forms permanent patterns such as wiring patterns, color filters, pillar materials, rib materials, spacers, partition walls It can be suitably used for the production of liquid crystal structure members such as holograms, micromachines, and proofs, and can be particularly suitably used for the formation of high-definition wiring patterns.
  • 16 ⁇ m thick polyethylene terephthalate film (16QS52, East (Co., Ltd.) is coated with a coating solution for the first layer (first photosensitive layer) having the following composition and dried to form the first layer (first photosensitive layer) 25 ⁇ m thick did.
  • first photosensitive layer On the formed first layer (first photosensitive layer), a coating solution for the second layer (second photosensitive layer) having the following composition was applied and dried to give a thickness of 5 m. A second layer (second photosensitive layer) was formed.
  • a 12 m thick polypropylene film (E501, manufactured by Oji Paper Co., Ltd.) was laminated as a protective film on the formed second layer (second photosensitive layer) to produce a pattern forming material. It was.
  • the glass transition temperature (Tg) and the melt viscosity at 60 ° C. of the first layer and the second layer were measured by the following methods. The results are shown in Table 3.
  • Samples for measurement in which the first layer and the second layer were formed with a thickness of 1 cm were prepared.
  • the viscosity of the sample for measurement was measured by increasing the temperature from room temperature at a rate of 20 ° CZ using a solid meter MR300 (manufactured by Rheology).
  • a copper-clad laminate (no through hole, copper thickness 12 / zm) whose surface was polished, washed with water and dried was prepared, and on the copper-clad laminate, a second of the pattern forming material was prepared.
  • Laminator MODEL8B-720-PH, manufactured by Taisei Laminator Co., Ltd.
  • a laminate was prepared in which the copper-clad laminate, the second layer (second photosensitive layer), the first layer (first photosensitive layer), and the support were laminated in this order.
  • the crimping conditions were a crimping roll temperature of 105 ° C, a crimping roll pressure of 3 kgZcm 2 , and a crimping speed of lmZ.
  • the thickness of the film composed of the first layer and the second layer laminated on the substrate was measured using a stylus type film thickness meter (Surfcom 1400D, manufactured by Tokyo Seimitsu Co., Ltd.), and a surface of 510 X 610 cm In product, 50 arbitrary points on the substrate surface were measured. As a result, the film thickness variation is ⁇ 0.1 ⁇ m.
  • the peeled off the laminate strength the support it was sprayed at a pressure of 0. 15 MPa 1 mass 0/0 aqueous sodium carbonate 30 ° C to the first photosensitive layer over the force over the entire surface of the copper-clad laminates, sodium carbonate
  • the time required from the start of spraying of the aqueous solution until the photosensitive layer on the copper clad laminate was dissolved and removed was measured, and this was taken as the shortest development time. As a result, the shortest image time was 25 seconds.
  • the following pattern forming apparatus having a 405 nm laser light source as the light irradiating means is used, from 0. lmj / cm 2 to 2 1/2 Exposure was performed by irradiating with different light energy amounts up to 100 mj / cm 2 at double intervals to cure a part of the photosensitive layer. After standing at room temperature for 10 minutes, the support was peeled off from the laminate, and an aqueous sodium carbonate solution (30 ° C, 1% by mass) was applied to the entire surface from the first photosensitive layer on the copper clad laminate.
  • Spraying was performed at a spray pressure of 0.15 MPa for twice the minimum development time determined in (1) above, and the uncured area was dissolved and removed, and the thickness of the remaining cured area was measured. Subsequently, the relationship between the light irradiation amount and the thickness of the cured layer was plotted to obtain a sensitivity curve. As a result, when the thickness of the hardened layer becomes the thickness of the second layer (5 ⁇ m), the amount of light energy S 1 is 4 mjZcm 2 , and the thickness of the hardened layer is the same as that of the first layer and the second layer.
  • the amount of light energy S2 when the thickness with the second layer (30 ⁇ m) is 40 mjZcm 2
  • the amount of light energy when the thickness of the hardened layer exceeds the thickness of the second layer (5 ⁇ m) S3 was 14 mjZcm 2 .
  • S1 is the light energy necessary to cure the second photosensitive layer
  • S2 is the light energy necessary to cure the first photosensitive layer
  • S3 is necessary before the first photosensitive layer is cured.
  • the combined laser light source shown in FIGS. 10 to 16 as the light irradiating means, and the micromirror array in which 1024 micromirrors are arranged in the main scanning direction shown in FIGS. 17 and 18 as the light modulating means are in the sub-scanning direction.
  • the pattern forming apparatus including the microlens array 472 and the optical systems 480 and 482 for forming an image of the light passing through the microlens array on the photosensitive layer was used.
  • a vacuum frame (not shown) in which the laminate is stored is arranged on a stage 152 of the pattern forming apparatus shown in FIG. 19, and the photosensitive layer 150 of the laminate is exposed.
  • 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.
  • the surface of a copper clad laminate having a through hole with a diameter of 3 mm having a copper plating layer on the inner wall was polished, washed with water, and dried to prepare a substrate.
  • a laminator (MODEL8B-720-PH) is formed on the copper clad laminate while peeling off the protective film so that the second layer (second photosensitive layer) of the pattern forming material is in contact with the copper clad laminate.
  • the copper clad laminate, the second layer (second photosensitive layer), the first layer (first photosensitive layer), and the support are laminated using a Taisei Laminator Co., Ltd.
  • a laminate was prepared in which and were laminated in this order.
  • the pressing conditions were a pressure roll temperature of 105 ° C, a pressure roll pressure of 3 kgZcm 2 , and a pressure bonding speed of lmZ.
  • the substrate was allowed to stand at room temperature for 10 minutes, and then the support was peeled off from the laminate, and the upper force of the first layer (first photosensitive layer) on the copper-clad laminate was also applied to the entire surface with an aqueous sodium carbonate solution ( (30 ° C, 1% by mass) was sprayed at a spray pressure of 0.15 MPa for twice the minimum development time obtained in (1) above, and uncured areas were dissolved and removed to form a cured layer pattern. .
  • an aqueous sodium carbonate solution (30 ° C, 1% by mass
  • the thickness of the cured layer pattern was measured. In addition, the pattern was observed with a microscope to observe the presence or absence of pattern defects. As a result, the thickness of the hardened layer was 5 ⁇ m ⁇ 0.05 ⁇ m, and no pattern defects were observed.
  • an iron chloride etchant (ferric chloride-containing etching solution) is sprayed on the surface of the laminate on which the hardened layer pattern is formed, and the hardened layer pattern is not formed and the exposed copper layer is not exposed. Was dissolved and removed. Thereafter, a 2% by mass aqueous solution of sodium hydroxide and sodium hydroxide was sprayed to remove the hardened layer pattern to obtain a printed wiring board.
  • Example 1 support was conducted in the same manner as in Example 1 except that the coating solution for the cushion layer was not added without adding 4,4 bis (jetylamino) benzophenone and benzophenone in the coating solution for the first layer.
  • a pattern forming material having a body, a first layer (cushion layer), a second layer (photosensitive layer), and a protective film in this order was produced.
  • a laminate having a substrate, a second layer (photosensitive layer), a first layer (cushion layer), and a support in this order, and a printed wiring board were produced.
  • Table 3 shows the glass transition temperatures (Tg) of the first layer and the second layer in the pattern forming material and the melt viscosity at 60 ° C.
  • Table 4 shows the film thickness variation, sensitivity, resolution, and etching line width variation in the laminate.
  • Example 1 a coating solution for the NORA layer having the following composition was applied on the first layer and dried to form a 1.6 m thick NORA layer.
  • a pattern forming material having a support, a first layer (first photosensitive layer), a barrier layer, a second layer (second photosensitive layer), and a protective film in this order was produced.
  • Table 3 shows the glass transition temperatures (Tg) of the first layer and the second layer in the pattern forming material and the melt viscosity at 60 ° C.
  • Table 4 shows the film thickness variation, sensitivity, resolution, and etching line width variation in the laminate.
  • the amount of light energy S2 required to cure the first photosensitive layer was the amount of light energy when the thickness of the cured layer reached 31.6 ⁇ m.
  • Example 1 the same procedure as in Example 1 was applied, except that a barrier layer coating solution similar to that in Example 3 was applied and dried to form a 1.6 ⁇ -thick noria layer.
  • a laminated body having a substrate, a second layer (photosensitive layer), a barrier layer, a first layer (cushion layer), and a support in this order, and a printed wiring board were produced. did.
  • Table 3 shows the glass transition temperatures (Tg) of the first layer and the second layer in the pattern forming material and the melt viscosity at 60 ° C.
  • Table 4 shows the film thickness variation, sensitivity, resolution, and etching line width variation in the laminate.
  • Example 1 the blending amount of dodecapropylene glycol ditalylate in the coating solution for the first layer (first photosensitive layer) was 3.5 parts by mass, A support, a first layer (first photosensitive layer), a second layer (second photosensitive layer), the same as in Example 1 except that the blending amount of dimetatalylate was 0.5 parts by mass, And the pattern formation material which has a protective film in this order was manufactured. Further, in the same manner as in Example 1, a laminated body having a substrate, a second layer (second photosensitive layer), a first layer (first photosensitive layer), and a support in this order, and a printed wiring board are manufactured. did.
  • Table 3 shows the glass transition temperatures (Tg) of the first layer and the second layer in the pattern forming material and the melt viscosity at 60 ° C.
  • Table 4 shows the film thickness variation, sensitivity, resolution, and etching line width variation in the laminate.
  • Example 2 the blending amount of dodecapolypropylene glycol diatalylate in the coating solution for the first layer (cushion layer) is 3.5 parts by mass, and the blending amount of tetraethylene glycol dimetatalylate is 0.5 parts by mass.
  • a pattern forming material having a support, a first layer (cushion layer), a second layer (photosensitive layer), and a protective film in this order was produced in the same manner as in Example 2 except that.
  • a laminate having a substrate, a second layer (photosensitive layer), a first layer (cushion layer), and a support in this order, and a printed wiring board were produced.
  • Table 3 shows the glass transition temperatures (Tg) of the first layer and the second layer in the pattern forming material and the melt viscosity at 60 ° C.
  • Table 4 shows the film thickness variation, sensitivity, resolution, and etching line width variation in the laminate.
  • Example 3 the blending amount of dodecapropylene glycol ditalarirate in the coating solution for the first layer (first photosensitive layer) is 3.5 parts by mass, and the blending amount of tetraethylenedaricol dimetatalylate is 0.
  • a support, a first layer (first photosensitive layer), a barrier layer, a second layer (second photosensitive layer), and a protective film were prepared in the same manner as in Example 3 except that the content was 5 parts by mass.
  • the pattern formation material which has in order was manufactured. Further, in the same manner as in Example 3, a laminate having a substrate, a second layer (second photosensitive layer), a barrier layer, a first layer (first photosensitive layer), and a support in this order, and a print A wiring board was manufactured.
  • Table 3 shows the temperature (Tg) and melt viscosity at 60 ° C.
  • Table 4 shows the film thickness variation, sensitivity, resolution, and etching line width variation in the laminate.
  • Example 4 the blending amount of dodecapolypropylene glycol diatalylate in the coating solution for the first layer (cushion layer) is 3.5 parts by mass, and the blending amount of tetraethylene glycol dimetatalylate is 0.5 parts by mass.
  • a pattern forming material having a support, a first layer (cushion layer), a barrier layer, a second layer (photosensitive layer), and a protective film in this order was produced in the same manner as in Example 4. did. Further, in the same manner as in Example 1, a laminate having a substrate, a second layer (photosensitive layer), a barrier layer, a first layer (cushion layer), and a support in this order, and a printed wiring board were produced. .
  • Table 1 shows the glass transition temperatures (Tg) of the first layer and the second layer in the pattern forming material and the melt viscosity at 60 ° C.
  • Table 2 shows the variation in film thickness, sensitivity, resolution, and etching line width in the laminate.
  • the pattern forming material of the present invention is capable of forming a pattern capable of forming a high-definition pattern excellent in uneven surface followability on the substrate surface and excellent in tent properties and etching uniformity.
  • Suitable for pattern formation formation of permanent patterns such as wiring patterns, manufacturing of liquid crystal structural members such as color filters, pillars, ribs, spacers, partition walls, holograms, micromachines, proofs, etc. In particular, it can be suitably used for forming a high-definition wiring pattern.
  • the pattern forming apparatus of the present invention includes the pattern forming material of the present invention, it forms various patterns, forms permanent patterns such as wiring patterns, color filters, pillar materials, rib materials, spacers, partition walls It can be suitably used for the production of liquid crystal structural members such as holograms, micromachines, and proofs, and can be particularly suitably used for the formation of high-definition wiring patterns.
  • the pattern forming method of the present invention uses the pattern forming material of the present invention, the formation of various patterns, the formation of permanent patterns such as wiring patterns, color filters, pillar materials, rib materials, and spacers. It can be suitably used for the production of liquid crystal structural members such as sir and partition walls, the production of holograms, micromachines, and proofs, and is particularly suitable for the formation of high-definition wiring patterns.

Abstract

A pattern forming material by which a highly fine pattern having an excellent characteristic of following unevenness of a base material surface and excellent uniformity in a tent film and etching can be formed, a pattern forming apparatus provided with the pattern forming material, and a pattern forming method using the pattern forming material are provided. The pattern forming material is successively provided with a first layer and a second layer on a supporting body and satisfies B≥A, where A is a glass transition temperature (Tg) of the first layer, and B is a glass transition temperature (Tg) of the second layer. The pattern forming apparatus provided with such pattern forming material is also provided. Furthermore, the pattern forming method which at least includes a step of exposing a photosensitive layer in the pattern forming material is provided.

Description

明 細 書  Specification
パターン形成材料、並びにパターン形成装置及びパターン形成方法 技術分野  Pattern forming material, pattern forming apparatus and pattern forming method
[0001] 本発明は、ドライ ·フィルム ·レジスト（DFR)等に好適なパターン形成材料、並びに 該パターン形成材料を備えたパターン形成装置及び前記パターン形成材料を用い たパターン形成方法に関する。  The present invention relates to a pattern forming material suitable for dry film resist (DFR), etc., a pattern forming apparatus provided with the pattern forming material, and a pattern forming method using the pattern forming material.
背景技術  Background art
[0002] 従来より、配線パターンなどの永久パターンを形成するに際して、支持体上に感光 性榭脂組成物を塗布、乾燥することにより感光層を形成させたパターン形成材料が 用いられている。前記永久パターンの製造方法としては、例えば、前記永久パターン が形成される銅張積層板等の基体上に、前記パターン形成材料を積層させて積層 体を形成し、該積層体における前記感光層に対して露光を行い、該露光後、前記感 光層を現像してパターンを形成させ、その後エッチング処理等を行うことにより前記 永久パターンが形成される。  Conventionally, when a permanent pattern such as a wiring pattern is formed, a pattern forming material in which a photosensitive layer is formed by applying and drying a photosensitive resin composition on a support has been used. As the method for producing the permanent pattern, for example, a laminate is formed by laminating the pattern forming material on a substrate such as a copper clad laminate on which the permanent pattern is formed, and the photosensitive layer in the laminate is formed on the photosensitive layer. The permanent pattern is formed by exposing to light, developing the light-sensitive layer to form a pattern after the exposure, and then performing an etching process or the like.
[0003] 一般に、 PWB (プリントワイヤードボード)等の基体の表面には、化学研磨による微 細な凹凸や、ガラス繊維の厚みムラに起因する凹凸が存在するため、高精細な永久 ノターンを形成するためには、積層されるパターン形成材料に凹凸追従性が要求さ れる。  [0003] Generally, the surface of a substrate such as PWB (printed wired board) has fine irregularities due to chemical polishing and irregularities caused by uneven thickness of the glass fiber, so that a high-definition permanent pattern is formed. In order to achieve this, the pattern forming material to be laminated must have an uneven follow-up property.
この問題に対応するために、支持体と感光層との間に、熱可塑性榭脂層を設け、 加熱及び加圧下で転写する際に前記基体表面の凹凸を吸収させる方法が提案され ている (特許文献 1参照)。  In order to cope with this problem, a method has been proposed in which a thermoplastic resin layer is provided between the support and the photosensitive layer, and the irregularities on the surface of the substrate are absorbed when transferred under heat and pressure ( (See Patent Document 1).
[0004] 一方、プリント配線板等の小型化や高性能化に対応するために、感光層を多層化 する技術が開発されている（特許文献 2参照)。特に、スルーホールやビアホールを 有するプリント配線板においては、ホール部の被覆性を高めるために、物性の異なる 複数の感光層を積層したパターン形成材料が知られて ヽる (特許文献 3及び 4参照） 。前記特許文献 3では、支持体の上に、加熱による流動性が小さい第一感光層を設 け、その上に加熱による流動性が大きい第二感光層を設けてなるパターン形成材料 を用い、基体への転写時の加熱により、流動性の大きな第二感光層がスルーホール 内に充填される技術が提案されて ヽる。 [0004] On the other hand, in order to cope with downsizing and high performance of printed wiring boards and the like, a technique for multilayering a photosensitive layer has been developed (see Patent Document 2). In particular, for printed wiring boards having through holes and via holes, pattern forming materials are known in which a plurality of photosensitive layers having different physical properties are laminated in order to improve the coverage of the holes (see Patent Documents 3 and 4). ) In Patent Document 3, a pattern forming material comprising a support on which a first photosensitive layer having low fluidity by heating is provided and a second photosensitive layer having high fluidity by heating is provided thereon. A technique for filling a through-hole with a second photosensitive layer having high fluidity by heating at the time of transfer to a substrate is proposed.
[0005] し力しながら、上述したこれらの多層構造のパターン形成材料を基体上に積層する 際、前記パターン形成材料は前記基体表面の凹凸追従性を有するものの、凹凸を 吸収することによって膜厚の不均一が生じるという問題がある。具体的には、前記基 体表面と接する感光層は、外層の感光層又は熱可塑性榭脂層よりも軟ィ匕点が低いと 、ラミネート時の加熱'加圧によって軟ィ匕し、基体の凹凸を吸収するため、前記基体 表面の凹部上は厚ぐ前記基体表面の凸部上は薄くなる。その結果、前記感光層の 露光'現像後、エッチング工程においてエッチングレートが変化し、前記基体の銅箔 層に対するオーバーエッチを生じて均一な線幅が得られな ヽと 、う問題や、均一な テント膜が得られな 、と 、う問題がある。  [0005] However, when the above-mentioned pattern forming material having the multilayer structure is laminated on the substrate, the pattern forming material has the unevenness following property of the surface of the substrate, but the film thickness is absorbed by absorbing the unevenness. There is a problem that non-uniformity occurs. Specifically, when the photosensitive layer in contact with the substrate surface has a softening point lower than that of the outer photosensitive layer or the thermoplastic resin layer, the photosensitive layer is softened by heating and pressurizing at the time of lamination. In order to absorb the unevenness, the concave portion on the surface of the base is thick, and the convex portion on the surface of the base is thin. As a result, after exposure and development of the photosensitive layer, the etching rate is changed in the etching process, resulting in overetching of the copper foil layer of the substrate, and a uniform line width cannot be obtained. There is a problem that a tent film cannot be obtained.
[0006] よって、基体表面の凹凸追従性に優れ、かつ、テント性及びエッチングの均一性に 優れた高精細なパターンを形成可能なパターン形成材料、並びに該パターン形成 材料を備えたパターン形成装置及び前記パターン形成材料を用いたパターン形成 方法は未だ提供されておらず、更なる改良開発が望まれているのが現状である。  [0006] Therefore, a pattern forming material that is capable of forming a high-definition pattern that is excellent in unevenness followability on the surface of the substrate and that has excellent tent properties and etching uniformity, and a pattern forming apparatus including the pattern forming material, and A pattern forming method using the pattern forming material has not yet been provided, and further improvement and development are desired.
[0007] 特許文献 1 :特開平 5— 72724号公報  [0007] Patent Document 1: Japanese Patent Laid-Open No. 5-72724
特許文献 2：特開平 3 - 17650号公報  Patent Document 2: Japanese Patent Laid-Open No. 3-17650
特許文献 3：特開平 8 - 54732号公報  Patent Document 3: JP-A-8-54732
特許文献 4:特開平 10— 111573号公報  Patent Document 4: Japanese Patent Laid-Open No. 10-111573
発明の開示  Disclosure of the invention
[0008] 本発明は、力かる現状に鑑みてなされたものであり、従来における前記諸問題を解 決し、以下の目的を達成することを課題とする。即ち、本発明は、基体表面の凹凸追 従性に優れ、かつ、テント性及びエッチングの均一性に優れた高精細なパターンを 形成可能なパターン形成材料、並びに該パターン形成材料を備えたパターン形成 装置及び前記パターン形成材料を用いたパターン形成方法を提供することを目的と する。  [0008] The present invention has been made in view of the current situation, and it is an object of the present invention to solve the above-described problems and achieve the following objects. That is, the present invention relates to a pattern forming material that is capable of forming a high-definition pattern that is excellent in unevenness followability on the surface of a substrate and that is excellent in tent properties and etching uniformity, and a pattern forming apparatus including the pattern forming material Another object of the present invention is to provide a pattern forming method using the pattern forming material.
[0009] 前記課題を解決するための手段としては、以下の通りである。即ち、  Means for solving the above-described problems are as follows. That is,
< 1 > 支持体上に、第一の層と第二の層とをこの順に有し、該第一の層のガラス 転移温度 (Tg)を A、該第二の層のガラス転移温度 (Tg)を Bとしたとき、 B≥Aである ことを特徴とするパターン形成材料である。該く 1>のパターン形成材料においては 、基体に接する前記第二の層のガラス転移温度が、前記第一の層のガラス転移温度 を超えないため、例えば、ラミネート時の温度を制御することにより、前記第二の層の 基体表面への追従性と膜厚の均一性とを両立させることができる。 <1> On a support, the first layer and the second layer are provided in this order, and the glass of the first layer A pattern forming material characterized in that B≥A, where A is the transition temperature (Tg) and B is the glass transition temperature (Tg) of the second layer. In the pattern forming material of <1>, since the glass transition temperature of the second layer in contact with the substrate does not exceed the glass transition temperature of the first layer, for example, by controlling the temperature during lamination. Thus, it is possible to achieve both the followability of the second layer to the substrate surface and the uniformity of the film thickness.
<2> 第一の層のガラス転移温度 Aが— 20〜30°Cであり、第二の層のガラス転 移温度 Bが 10〜40°Cである前記く 1 >に記載のパターン形成材料である。  <2> The pattern forming material according to <1>, wherein the glass transition temperature A of the first layer is -20 to 30 ° C, and the glass transition temperature B of the second layer is 10 to 40 ° C. It is.
<3> 第二の層の溶融粘度力 40〜： L00°Cの範囲にお！/、て、 500〜30, 000 (P a · S)である前記く 1 >から < 2 >の 、ずれかに記載のパターン形成材料である。  <3> Melt viscosity power of the second layer 40 ~: In the range of L00 ° C! The pattern forming material according to any one of <1> to <2>, which is 500 to 30,000 (Pa · S).
<4> 第一の層の厚みが 5〜30 μ m、第二の層の厚みが 2〜15 μ mである前記 < 1 >から < 3 >のいずれかに記載のパターン形成材料である。  <4> The pattern forming material according to any one of <1> to <3>, wherein the first layer has a thickness of 5 to 30 μm, and the second layer has a thickness of 2 to 15 μm.
<5> 第一の層がクッション層であり、第二の層が感光層である前記 <1>から < 4 >の 、ずれかに記載のパターン形成材料である。  <5> The pattern forming material according to any one of <1> to <4>, wherein the first layer is a cushion layer and the second layer is a photosensitive layer.
< 6 > クッション層力 熱可塑性榭脂を含む前記く 5 >に記載のパターン形成材 料である。  <6> Cushion layer strength The pattern forming material according to <5>, comprising a thermoplastic resin.
<7> 熱可塑性榭脂の軟化点が、 80°C以下である前記 <5>に記載のパターン 形成材料である。  <7> The pattern forming material according to <5>, wherein the thermoplastic resin has a softening point of 80 ° C or lower.
<8> 第一の層が第一感光層であり、第二の層が第二感光層である前記 <1> 力ら < 4 >の!、ずれかに記載のパターン形成材料。  <8> The pattern forming material according to <1> above, wherein the first layer is a first photosensitive layer and the second layer is a second photosensitive layer.
<9> 405nmの波長の光を照射した際において、第一感光層のパターン形成可 能な最小露光量が、第二感光層のパターン形成可能な最小露光量よりも大きい前記 <8>に記載のパターン形成材料である。  <9> When the light having a wavelength of 405 nm is irradiated, the minimum exposure amount capable of pattern formation of the first photosensitive layer is larger than the minimum exposure amount capable of pattern formation of the second photosensitive layer. Pattern forming material.
<10> 感光層が、バインダーと、重合性化合物と、光重合開始剤とを含む前記 < 5 >から < 9 >のいずれかに記載のパターン形成材料である。  <10> The pattern forming material according to any one of <5> to <9>, wherein the photosensitive layer contains a binder, a polymerizable compound, and a photopolymerization initiator.
<11> ノ インダ一力 酸性基を有する前記く 10 >に記載のパターン形成材料 である。  <11> Ninder strength The pattern forming material according to 10 above, which has an acidic group.
< 12> バインダーが、ビニル共重合体である前記く 10>からく 11>のいずれ かに記載のパターン形成材料である。 < 13 > バインダーの酸価力 100〜250 (mgKOH/g)である前記く 10>から く 12 >の!、ずれかに記載のパターン形成材料である。 <12> The pattern forming material according to any one of 10) to 11), wherein the binder is a vinyl copolymer. <13> The pattern forming material according to any one of 10> to 12>, wherein the binder has an acid value of 100 to 250 (mgKOH / g).
< 14> 重合性化合物が、ウレタン基及びァリール基の少なくともいずれかを有す るモノマーを含む前記 < 10>力ら< 13 >のいずれかに記載のパターン形成材料で ある。  <14> The pattern forming material according to any one of <10> and <13>, wherein the polymerizable compound contains a monomer having at least one of a urethane group and an aryl group.
< 15 > 光重合開始剤が、ハロゲン化炭化水素誘導体、へキサァリールビイミダゾ ール、ォキシム誘導体、有機過酸化物、チォ化合物、ケトンィ匕合物、芳香族ォ -ゥム 塩及びメタ口セン類力も選択される少なくとも 1種を含む前記く 10>力らく 14>のい ずれかに記載のパターン形成材料である。  <15> Photopolymerization initiators are halogenated hydrocarbon derivatives, hexaryl biimidazoles, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts and The pattern forming material according to any one of the above-mentioned 10> force 14>, which includes at least one kind of selected force.
< 16 > 感光層が、バインダーを 30〜90質量％含有し、重合性化合物を 5〜60 質量％含有し、光重合開始剤を 0. 1〜30質量％含有する前記く 10>からく 15 > の!、ずれかに記載のパターン形成材料である。  <16> The above-mentioned photosensitive layer containing 30 to 90% by mass of a binder, 5 to 60% by mass of a polymerizable compound, and 0.1 to 30% by mass of a photopolymerization initiator. > No! Is the pattern forming material described in any of the above.
< 17> 第一の層と第二の層との間に、物質の移動を制御可能なバリア層を有す る前記 < 1 >から < 16 >のいずれかに記載のパターン形成材料である。  <17> The pattern forming material according to any one of <1> to <16>, wherein a barrier layer capable of controlling the movement of a substance is provided between the first layer and the second layer.
< 18 > ノリア層が、ビュル重合体及びビュル共重合体の少なくとも 、ずれかを含 む前記く 17 >に記載のパターン形成材料である。  <18> The pattern forming material according to <17>, wherein the Noria layer includes at least one of a bull polymer and a bull copolymer.
< 19 > 支持体が、合成樹脂を含み、かつ透明である前記く 1 >からく 18 >のい ずれかに記載のパターン形成材料である。  <19> The pattern forming material according to any one of the above <1> to <18>, wherein the support contains a synthetic resin and is transparent.
< 20> 支持体が、長尺状である前記く 1 >からく 19 >のいずれかに記載のパタ ーン形成材料である。  <20> The pattern forming material according to any one of the above <1> to <19>, wherein the support is long.
< 21 > パターン形成材料力 長尺状であり、ロール状に巻かれてなる前記く 1 > から < 20 >のいずれかに記載のパターン形成材料である。  <21> Pattern forming material force The pattern forming material according to any one of <1> to <20>, which is long and wound in a roll shape.
< 22> パターン形成材料における感光層上に保護フィルムを有する前記く 1 > からく 21 >のいずれかに記載のパターン形成材料である。  <22> The pattern forming material according to any one of the above items <1>, <21>, which has a protective film on the photosensitive layer in the pattern forming material.
< 23 > 前記く 1 >力もく 22 >の!、ずれかに記載のパターン形成材料を備えて おり、  <23> Said 1> Strength 22> !, with the pattern forming material as described in
光を照射可能な光照射手段と、該光照射手段からの光を変調し、前記パターン形 成材料における感光層に対して露光を行う光変調手段とを少なくとも有することを特 徴とするパターン形成装置である。 A light irradiating means capable of irradiating light; and a light modulating means for modulating light from the light irradiating means and exposing the photosensitive layer in the pattern forming material. This is a pattern forming apparatus.
< 24> 光変調手段が、形成するパターン情報に基づいて制御信号を生成する パターン信号生成手段を更に有してなり、光照射手段から照射される光を該パター ン信号生成手段が生成した制御信号に応じて変調させる前記 < 23 >に記載のバタ ーン形成装置である。該< 24 >に記載のパターン形成装置においては、前記光変 調手段が前記パターン信号生成手段を有することにより、前記光照射手段から照射 される光が該パターン信号生成手段により生成した制御信号に応じて変調される。  <24> The light modulation unit further includes a pattern signal generation unit that generates a control signal based on the pattern information to be formed, and the control generated by the pattern signal generation unit generates light emitted from the light irradiation unit. The pattern forming apparatus according to <23>, wherein the pattern is modulated according to a signal. In the pattern forming apparatus according to <24>, since the light modulation unit includes the pattern signal generation unit, the light emitted from the light irradiation unit is converted into a control signal generated by the pattern signal generation unit. Modulated accordingly.
< 25 > 光変調手段が、 n個の描素部を有してなり、該 n個の描素部の中から連続 的に配置された任意の n個未満の前記描素部を、形成するパターン情報に応じて制 御可能である前記く 23 >からく 24 >のいずれかに記載のパターン形成装置である 。該< 25 >に記載のパターン形成装置においては、前記光変調手段における n個 の描素部の中から連続的に配置された任意の n個未満の描素部をパターン情報に 応じて制御することにより、前記光照射手段力 の光が高速で変調される。  <25> The light modulation means has n pixel parts, and forms any less than n of the pixel parts continuously arranged from the n pixel parts. 25. The pattern forming apparatus according to any one of 23> Karaku 24>, which can be controlled according to pattern information. In the pattern forming apparatus according to <25>, any less than n pixel parts arranged continuously from the n pixel parts in the light modulation unit are controlled according to pattern information. As a result, the light of the light irradiation means power is modulated at high speed.
< 26 > 光変調手段が、空間光変調素子である前記く 23 >からく 25 >のいずれ かに記載のパターン形成装置である。  <26> The pattern forming apparatus according to any one of <23>, <25>, wherein the light modulation means is a spatial light modulation element.
< 27> 空間光変調素子が、デジタル 'マイクロミラー'デバイス (DMD)である前 記 < 26 >に記載のパターン形成装置である。  <27> The pattern forming apparatus according to <26>, wherein the spatial light modulation element is a digital 'micromirror' device (DMD).
< 28 > 描素部が、マイクロミラーである前記く 25 >からく 27>のいずれかに記 載のパターン形成装置である。  <28> The pattern forming apparatus according to any one of the above <25>, <27>, wherein the pixel part is a micromirror.
< 29 > 光照射手段が、 2以上の光を合成して照射可能である前記く 23 >からく 28 >の 、ずれかに記載のパターン形成装置である。該く 29 >に記載のパターン形 成装置においては、前記光照射手段が 2以上の光を合成して照射可能であることに より、露光が焦点深度の深い露光光によって行われる。この結果、前記パターン形成 材料への露光が極めて高精細に行われる。例えば、その後、前記感光層を現像する と、極めて高精細なパターンが形成される。  <29> The pattern forming apparatus according to any one of the above <23>, <28>, wherein the light irradiation means can synthesize and irradiate two or more lights. In the pattern forming apparatus described in 29> above, since the light irradiating means can synthesize and irradiate two or more lights, exposure is performed with exposure light having a deep focal depth. As a result, the pattern forming material is exposed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.
< 30> 光照射手段が、複数のレーザと、マルチモード光ファイバと、該複数のレ 一ザ力 それぞれ照射されたレーザ光を集光して前記マルチモード光ファイバに結 合させる集合光学系とを有する前記く 23 >からく 29 >の 、ずれかに記載のパター ン形成装置である。該< 30 >に記載のパターン形成装置においては、前記光照射 手段が、前記複数のレーザからそれぞれ照射されたレーザ光が前記集合光学系に より集光され、前記マルチモード光ファーバーに結合可能であることにより、露光が焦 点深度の深い露光光で行われる。この結果、前記パターン形成材料への露光が極 めて高精細に行われる。例えば、その後、前記感光層を現像すると、極めて高精細 なパターンが形成される。 <30> The light irradiating means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that collects the laser beams irradiated with the plurality of laser forces and couples them to the multimode optical fiber. The putter according to any one of the above Forming device. In the pattern forming apparatus according to <30>, the light irradiating means may collect the laser light respectively emitted from the plurality of lasers by the collective optical system and be coupled to the multimode optical fiber. As a result, exposure is performed with exposure light having a deep focal depth. As a result, the exposure to the pattern forming material is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, a very fine pattern is formed.
< 31 > 前記 < 1 >から < 22 >のいずれかに記載のパターン形成材料における 該感光層に対し、露光を行うことを少なくとも含むことを特徴とするパターン形成方法 である。  <31> A pattern forming method comprising at least exposing the photosensitive layer in the pattern forming material according to any one of <1> to <22>.
< 32> 基体上にパターン形成材料を加熱及び加圧の少なくともいずれかを行い ながら積層し、露光する前記く 31 >に記載のパターン形成方法である。  <32> The pattern forming method according to <31>, wherein the pattern forming material is laminated on the substrate while being heated and pressurized and exposed.
< 33 > 露光が、形成するパターン情報に基づいて像様に行われる前記く 31 > からく 32 >のいずれかに記載のパターン形成方法である。  <33> The pattern forming method according to any one of <31>, <32>, wherein the exposure is performed imagewise based on pattern information to be formed.
< 34> 露光が、形成するパターン情報に基づいて制御信号を生成し、該制御信 号に応じて変調させた光を用いて行われる前記く 31 >からく 33 >に記載のパター ン形成方法である。  <34> The pattern forming method according to <31>, <33>, wherein the exposure is performed using light modulated based on the pattern information to be formed and modulated in accordance with the control signal. It is.
< 35 > 露光が、光を照射する光照射手段と、形成するパターン情報に基づいて 前記光照射手段から照射される光を変調させる光変調手段とを用いて行われる前記 < 31 >から < 34 >のいずれかに記載のパターン形成方法である。  <35> From the above <31> to <34, wherein the exposure is performed using a light irradiation unit that emits light and a light modulation unit that modulates light emitted from the light irradiation unit based on pattern information to be formed The pattern forming method according to any one of the above.
< 36 > 露光が、光変調手段により光を変調させた後、前記光変調手段における 描素部の出射面の歪みによる収差を補正可能な非球面を有するマイクロレンズを配 列したマイクロレンズアレイを通して行われる前記く 31 >からく 35 >のいずれかに 記載のパターン形成方法である。  <36> After the light is modulated by the light modulation means, the exposure is performed through a microlens array in which microlenses having aspherical surfaces capable of correcting aberrations due to distortion of the exit surface of the picture element portion in the light modulation means are arranged. The pattern forming method according to any one of the above 31> Karaku 35>.
< 37> 非球面が、トーリック面である前記く 36 >に記載のパターン形成方法で ある。該く 37 >に記載のパターン形成方法においては、前記非球面がトーリック面 であることにより、前記描素部における放射面の歪みによる収差が効率よく補正され 、ノターン形成材料上に結像させる像の歪みが効率よく抑制される。この結果、前記 パターン形成材料への露光が極めて高精細に行われる。例えば、その後、前記感光 層を現像すると、極めて高精細なパターンが形成される。 <37> The pattern forming method according to 36, wherein the aspherical surface is a toric surface. In the pattern forming method described in 37> above, since the aspherical surface is a toric surface, the aberration due to the distortion of the radiation surface in the pixel portion is efficiently corrected, and the image formed on the noturn forming material is imaged. Is efficiently suppressed. As a result, the pattern forming material is exposed with extremely high precision. For example, the photosensitive When the layer is developed, a very fine pattern is formed.
< 38 > 露光が、アパーチャアレイを通して行われる前記く 31 >からく 37>のい ずれかに記載のパターン形成方法である。該く 38 >に記載のパターン形成方法に おいては、露光が前記アパーチャアレイを通して行われることにより、消光比が向上 する。この結果、露光が極めて高精細に行われる。例えば、その後、前記感光層を現 像すると、極めて高精細なパターンが形成される。  <38> The pattern forming method according to any one of <31>, <37>, wherein the exposure is performed through an aperture array. In the pattern forming method described in 38>, the extinction ratio is improved by performing exposure through the aperture array. As a result, the exposure is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.
< 39 > 露光が、露光光と感光層とを相対的に移動させながら行われる前記く 31 >からく 38 >のいずれか〖こ記載のパターン形成方法である。該く 39 >に記載のパ ターン形成方法においては、前記変調させた光と前記感光層とを相対的に移動させ ながら露光することにより、露光が高速に行われる。例えば、その後、前記感光層を 現像すると、高精細なパターンが形成される。  <39> The pattern forming method according to any one of <31>, <38>, wherein the exposure is performed while relatively moving the exposure light and the photosensitive layer. In the pattern forming method described in the above item 39>, exposure is performed at a high speed by performing exposure while relatively moving the modulated light and the photosensitive layer. For example, when the photosensitive layer is subsequently developed, a high-definition pattern is formed.
<40> 露光が、感光層の一部の領域に対して行われる前記 < 31 >から < 39 > の!、ずれかに記載のパターン形成方法である。  <40> The pattern forming method according to <31> to <39>, wherein the exposure is performed on a partial region of the photosensitive layer.
く 41 > 露光が行われた後、感光層の現像を行う前記く 31 >からく 40>のいず れかに記載のパターン形成方法である。  <41> The pattern forming method according to any one of <31> to <40>, wherein the photosensitive layer is developed after the exposure.
<42> 現像が行われた後、永久パターンの形成を行う前記く 41 >に記載のパ ターン形成方法である。  <42> The pattern forming method according to the above item 41, wherein a permanent pattern is formed after development.
<43 > 永久パターンが、配線パターンであり、該永久パターンの形成がエツチン グ処理及びメツキ処理の少なくともいずれかにより行われる前記 < 42 >に記載のパ ターン形成方法である。  <43> The pattern formation method according to <42>, wherein the permanent pattern is a wiring pattern, and the formation of the permanent pattern is performed by at least one of an etching process and a plating process.
[0012] 本発明によると、従来における問題を解決することができ、基体表面の凹凸追従性 に優れ、かつ、テント性及びエッチングの均一性に優れた高精細なパターンを形成 可能なパターン形成材料、並びに該パターン形成材料を備えたパターン形成装置 及び前記パターン形成材料を用いたパターン形成方法を提供することができる。 図面の簡単な説明 [0012] According to the present invention, a pattern forming material that can solve the conventional problems, can form a high-definition pattern that is excellent in uneven surface followability on the substrate surface, and excellent in tent properties and etching uniformity. And a pattern forming apparatus including the pattern forming material and a pattern forming method using the pattern forming material. Brief Description of Drawings
[0013] [図 1]図 1は、マイクロレンズアレイを構成するマイクロレンズの正面図の一例である。  FIG. 1 is an example of a front view of a microlens constituting a microlens array.
[図 2]図 2は、マイクロレンズアレイを構成するマイクロレンズの側面図の一例である。  FIG. 2 is an example of a side view of a microlens constituting a microlens array.
[図 3]図 3は、マイクロレンズアレイを構成するマイクロレンズの正面図の一例である。 [図 4]図 4は、マイクロレンズアレイを構成するマイクロレンズの側面図の一例である。 FIG. 3 is an example of a front view of a microlens constituting a microlens array. FIG. 4 is an example of a side view of a microlens constituting a microlens array.
[図 5]図 5は、マイクロレンズによる集光状態を 1つの断面内について示す概略図の一 例である。 [FIG. 5] FIG. 5 is an example of a schematic diagram showing a condensing state by a microlens in one cross section.
[図 6]図 6は、マイクロレンズによる集光状態を 1つの断面内図 5と別の断面内につい て示す概略図の一例である。  [FIG. 6] FIG. 6 is an example of a schematic view showing a condensing state by a microlens in one cross-section in FIG. 5 and another cross-section.
[図 7]図 7は、結合光学系の異なる他の露光ヘッドの構成を示す光軸に沿った断面 図の一例である。  FIG. 7 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.
[図 8]図 8は、マイクロレンズアレイ等を使用しない場合に被露光面に投影される光像 を示す平面図の一例である。  FIG. 8 is an example of a plan view showing an optical image projected on an exposed surface when a microlens array or the like is not used.
[図 9]図 9は、マイクロレンズアレイ等を使用した場合に被露光面に投影される光像を 示す平面図の一例である。  [FIG. 9] FIG. 9 is an example of a plan view showing an optical image projected on an exposed surface when a microlens array or the like is used.
[図 10]図 10は、ファイバアレイ光源の構成を示す斜視図である。  FIG. 10 is a perspective view showing a configuration of a fiber array light source.
[図 11]図 11は、ファイバアレイ光源のレーザ出射部における発光点の配列を示す正 面図の一例である。  [FIG. 11] FIG. 11 is an example of a front view showing an arrangement of light emitting points in a laser emitting portion of a fiber array light source.
[図 12]図 12は、マルチモード光ファイバの構成を示す図の一例である。  FIG. 12 is an example of a diagram showing a configuration of a multimode optical fiber.
[図 13]図 13は、合波レーザ光源の構成を示す平面図の一例である。  FIG. 13 is an example of a plan view showing a configuration of a combined laser light source.
[図 14]図 14は、レーザモジュールの構成を示す平面図の一例である。  FIG. 14 is an example of a plan view showing a configuration of a laser module.
[図 15]図 15は、図 14に示すレーザモジュールの構成を示す側面図の一例である。  FIG. 15 is an example of a side view showing the configuration of the laser module shown in FIG.
[図 16]図 16は、図 14に示すレーザモジュールの構成を示す部分側面図である。  FIG. 16 is a partial side view showing the configuration of the laser module shown in FIG.
[図 17]図 17は、 DMDの使用領域の例を示す図の一例である。  FIG. 17 is an example of a diagram illustrating an example of a DMD usage area.
[図 18]図 18は、図 17と同様の DMDの使用領域の例を示す図の一例である。  FIG. 18 is an example of a diagram showing an example of a DMD usage area similar to FIG.
[図 19]図 19は、パターン形成装置の一例の外観を示す概略斜視図の一例である。 発明を実施するための最良の形態  FIG. 19 is an example of a schematic perspective view showing an appearance of an example of a pattern forming apparatus. BEST MODE FOR CARRYING OUT THE INVENTION
(パターン形成材料） (Pattern forming material)
本発明のパターン形成材料は、支持体上に、第一の層と第二の層とをこの順に有 し、該第一の層のガラス転移温度 (Tg)を A、該第二の層のガラス転移温度 (Tg)を B としたとき、 B≥Aの関係を満たす。  The pattern forming material of the present invention has a first layer and a second layer in this order on a support, the glass transition temperature (Tg) of the first layer is A, and the second layer has a glass transition temperature (Tg). When the glass transition temperature (Tg) is B, the relationship B≥A is satisfied.
前記第一の層と前記第二の層の態様としては、例えば、（1)第一の層がクッション 層であり、第二の層が感光層である態様、及び (2)第一の層が第一感光層であり、第 二の層が第二感光層である態様が挙げられる。 As an aspect of the first layer and the second layer, for example, (1) the first layer is a cushion And an embodiment in which the second layer is a photosensitive layer, and (2) an embodiment in which the first layer is a first photosensitive layer and the second layer is a second photosensitive layer.
また、前記パターン形成材料は、必要に応じて前記第一の層と前記第二の層との 間に、物質の移動を抑制可能なバリア層を有して 、てもよ 、。  Further, the pattern forming material may have a barrier layer capable of suppressing the movement of a substance between the first layer and the second layer as necessary.
[0015] ガラス転移温度 (Tg)— [0015] Glass transition temperature (Tg) —
前記第二の層のガラス転移温度は、ラミネート時の温度範囲内であることが好ましく 、ラミネート時の温度条件の制御により、前記第二の層の該基板への凹凸追従性を 制御できる範囲であることが好まし 、。  The glass transition temperature of the second layer is preferably within the temperature range at the time of lamination, and within the range in which the unevenness followability of the second layer to the substrate can be controlled by controlling the temperature conditions at the time of lamination. I prefer to be there.
前記第二の層のガラス転移温度 Bは、—10〜40°Cであることが好ましぐ 10-40 °Cであることがより好ましい。前記第二の層のガラス転移温度 Bが、 40°Cを超えると、 一般的なラミネート条件下において、基体表面の凹凸への追従性が低下することが あり、— 10°C未満であると、一般的なラミネート条件下において、基体表面の凹凸を 吸収し、膜厚が不均一となることがある。  The glass transition temperature B of the second layer is preferably −10 to 40 ° C., more preferably 10 to 40 ° C. When the glass transition temperature B of the second layer exceeds 40 ° C, the followability to irregularities on the substrate surface may be reduced under general lamination conditions, and is less than −10 ° C. Under general lamination conditions, irregularities on the surface of the substrate may be absorbed, resulting in non-uniform film thickness.
一方、第一の層のガラス転移温度 Aは、前記第二の層の B以下であればとくに制限 はないが、 20〜30°Cであることが好ましぐ 20〜20°Cであることがより好ましい 。前記第一の層のガラス転移温度 Aが、前記第二の層のガラス転移温度 Bを超えると 、前記第二の層の変形が抑制され、膜厚の不均一を生じることがある。  On the other hand, the glass transition temperature A of the first layer is not particularly limited as long as it is equal to or lower than B of the second layer, but it is preferably 20-30 ° C and 20-20 ° C. Is more preferable. When the glass transition temperature A of the first layer exceeds the glass transition temperature B of the second layer, the deformation of the second layer is suppressed and the film thickness may be nonuniform.
[0016] 前記ガラス転移温度の測定方法としては、特に制限はなぐ目的に応じて適宜選択 することができ、例えば、熱分析装置を用いた TMA法、示差走査熱量計を用いた D SC法、粘性率弾性測定装置を用いた DMA法などの公知の方法が挙げられる。 測定用サンプルとしては、例えば、作製した前記第一の層及び前記第二の層を、ミ クロトーム等を用い、それぞれ 10〜500mg採取したものを用いることができる。 [0016] The measuring method of the glass transition temperature can be appropriately selected according to the purpose without any particular limitation. For example, the TMA method using a thermal analyzer, the DSC method using a differential scanning calorimeter, A known method such as a DMA method using a viscosity elasticity measuring apparatus may be used. As the measurement sample, for example, 10 to 500 mg each of the prepared first layer and the second layer collected using a microtome can be used.
[0017] 溶融粘度 [0017] Melt viscosity
前記第二の層の溶融粘度は、 40〜100°Cの範囲において、 500〜30,000 (Pa' S )であることが好ましぐ 1,000-30,000 (Pa · S)であることがより好まし!/、。  The melt viscosity of the second layer is preferably from 500 to 30,000 (Pa 'S), more preferably from 1,000 to 30,000 (Pa · S) in the range of 40 to 100 ° C! /.
前記溶融粘度が、 30,000 (Pa' S)を超えると、基体表面の凹凸を吸収することによ つて膜厚が不均一になることがあり、前記溶融粘度が 500 (Pa' S)未満であると、基 体への転写性 (接着性)が不足することがある。 [0018] 前記溶融粘度の測定方法としては、特に制限はなぐ 目的に応じて適宜選択するこ とができ、例えば、固体液体動的粘弾性測定装置、キヤビラリレオメータ、円錐 ·円板 レオメータ、一軸伸長粘度、メルトインデクサ等一を用いて測定する方法が挙げられ る。 When the melt viscosity exceeds 30,000 (Pa 'S), the film thickness may become non-uniform by absorbing irregularities on the substrate surface, and the melt viscosity is less than 500 (Pa' S). In addition, transferability (adhesiveness) to the substrate may be insufficient. [0018] The method for measuring the melt viscosity is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include a solid-liquid dynamic viscoelasticity measuring device, a cantilever rheometer, a cone / disk rheometer, Examples thereof include a measurement method using a uniaxial elongation viscosity, a melt indexer and the like.
測定用サンプルとしては、測定装置に応じて適宜調製することができ、例えば、固 体液体動的粘弾性測定装置用サンプルとしては、前記第一の層及び前記第二の層 力もミクロトーム等を用いて採取したものを用いることができる。  The measurement sample can be appropriately prepared according to the measurement device. For example, as the sample for the solid liquid dynamic viscoelasticity measurement device, the first layer and the second layer force also use a microtome or the like. Can be used.
[0019] 前記第一の層の厚みは、 5〜30 μ mであることが好ましぐ 10〜30 μ mであること 力 り好ましい。前記第一の層の厚みが 30 mを超えると、解像度が低下したり、現 像時の負荷が大きくなることがあり、 5 m未満であると基体への転写性が悪化するこ とがある。 [0019] The thickness of the first layer is preferably 5 to 30 µm, more preferably 10 to 30 µm. If the thickness of the first layer exceeds 30 m, the resolution may decrease and the load during image formation may increase, and if it is less than 5 m, the transferability to the substrate may deteriorate. .
また、前記第二の層の厚みは、 2〜15 mであることが好ましぐ 2〜10 μ mである ことがより好ましい。前記第二の層の厚みが 15 /z mを超えると、エッチング性が悪ィ匕 することがあり、 2 m未満であるとエッチング時に硬化膜が剥離することがある。  The thickness of the second layer is preferably 2 to 10 m, more preferably 2 to 15 m. When the thickness of the second layer exceeds 15 / zm, the etching property may be deteriorated, and when it is less than 2 m, the cured film may be peeled off during the etching.
[0020] <クッション層 >  [0020] <Cushion layer>
前記クッション層としては、前記第一の層のガラス転移温度、溶融粘度、及び厚み の範囲を満たす限り、特に制限はなぐ 目的に応じて適宜選択することができるが、 例えば、熱可塑性榭脂を含むものが好ましい。  The cushion layer is not particularly limited as long as it satisfies the glass transition temperature, melt viscosity, and thickness ranges of the first layer, and can be appropriately selected according to the purpose. The inclusion is preferred.
[0021] 前記クッション層がアルカリ性液に対して膨潤性乃至可溶性である場合には、前記 熱可塑性榭脂としては、アルカリ可溶性の熱可塑性ポリマーを主に含んでなり、必要 に応じて他の成分を含んで 、てもよ 、。  [0021] When the cushion layer is swellable or soluble in an alkaline liquid, the thermoplastic resin mainly comprises an alkali-soluble thermoplastic polymer, and other components as necessary. Including, ok.
[0022] 前記熱可塑性ポリマーの酸価 (mgKOH/g)は、特に制限はなぐ 目的に応じて適 宜選択することができる力 50〜300力 S好ましく、 60〜270カ Sより好ましく、 70〜250 が特に好ましい。酸価が前記範囲にあることにより、前記クッション層の現像性を確保 することができる。酸価が 50未満であると、現像不良を生じる場合があり、 300を超え ると、前記クッション層が硬くなりすぎ、凹凸追従性やラミネート性が低下する場合が ある。  [0022] The acid value (mgKOH / g) of the thermoplastic polymer is not particularly limited. A force that can be appropriately selected according to the purpose 50 to 300 force S, preferably 60 to 270 S, more preferably 70 to 250 is particularly preferred. When the acid value is within the above range, the developability of the cushion layer can be ensured. When the acid value is less than 50, development failure may occur. When the acid value exceeds 300, the cushion layer becomes too hard, and uneven followability and laminating properties may be deteriorated.
[0023] また、前記熱可塑性ポリマーの重量平均分子量は、特に制限は無ぐ 目的に応じて 適宜選択すること力 Sできる力 1, 000〜300, 000力 S好ましく、 3, 000〜200, 000 力 り好ましぐ 5, 000-150, 000が特に好ましい。重量平均分子量が前記範囲に あることにより、前記クッション層の現像性を確保することができ、前記粘性率 r? を調 節することが容易となる。さらに、上記酸価の範囲との組合せによって、より一層その 効果が得られる。重量平均分子量が 1, 000未満であると、膜が脆弱になったり、ラミ ネート時に前記クッション層の染み出しが起こったりする場合がある。 300, 000を超 えると、前記クッション層が硬くなりすぎ、凹凸追従性やラミネート性が低下する場合 がある。 [0023] The weight average molecular weight of the thermoplastic polymer is not particularly limited. The force to be selected as appropriate S The force that can be applied S 1,000-300,000 force S is preferable, 3,000-200,000 force is more preferable 5,000-150,000 is particularly preferable. When the weight average molecular weight is within the above range, the developability of the cushion layer can be ensured, and the viscosity r? Can be easily adjusted. Further, the effect can be further obtained by the combination with the above acid value range. If the weight average molecular weight is less than 1,000, the membrane may become fragile or the cushion layer may exude during lamination. If it exceeds 300,000, the cushion layer may become too hard, and the unevenness followability and laminating properties may deteriorate.
[0024] なお、前記熱可塑性ポリマーの前記クッション層中の含有量は、特に制限はなぐ 目的に応じて適宜選択することができる力 例えば、前記クッション層の全固形分に 対して、 35質量％以上含有されていることが好ましぐ 55質量％以上含有されている ことがより好ましい。  [0024] The content of the thermoplastic polymer in the cushion layer is not particularly limited. A force that can be appropriately selected according to the purpose. For example, 35 mass% with respect to the total solid content of the cushion layer. It is preferable that the content is 55% by mass or more.
[0025] 前記熱可塑性ポリマーの軟ィ匕点 (Vicat)としては、特に制限はなぐ 目的に応じて 適宜選択することができる力 例えば、前記クッション層の軟ィ匕点が 80°C以下となる ように、実質的な軟ィ匕点が 80°C以下であるものが好ましい。軟化点が 80°C以下のァ ルカリ可溶性の熱可塑性ポリマーとしては、例えば、エチレンとアクリル酸エステル共 重合体のケンィ匕物、スチレンと (メタ）アクリル酸エステル共重合体のケンィ匕物、ビ- ルトルエンと (メタ)アクリル酸エステル共重合体のケンィ匕物、ポリ（メタ）アクリル酸エス テル、（メタ)アクリル酸ブチルと酢酸ビニル等の (メタ)アクリル酸エステル共重合体等 のケンィ匕物、（メタ)アクリル酸エステルと (メタ)アクリル酸との共重合体、スチレンと (メ タ）アクリル酸エステルと (メタ)アクリル酸との共重合体、スチレンと (メタ)アクリル酸と の共重合体などが挙げられる。  [0025] The soft soft point (Vicat) of the thermoplastic polymer is not particularly limited. The force can be appropriately selected according to the purpose. For example, the soft soft point of the cushion layer is 80 ° C or lower. Thus, those having a substantial soft spot of 80 ° C or less are preferred. Examples of alkali-soluble thermoplastic polymers having a softening point of 80 ° C. or lower include ethylene and acrylate copolymer cans, styrene and (meth) acrylate copolymer cans and vinyls. -Kento of rutoluene and (meth) acrylic acid ester copolymer, poly (meth) acrylic acid ester, (meth) acrylic acid ester copolymer such as (meth) acrylic acid butyl and vinyl acetate , (Meth) acrylic acid ester and (meth) acrylic acid copolymer, styrene, (meth) acrylic acid ester and (meth) acrylic acid copolymer, styrene and (meth) acrylic acid A copolymer etc. are mentioned.
[0026] 前記軟化点が 80°C以下の熱可塑性榭脂としては、上述した熱可塑性榭脂の他、「 プラスチック性能便覧」（日本プラスチック工業連盟、全日本プラスチック成形工業連 合会編著、工業調査会発行、 1968年 10月 25日発行）による軟ィ匕点が約 80°C以下 の有機高分子の内、アルカリ性液に可溶なものが挙げられる。また、軟ィ匕点が 80°C 以上の有機高分子物質においても、該有機高分子物質中に該有機高分子物質と相 溶性のある各種の可塑剤を添加して実質的な軟ィ匕点を 80°C以下に下げることも可 能である。 [0026] The thermoplastic resin having a softening point of 80 ° C or lower includes, in addition to the above-described thermoplastic resin, “Plastic Performance Handbook” (edited by the Japan Plastics Industry Federation, All Japan Plastics Molding Industry Association, industrial research). Of organic polymers with a soft spot of about 80 ° C or less (published on October 25, 1968) by the Society). In addition, even in an organic polymer material having a soft softening point of 80 ° C or higher, various plasticizers compatible with the organic polymer material are added to the organic polymer material so that a substantial softness can be obtained. It is also possible to lower the point below 80 ° C Noh.
[0027] 前記可塑剤としては、特に制限はなぐ 目的に応じて適宜選択することができるが、 例えば、ポリプロピレングリコール、ポリエチレングリコール、ジォクチルフタレート、ジ へプチノレフタレート、ジブチノレフタレート、トリクレジルフォスフェート、クレジノレジフエ -ルフォスフェート、ビフエ-ルジフエ-ルフォスフェート等のアルコール類やエステ ル類；トルエンスルホンアミド等のアミド類、などが挙げられる。  [0027] The plasticizer is not particularly limited and may be appropriately selected depending on the purpose. For example, polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptino phthalate, dibutino phthalate, tricres Alcohols and esters such as zircphosphate, crezinoresiphosphate and biphenyldiphosphate, amides such as toluenesulfonamide, and the like.
[0028] また、前記クッション層がアルカリ性液に対して膨潤性乃至可溶性である場合には 、前記パターン形成材料の層間接着力としては、特に制限はなぐ 目的に応じて適 宜選択することができるが、例えば、各層の層間接着力の中で、前記支持体と前記ク ッシヨン層との間の層間接着力力 最も小さいことが好ましい。このような層間接着力 とすることにより、前記積層体から前記支持体のみを剥離し、前記クッション層を介し て前記感光層を露光した後、アルカリ性の現像液を用いて該感光層を現像すること ができる。また、前記支持体を残したまま、前記感光層を露光した後、前記積層体か ら前記支持体のみを剥離し、アルカリ性の現像液を用いて該感光層を現像することも できる。  [0028] When the cushion layer is swellable or soluble in an alkaline liquid, the interlayer adhesive force of the pattern forming material is not particularly limited and can be appropriately selected according to the purpose. However, for example, it is preferable that the interlayer adhesive force between the support and the cushion layer is the smallest among the interlayer adhesive strengths of the respective layers. With such an interlayer adhesive strength, only the support is peeled off from the laminate, the photosensitive layer is exposed through the cushion layer, and then the photosensitive layer is developed using an alkaline developer. be able to. In addition, after exposing the photosensitive layer while leaving the support, only the support is peeled off from the laminate, and the photosensitive layer can be developed using an alkaline developer.
[0029] 前記層間接着力の調整方法としては、特に制限はなぐ 目的に応じて適宜選択す ることができ、例えば、前記熱可塑性榭脂中に公知のポリマー、過冷却物質、密着改 良剤、界面活性剤、離型剤などを添加する方法が挙げられる。  [0029] The method for adjusting the interlayer adhesive force is not particularly limited, and can be appropriately selected according to the purpose. For example, a known polymer, supercooling substance, or adhesion improver in the thermoplastic resin can be selected. , A method of adding a surfactant, a release agent and the like.
[0030] 前記クッション層がアルカリ性液に対して不溶性である場合には、前記熱可塑性榭 脂としては、例えば、主成分がエチレンを必須の共重合成分とする共重合体が挙げ られる。  [0030] When the cushion layer is insoluble in an alkaline liquid, examples of the thermoplastic resin include a copolymer whose main component is an essential copolymer component of ethylene.
前記エチレンを必須の共重合成分とする共重合体としては、特に制限はなぐ 目的 に応じて適宜選択することができる力 例えば、エチレン 酢酸ビニル共重合体 (EV A)、エチレン—ェチルアタリレート共重合体 (EEA)などが挙げられる。  The copolymer having ethylene as an essential copolymer component is not particularly limited and can be appropriately selected according to the purpose. For example, ethylene vinyl acetate copolymer (EV A), ethylene-ethyl acrylate. Copolymer (EEA) and the like.
[0031] 前記クッション層がアルカリ性液に対して不溶性である場合には、前記パターン形 成材料の層間接着力としては、特に制限はなぐ 目的に応じて適宜選択することがで きるが、例えば、各層の層間接着力の中で、前記第二の層である感光層と前記クッシ ヨン層との接着力が、最も小さいことが好ましい。このような層間接着力とすることによ り、前記積層体から前記支持体及びクッション層を剥離し、前記感光層を露光した後 、アルカリ性の現像液を用いて該感光層を現像することができる。また、前記支持体 を残したまま、前記感光層を露光した後、前記積層体から前記支持体と前記クッショ ン層を剥離し、アルカリ性の現像液を用いて該感光層を現像することもできる。 [0031] When the cushion layer is insoluble in an alkaline liquid, the interlayer adhesive force of the pattern forming material can be appropriately selected according to the purpose without any particular limitation. Of the interlayer adhesive strength of each layer, the adhesive strength between the photosensitive layer as the second layer and the cushion layer is preferably the smallest. By using such an interlayer adhesion force Thus, after peeling off the support and cushion layer from the laminate and exposing the photosensitive layer, the photosensitive layer can be developed using an alkaline developer. Further, after exposing the photosensitive layer while leaving the support, the support and the cushion layer are peeled off from the laminate, and the photosensitive layer can be developed using an alkaline developer. .
[0032] 前記層間接着力の調整方法としては、特に制限はなぐ目的に応じて適宜選択す ることができ、例えば、前記熱可塑性榭脂中に各種のポリマー、過冷却物質、密着改 良剤、界面活性剤、離型剤などを添加する方法、以下に説明するエチレン共重合比 を調整する方法などが挙げられる。  [0032] The method for adjusting the interlayer adhesion can be appropriately selected according to the purpose for which there is no particular limitation. For example, various polymers, supercooled substances, adhesion improvers in the thermoplastic resin can be selected. , A method of adding a surfactant, a release agent, and the like, and a method of adjusting the ethylene copolymerization ratio described below.
[0033] 前記エチレンを必須の共重合成分とする共重合体におけるエチレン共重合比とし ては、特に制限はなぐ目的に応じて適宜選択することができる力 例えば、 60-90 質量％が好ましぐ 60〜80質量％がより好ましぐ 65〜80質量％が特に好ましい。 前記エチレンの共重合比が、 60質量％未満になると、前記クッション層と前記感光 層との層間接着力が高くなり、該クッション層と該感光層との界面で剥離することが困 難となることがあり、 90質量％を超えると、前記クッション層と前記感光層との層間接 着力が小さくなりすぎるため、該クッション層と該感光層との間で非常に剥離しやすく なり、前記クッション層を含むパターン形成材料の製造が困難となることがある。  [0033] The ethylene copolymerization ratio in the copolymer having ethylene as an essential copolymerization component is a force that can be appropriately selected according to the purpose without any particular limitation. For example, 60-90% by mass is preferable. 60-80% by mass is more preferred. 65-80% by mass is particularly preferred. When the ethylene copolymerization ratio is less than 60% by mass, the interlayer adhesive force between the cushion layer and the photosensitive layer increases, and it becomes difficult to peel off at the interface between the cushion layer and the photosensitive layer. If the amount exceeds 90% by mass, the indirect adhesion between the cushion layer and the photosensitive layer becomes too small, and the cushion layer and the photosensitive layer are very easily peeled off. It may be difficult to produce a pattern forming material containing
[0034] 前記クッション層がアルカリ性液に対して不溶性であり、かつ、前記クッション層と前 記第二の層である感光層との間にバリア層が存在する場合には、各層の層間接着力 の中で、前記感光層と前記ノリア層との層間接着力が最も小さいことが好ましい。こ のような層間接着力とすることにより、前記積層体から、前記支持体、前記クッション 層、及び前記バリア層を剥離し、前記感光層を露光した後、アルカリ性の現像液を用 いて該感光層を現像することができる。また、前記支持体を剥離せずに残したまま、 前記クッション層を介して前記感光層を露光した後、前記積層体から前記支持体、前 記クッション層、及び前記バリア層を剥離し、アルカリ性の現像液を用いて該感光層 を現像することちできる。  [0034] When the cushion layer is insoluble in an alkaline solution and a barrier layer is present between the cushion layer and the photosensitive layer as the second layer, the interlayer adhesion of each layer Among them, it is preferable that the interlayer adhesive force between the photosensitive layer and the noria layer is the smallest. With such an interlayer adhesive strength, the support, the cushion layer, and the barrier layer are peeled from the laminate, and the photosensitive layer is exposed, and then the photosensitive layer is exposed to an alkaline developer. The layer can be developed. Further, the photosensitive layer is exposed through the cushion layer while leaving the support without being peeled, and then the support, the cushion layer, and the barrier layer are peeled from the laminate, and the alkaline layer The photosensitive layer can be developed using a developing solution.
[0035] 前記層間接着力の調整方法としては、特に制限はなぐ目的に応じて適宜選択す ることができるが、例えば、前記感光層に離形剤を含有させる方法、前記クッション層 と前記バリア層との接着面を表面処理する方法、前記支持体と前記クッション層との 接着面を表面処理する方法、各層の少なくともいずれかに含まれる成分の中から選 択される少なくとも 1種の含有量を調整する方法、及び、接着力を向上させる成分を 含有させる乃至塗布する方法などが挙げられ、これらの方法は 1種単独で使用しても よぐ 2種以上を併用してもよい。 [0035] The method for adjusting the interlayer adhesive force can be appropriately selected according to the purpose without any particular limitation. For example, a method of containing a release agent in the photosensitive layer, the cushion layer and the barrier A method for surface-treating an adhesive surface with a layer, the support and the cushion layer A method of surface-treating the adhesive surface, a method of adjusting at least one content selected from components contained in at least one of the layers, and a method of containing or applying a component that improves the adhesive force These methods may be used alone or in combination of two or more.
[0036] 前記離形剤としては、特に制限はなぐ公知の離形剤の中から適宜選択することが でき、例えば、シリコーンィ匕合物、弗素化アルキル基を有する化合物などが挙げられ る。 [0036] The release agent can be appropriately selected from known release agents with no particular limitations. Examples thereof include silicone compounds and compounds having a fluorinated alkyl group.
[0037] 前記シリコーン化合物としては、例えば、ダイセル UCB社製、エベクリル 1360、同 350、東芝シリコーン社製ジメチルシリコーンオイル TSF400、メチルフエ-ルシリコ 一ン才ィノレ TSF4300、
Figure imgf000015_0001
TSF4446, T SF4460、 TSF4452等力挙げられる。 [0037] Examples of the silicone compound include Daicel UCB Co., Ltd., Evecril 1360, 350, Toshiba Silicone Co., Ltd., dimethyl silicone oil TSF400, methylphenol silicone, 1-year-old Inole TSF4300,
Figure imgf000015_0001
TSF4446, TSF4460, TSF4452 etc. are listed.
[0038] 前記弗素化アルキル基を有する化合物としては、例えば、弗素系界面活性剤（例 えば、大日本インキ化学工業社製パーフルォロアルキル基'親水性基含有オリゴマ 一 F—171、パーフルォロアルキル基'親油性基含有オリゴマー F— 173、パーフル ォロアルキル基.親水性基.親油性基含有オリゴマー F— 177、パーフルォロアルキ ル基 '親油性基含有ウレタン F— 183、 F— 184、弗素系グラフトポリマー等）、弗素系 グラフトポリマー（例えば、東亜合成化学社製、ァロン GF— 300、 GF— 150等）が挙 げられる。  [0038] Examples of the compound having a fluorinated alkyl group include a fluorine-based surfactant (for example, perfluoroalkyl group 'hydrophilic group-containing oligomer F-171, manufactured by Dainippon Ink & Chemicals, Inc. Fluoroalkyl group 'Olipophilic group-containing oligomer F-173, perfluoroalkyl group.Hydrophilic group.Olipophilic group-containing oligomer F-177, Perfluoroalkyl group' Lipophilic group-containing urethane F-183, F — 184, fluorine-based graft polymers, etc.) and fluorine-based graft polymers (for example, ALON GF-300, GF-150, etc., manufactured by Toa Gosei Chemical Co., Ltd.).
[0039] 前記表面処理としては、例えば、プラズマ処理、電子線処理、グロ一放電処理、コ ロナ放電処理、紫外線照射処理などが挙げられる。  [0039] Examples of the surface treatment include plasma treatment, electron beam treatment, glow discharge treatment, corona discharge treatment, and ultraviolet irradiation treatment.
[0040] 前記含有量を調整する方法としては、例えば、前記クッション層が前記エチレンを 必須とする共重合体を含む場合には、前記共重合体におけるエチレン共重合比を 6 0質量％未満とする方法が挙げられる。  [0040] As a method for adjusting the content, for example, when the cushion layer includes a copolymer essentially containing ethylene, the ethylene copolymerization ratio in the copolymer is less than 60% by mass. The method of doing is mentioned.
[0041] 前記接着力を向上させる成分としては、例えば、フエノール性物質 (例えば、クレゾ 一ルノボラック榭脂、フエノールレジン等）、ポリ塩ィ匕ビユリデン榭脂、スチレンブタジ ェンゴム、ゼラチン、ポリビュルアルコール、セルロース類などが挙げられる。これらは 、必要に応じて、前記支持体、クッション層、及びバリア層の少なくともいずれかに含 有させてもよぐ前記支持体と前記クッション層との接触面、前記クッション層と前記バ リア層との接触面に対して塗布してもよい。 [0041] Examples of the component for improving the adhesive strength include phenolic substances (for example, cresol monovolac resin, phenol resin, etc.), polysalt-vinylidene resin, styrene butadiene rubber, gelatin, polybulu alcohol, cellulose And the like. These may be included in at least one of the support, the cushion layer, and the barrier layer, if necessary, on the contact surface between the support and the cushion layer, the cushion layer, and the barrier layer. You may apply | coat with respect to a contact surface with a rear layer.
[0042] 前記架橋剤としては、例えば、硼砂、硼酸、硼酸塩 (例えば、オルト硼酸塩、 InBO  [0042] Examples of the crosslinking agent include borax, boric acid, borates (for example, orthoborate, InBO
3 Three
、 ScBO 、 YBO 、 LaBO 、 Mg (BO ) 、 Co (BO ) 、二硼酸塩（例えば、 Mg B O, ScBO, YBO, LaBO, Mg (BO), Co (BO), diborate (eg Mg B O
3 3 3 3 3 2 3 3 2 2 23 3 3 3 3 2 3 3 2 2 2
、 Co B O )、メタ硼酸塩（例えば、 LiBO 、 Ca (BO ) 、 NaBO 、 KBO )、四硼酸, Co B O), metaborate (eg, LiBO, Ca (BO), NaBO, KBO), tetraboric acid
5 2 2 5 2 2 2 2 2 塩（例えば、 Na Β Ο · 10Η 0)、五硼酸塩（例えば、 KB Ο ·4Η 0、 Ca Β Ο · 7 5 2 2 5 2 2 2 2 2 Salt (eg Na Β Ο · 10Η 0), pentaborate (eg KB Ο · 4Η 0, Ca Β Ο · 7
2 4 7 2 5 8 2 2 6 11 2 4 7 2 5 8 2 2 6 11
Η 0、 CsB Ο )等のホウ素化合物が挙げられる。これらの中でも、速やかに架橋反Boron compounds such as Η0 and CsBΟ) are mentioned. Among these, the cross-linking reaction
2 5 5 2 5 5
応を起こすことができる点で、硼砂、硼酸、硼酸塩が好ましぐ硼酸がより好ましい。ま た、ホルムアルデヒド、グリオキザール、グルタールアルデヒド等のアルデヒド系化合 物；ジァセチル、シクロペンタンジオン等のケトン系化合物；ビス (2-クロ口ェチル尿 素）ー2 ヒドロキシ 4, 6 ジクロロー 1, 3, 5 トリアジン、 2, 4 ジクロロー 6— S —トリァジン'ナトリウム塩等の活性ハロゲン化合物；ジビニルスルホン酸、 1, 3 ビ- ルスルホ-ルー 2—プロパノール、 Ν, Ν，一エチレンビス（ビ-ルスルホ-ルァセタミ ド）、 1, 3, 5 トリアタリロイル—へキサヒドロ S トリァジン等の活性ビュル化合物； ジメチロール尿素、メチロールジメチルヒダントイン等の Ν—メチロール化合物；メラミ ン榭脂（例えば、メチロールメラミン、アルキル化メチロールメラミン）；エポキシ榭脂； 1 , 6—へキサメチレンジイソシァネート等のイソシァネート系化合物；米国特許明細書 第 3017280号、同第 2983611号に記載のアジリジン系化合物;米国特許明細書第 3100704号に記載のカルボキシイミド系化合物；グリセロールトリグリシジルエーテル 等のエポキシ系化合物； 1, 6 へキサメチレン— Ν, Ν，—ビスエチレン尿素等のェ チレンイミノ系化合物；ムコクロル酸、ムコフエノキシクロル酸等のハロゲン化カルボキ シアルデヒド系化合物； 2, 3 ジヒドロキシジォキサン、 2, 3 ジヒドロキシ— 1, 4— ジォキサン等のジォキサン系化合物；乳酸チタン、硫酸アルミ、クロム明ばん、カリ明 ばん、酢酸ジルコニル、酢酸クロム等の金属含有化合物、テトラエチレンペンタミン等 のポリアミン化合物、アジピン酸ジヒドラジド等のヒドラジドィ匕合物、ォキサゾリン基を 2 個以上含有する低分子又はポリマー、などが挙げられる。これらは、 1種単独で使用 してもよく、 2種以上を併用してもよい。  Boric acid, more preferably borax, boric acid, and borate, is more preferred because it can cause a reaction. Aldehyde compounds such as formaldehyde, glyoxal, and glutaraldehyde; ketone compounds such as diacetyl and cyclopentanedione; bis (2-chlorodiethylurea) -2 hydroxy 4, 6 dichloro 1, 3, 5 Active halogen compounds such as triazine, 2, 4 dichloro-6-S-triazine 'sodium salt; divinyl sulfonic acid, 1,3 berylsulfolulu 2-propanol, Ν, Ν, monoethylenebis (birusulfuluolacetamide) ), 1, 3, 5 Tributyloyl-hexahydro S Triazine and other active bur compounds; dimethylol urea, methylol dimethylhydantoin and other Ν-methylol compounds; Epoxy resin; 1, 6-hexamethylene diisocyanate and other isocyanates 1 Aziridine compounds described in US Pat. Nos. 3017280 and 2983611; Carboximide compounds described in US Pat. No. 3100704; Epoxy compounds such as glycerol triglycidyl ether; 1 , 6 Hexamethylene — Ν, Ν, — Ethyleneimino compounds such as bisethyleneurea; Halogenated carboxylic aldehyde compounds such as mucochloric acid and mucophenoxycyclolic acid; 2, 3 Dihydroxydioxane, 2, 3 Dioxane compounds such as dihydroxy-1, 4-dioxane; titanium-containing lactate, aluminum sulfate, chromium alum, potassium alum, metal-containing compounds such as zirconyl acetate and chromium acetate, polyamine compounds such as tetraethylenepentamine, adipic acid dihydrazide Hydrazide compounds, such as small molecules or polymers containing two or more oxazoline groups Mer, and the like. These may be used alone or in combination of two or more.
[0043] 前記シランカップリング剤としては、例えば、 Ν— 2 (アミノエチル） 3 ァミノプロピル メチルジメトキシシラン、 Ν— 2 (アミノエチル） 3 ァミノプロピルトリメトキシシラン、 Ν— 2 (アミノエチル） 3 ァミノプロピルトリエトキシシラン、 3 ァミノプロピルトリメトキシシ ラン、 3 ァミノプロピルトリエトキシシラン、 3 トリエトキシシリル一 N— (1, 3 ジメチ [0043] Examples of the silane coupling agent include: Ν-2 (aminoethyl) 3aminopropyl methyldimethoxysilane, Ν-2 (aminoethyl) 3aminopropyltrimethoxysilane, Ν- 2 (Aminoethyl) 3 Aminopropyltriethoxysilane, 3 Aminopropyltrimethoxysilane, 3 Aminopropyltriethoxysilane, 3 Triethoxysilyl mono N— (1, 3 Dimethyl
N— (ビュルベンジル） 2 アミノエチル一 3 ァミノプロピルトリメトキシシランなどが 挙げられる。また、信越ィ匕学社製のシランカップリング剤も好適に使用することができ る。 N- (Buylbenzyl) 2 aminoethyl 1 3 aminopropyltrimethoxysilane and the like. In addition, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be suitably used.
[0044] 前記架橋剤及びシランカップリング剤の少なくともいずれかを含有させる層としては 、特に制限はなぐ目的に応じて適宜選択することができるが、例えば、前記クッショ ン層及び前記ノリア層が好ましぐ前記クッション層単独がより好ましい。  [0044] The layer containing at least one of the cross-linking agent and the silane coupling agent can be appropriately selected depending on the purpose without any particular limitation. For example, the cushion layer and the noria layer are preferable. More preferably, the cushion layer alone is more preferable.
[0045] また、上述の方法以外にも、前記支持体に含まれる成分の少なくとも 1種と、前記ク ッシヨン層に含まれる成分力 選択される少なくとも 1種と、前記ノリア層に含まれる成 分から選択される少なくとも 1種とを親水性の物質にし、前記感光層に含まれる成分 から選択される少なくとも 1種を疎水性の物質にする方法、前記支持体に含まれる成 分の少なくとも 1種と、前記クッション層に含まれる成分力 選択される少なくとも 1種と 、前記バリア層に含まれる成分から選択される少なくとも 1種とを疎水性の物質にし、 前記感光層に含まれる成分から選択される少なくとも 1種を親水性の物質にする方法 などが挙げられる。  [0045] In addition to the above-described method, at least one of the components included in the support, at least one selected from the component force included in the cushion layer, and the components included in the noria layer. A method of making at least one selected from a hydrophilic substance and at least one selected from the components contained in the photosensitive layer into a hydrophobic substance, at least one of the components contained in the support; The component force contained in the cushion layer is selected from the components contained in the photosensitive layer, wherein at least one selected from the component force and at least one selected from the components contained in the barrier layer are made into a hydrophobic substance. For example, there is a method of making at least one kind of hydrophilic substance.
[0046] 前記成分が、ポリビュルアルコールである場合には、該ポリビュルアルコールのけ ん化度が 85%以下のものや、変性ポリビュルアルコールを適宜選択して使用するこ とができる。また、前記ポリビュルアルコールは、前記架橋剤や前記シランカップリン グ剤等と併用してもよい。  [0046] In the case where the component is polybulal alcohol, the polybulal alcohol having a saponification degree of 85% or less or a modified polybulal alcohol can be appropriately selected and used. Further, the polybulal alcohol may be used in combination with the crosslinking agent, the silane coupling agent, or the like.
前記変性ポリビュルアルコールとしては、例えば、ァ-オン変性ポリビュルアルコー ル（例えば、カルボキシ変性ポリビュルアルコール等）、カチオン変性ポリビュルアル コール、ァセトァセチル化ポリビュルアルコール、シラノール変性ポリビュルアルコー ル、疎水基変性ポリビュルアルコール（例えば、末端アルキルポリビュルアルコール 等）、親水基変性ポリビニルアルコール (例えば、エチレンオキサイド変性ポリビュル アルコール等）、末端チオールポリビュルアルコール、ェクセバール (クラレネ土製）、な どが挙げられる。 [0047] 前記クッション層は、前記熱可塑性榭脂及び必要に応じて他の成分を有機溶剤に 溶解して塗布液 (熱可塑性榭脂層用塗布液)を調製し、公知の塗布方法により仮支 持体上に塗布等して形成することができる。前記有機溶剤としては、メチルェチルケ トン、 1—メトキシ— 2—プロパノール等が挙げられる。 Examples of the modified polybulal alcohol include cation-modified polybulal alcohol (for example, carboxy-modified polybulal alcohol), cation-modified polybulal alcohol, acetoacetylated polybulal alcohol, silanol-modified polybulal alcohol, hydrophobic group-modified polybutyl alcohol. Examples include polybulal alcohol (for example, terminal alkylpolybulal alcohol), hydrophilic group-modified polyvinyl alcohol (for example, ethylene oxide-modified polybulal alcohol), terminal thiol polybulal alcohol, exeval (manufactured by KURARENE), and the like. [0047] The cushion layer is prepared by dissolving the thermoplastic resin and, if necessary, other components in an organic solvent to prepare a coating solution (a coating solution for a thermoplastic resin layer). It can be formed by coating on the support. Examples of the organic solvent include methyl ethyl ketone and 1-methoxy-2-propanol.
[0048] <感光層>  [0048] <Photosensitive layer>
前記感光層は、バインダーと、重合性化合物と、光重合開始剤とを含み、必要に応 じて適宜その他の成分を含む。  The photosensitive layer contains a binder, a polymerizable compound, and a photopolymerization initiator, and appropriately contains other components as necessary.
前記第一の層が前記クッション層であり、前記第二の層が感光層である態様におい て、前記感光層としては、前記第二の層のガラス転移温度、溶融粘度、及び厚みの 範囲を満たす限り、特に制限はなぐ目的に応じて適宜選択することができる。  In the aspect in which the first layer is the cushion layer and the second layer is a photosensitive layer, the photosensitive layer has a glass transition temperature, a melt viscosity, and a thickness range of the second layer. As long as it is satisfied, it can be appropriately selected according to the purpose for which there is no restriction.
[0049] 前記第一の層が第一感光層であり、前記第二の層が第二感光層である態様にお いて、前記第一感光層は、前記第一の層のガラス転移温度、溶融粘度、及び厚みの 範囲を満たし、前記第二感光層は、前記第二の層のガラス転移温度、溶融粘度、及 び厚みの範囲を満たす。また、前記第二の感光層の光感度は、前記第一の感光層 の光感度よりも高いことが好ましぐ具体的には、 405nmの波長の光を照射した際に おいて、第一感光層のパターン形成可能な最小露光量が、第二感光層のパターン 形成可能な最小露光量よりも大き 、ことが好ま U、。 [0049] In an aspect in which the first layer is a first photosensitive layer and the second layer is a second photosensitive layer, the first photosensitive layer has a glass transition temperature of the first layer, The range of melt viscosity and thickness is satisfied, and the second photosensitive layer satisfies the range of glass transition temperature, melt viscosity, and thickness of the second layer. In addition, it is preferable that the photosensitivity of the second photosensitive layer is higher than the photosensitivity of the first photosensitive layer. Specifically, the first photosensitive layer is irradiated with light having a wavelength of 405 nm. It is preferable that the minimum exposure amount that can be patterned on the photosensitive layer is larger than the minimum exposure amount that can be patterned on the second photosensitive layer.
露光時に前記支持体側から照射した光は、前記支持体を有する場合は、前記支持 体と、前記第一感光層と、前記第二感光層との順に進み、前記第二感光層の硬化は 、前記第一感光層よりも先に、少ない光エネルギー量で始まる。前記第二感光層の 全体が硬化した後、前記光エネルギー量を増加すると、前記第一感光層の硬化が始 まり、さらに前記光エネルギー量を多くすると、前記第一感光層の全体が硬化する。  The light irradiated from the support side during exposure proceeds in the order of the support, the first photosensitive layer, and the second photosensitive layer when the support is provided, and the curing of the second photosensitive layer is Before the first photosensitive layer, the process starts with a small amount of light energy. When the amount of light energy is increased after the entire second photosensitive layer is cured, curing of the first photosensitive layer starts, and when the amount of light energy is further increased, the entire first photosensitive layer is cured. .
[0050] 前記第二感光層の硬化が始まる光エネルギー量は、 0. 05〜： LOmjZcm2の範囲 にあることが好ましぐ 0. l〜5mjZcm2の範囲にあることがより好ましぐ 0. 15〜2.5 mjZcm2の範囲にあることが特に好ましい。 [0050] The amount of light energy at which the second photosensitive layer begins to cure is preferably in the range of 0.05-: LOmjZcm 2 , more preferably in the range of 0.1-5 mjZcm 2 0 A range of 15 to 2.5 mjZcm 2 is particularly preferred.
また、前記第二感光層を硬化させるために必要な光エネルギー量は、 0. l〜20mj /cm2の範囲にあることが好ましぐ 0. 2〜15mj/cm2の範囲にあることがより好まし ぐ 0.4〜： LOmj/cm2の範囲であることが特に好ましい。 [0051] 前記第二感光層を硬化させるために必要な光エネルギー量 Aと、前記第一感光層 を硬化させるために必要な光エネルギー量 Bとの比（AZB)は、 0. 005〜0. 5の範 囲にあること力 S好ましく、 0.01〜0.4の範囲にあること力 Sより好ましく、 0. 02〜0. 35 の範囲にあることが特に好ましい。 Further, the amount of light energy required of the second photosensitive layer in order to cure, in the range of preferably tool 0. 2~15mj / cm 2 in the range of 0. l~20mj / cm 2 More preferably 0.4 to: LOmj / cm 2 is particularly preferable. [0051] The ratio (AZB) of the amount of light energy A required to cure the second photosensitive layer to the amount of light energy B necessary to cure the first photosensitive layer is 0.005-0. A force S in the range of 5 is preferable, a force in the range of 0.01 to 0.4 is more preferable than a force S, and a range of 0.02 to 0.35 is particularly preferable.
前記第二感光層を硬化させるために必要な光エネルギー量 Aと、前記第一感光層 の硬化が始まるまで必要な光エネルギー量 Cとの比（CZA)は、 1〜10の範囲にあ ることが好ましぐ 1.1〜9の範囲にあることがより好ましぐ 1.3〜8の範囲であることが 特に好ましい。前記光エネルギー量 Cは、 0.1〜200mjZcm2の範囲にあることが好 ましぐ l〜100mjZcm2の範囲にあることがより好ましぐ 2〜50miZcm2の範囲で あることが特に好ましい。 The ratio (CZA) between the amount of light energy A required to cure the second photosensitive layer and the amount of light energy C required until the first photosensitive layer begins to cure (CZA) is in the range of 1-10. It is particularly preferable that it is in the range of 1.1-9, and it is particularly preferable that it is in the range of 1.3-8. The light energy C is particularly preferably in the range of 0.1～200MjZcm 2 is in the range of more preferably tool 2～50MiZcm 2 in the range of good Mashigu l~100mjZcm 2.
[0052] バインダ [0052] Binder
前記ノインダ一としては、例えば、アルカリ性液に対して膨潤性であることが好まし ぐアルカリ性液に対して可溶性であることがより好ましい。  For example, the noinder is more preferably soluble in an alkaline liquid, preferably swellable in an alkaline liquid.
アルカリ性液に対して膨潤性又は溶解性を示すバインダーとしては、例えば、酸性 基を有するものが好適に挙げられる。  Suitable examples of the binder exhibiting swellability or solubility with respect to the alkaline liquid include those having an acidic group.
[0053] 前記酸性基としては、特に制限はなぐ 目的に応じて適宜選択することができ、例え ば、カルボキシル基、スルホン酸基、リン酸基などが挙げられ、これらの中でもカルボ キシノレ基が好ましい。 [0053] The acidic group is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a carboxyl group, a sulfonic acid group, and a phosphoric acid group, and among these, a carboxyxenore group is preferable. .
カルボキシル基を有するバインダーとしては、例えば、カルボキシル基を有するビ- ル共重合体、ポリウレタン榭脂、ポリアミド酸榭脂、変性エポキシ榭脂などが挙げられ 、これらの中でも、塗布溶媒への溶解性、アルカリ現像液への溶解性、合成適性、膜 物性の調整の容易さ等の観点力 カルボキシル基を有するビニル共重合体が好まし い。  Examples of the binder having a carboxyl group include a vinyl copolymer having a carboxyl group, polyurethane resin, polyamic acid resin, and modified epoxy resin. Among these, solubility in a coating solvent, Viewpoints such as solubility in alkaline developer, suitability for synthesis, and ease of adjustment of film properties. Vinyl copolymers having a carboxyl group are preferred.
[0054] 前記カルボキシル基を有するビニル共重合体は、少なくとも（ 1)カルボキシル基を 有するビニルモノマー、及び（2)これらと共重合可能なモノマーとの共重合により得る ことができ、例えば、特開 2005— 258431号公報の段落 0164から 0205に記載され ている化合物が挙げられる。  [0054] The vinyl copolymer having a carboxyl group can be obtained by copolymerization with at least (1) a vinyl monomer having a carboxyl group, and (2) a monomer copolymerizable therewith. Examples thereof include compounds described in paragraphs 0164 to 0205 of 2005-258431.
[0055] 前記感光層における前記バインダーの含有量としては、特に制限はなぐ 目的に応 じて適宜選択することができる力 例えば、 10〜90質量％が好ましぐ 20〜80質量 %がより好ましぐ 40〜80質量％が特に好ましい。 [0055] The binder content in the photosensitive layer is not particularly limited. For example, 10 to 90% by mass is preferable, and 20 to 80% by mass is more preferable, and 40 to 80% by mass is particularly preferable.
前記含有量が 10質量％未満であると、アルカリ現像性やプリント配線板形成用基 板 (例えば、銅張積層板)との密着性が低下することがあり、 90質量％を超えると、現 像時間に対する安定性や、硬化膜 (テント膜)の強度が低下することがある。なお、前 記含有量は、前記バインダーと必要に応じて併用される高分子結合剤との合計の含 有量であってもよい。  If the content is less than 10% by mass, the alkali developability and the adhesion to a printed wiring board forming substrate (for example, a copper-clad laminate) may be deteriorated. The stability against image time and the strength of the cured film (tent film) may be reduced. The above content may be the total content of the binder and the polymer binder used in combination as necessary.
また、前記第一感光層と前記第二感光層とを有する態様において、感度調整のた めに、上記の範囲内で前記第二感光層に含有されて!、るバインダーの含有率が前 記第一感光層に含有されて!、るバインダーの含有率より低く（重合性化合物の含有 率を高く）するなどの調整を行ってもょ 、。  Further, in the embodiment having the first photosensitive layer and the second photosensitive layer, the binder content in the second photosensitive layer is included in the second photosensitive layer within the above range for sensitivity adjustment. If it is contained in the first photosensitive layer !, make adjustments such as lowering the binder content (higher content of the polymerizable compound).
[0056] 前記バインダーの酸価としては、特に制限はなぐ目的に応じて適宜選択すること ができるが、例えば、 100〜250 (mgKOH/g)が好ましぐ 120〜220 (mgKOHZ g)がより好ましぐ 150〜220 (mgKOH/g)が特に好ましい。 [0056] The acid value of the binder can be appropriately selected depending on the purpose for which there is no particular limitation. For example, 100 to 250 (mgKOH / g) is preferable, and 120 to 220 (mgKOHZ g) is more preferable. The preferred range is 150 to 220 (mgKOH / g).
前記酸価が、 lOO (mgKOHZg)未満であると、現像性が不足したり、解像性が劣 り、配線パターン等の永久パターンを高精細に得ることができないことがあり、 250 (m gKOH/g)を超えると、パターンの耐現像液性及び密着性の少なくともいずれかが 悪化し、配線パターン等の永久パターンを高精細に得ることができな ヽことがある。  If the acid value is less than lOO (mgKOHZg), developability may be insufficient, resolution may be inferior, and permanent patterns such as wiring patterns may not be obtained with high definition. When the amount exceeds / g), at least one of the developer resistance and adhesion of the pattern deteriorates, and a permanent pattern such as a wiring pattern may not be obtained with high definition.
[0057] 一重合性化合物 [0057] Monopolymeric compound
前記重合性化合物としては、特に制限はなぐ目的に応じて適宜選択することがで きるが、例えば、ウレタン基及びァリール基の少なくともいずれかを有するモノマー又 はオリゴマーが好適に挙げられる。また、これらは、重合性基を 2種以上有することが 好ましい。  The polymerizable compound can be appropriately selected according to the purpose without any particular limitation. For example, a monomer or oligomer having at least one of a urethane group and an aryl group is preferably exemplified. These preferably have two or more polymerizable groups.
[0058] 前記重合性基としては、例えば、エチレン性不飽和結合 (例えば、（メタ)アタリロイ ル基、（メタ）アクリルアミド基、スチリル基、ビュルエステルやビュルエーテル等のビ- ル基、ァリルエーテルゃァリルエステル等のァリル基など）、重合可能な環状エーテ ル基 (例えば、エポキシ基、ォキセタン基等)などが挙げられ、これらの中でもェチレ ン性不飽和結合が好まし 、。 [0059] ウレタン基を有するモノマ [0058] Examples of the polymerizable group include an ethylenically unsaturated bond (for example, a (meth) atalyl group, a (meth) acrylamide group, a styryl group, a beryl group such as a butyl ester or a butyl ether, a allylic ether or the like. Aryl groups such as aryl esters) and polymerizable cyclic ether groups (for example, epoxy groups, oxetane groups, etc.), among which ethylenically unsaturated bonds are preferred. [0059] Monomer having urethane group
前記ウレタン基を有するモノマーとしては、ウレタン基を有する限り、特に制限は無 く、目的に応じて適宜選択することができる力 例えば、特開 2005— 258431号公 報の段落 0210から 0262に記載されている化合物などが挙げられる。  The monomer having a urethane group is not particularly limited as long as it has a urethane group, and can be appropriately selected according to the purpose. For example, it is described in paragraphs 0210 to 0262 of JP 2005-258431 A. And the like.
[0060] ァリール基を有するモノマ  [0060] Monomers having aryl groups
前記ァリール基を有するモノマーとしては、ァリール基を有する限り、特に制限はな く、目的に応じて適宜選択することができる力 例えば、特開 2005— 258431号公 報の段落 0263から 0271に記載されて 、る化合物などが挙げられる。  The monomer having an aryl group is not particularly limited as long as it has an aryl group, and can be appropriately selected according to the purpose. For example, it is described in paragraphs 0263 to 0271 of JP 2005-258431 A. And the like.
[0061] その他の重合性モノマ  [0061] Other polymerizable monomers
本発明のパターン形成方法には、前記ウレタン基を含有するモノマー、ァリール基 を有するモノマー以外の重合性モノマーを用いてもょ 、。  In the pattern forming method of the present invention, a polymerizable monomer other than the monomer having a urethane group and the monomer having an aryl group may be used.
[0062] 前記ウレタン基を含有するモノマー、芳香環を含有するモノマー以外の重合性モノ マーとしては、例えば、特開 2005— 258431号公報の段落 0272から 0284に記載 されて 、る化合物などが挙げられる。 [0062] Examples of the polymerizable monomer other than the monomer containing a urethane group and the monomer containing an aromatic ring include the compounds described in paragraphs 0272 to 0284 of JP-A-2005-258431. It is done.
[0063] 前記感光層における重合性ィ匕合物の含有量としては、例えば、 5〜90質量％が好 ましぐ 15〜60質量％がより好ましぐ 20〜50質量％が特に好ましい。 [0063] The content of the polymerizable compound in the photosensitive layer is, for example, preferably 5 to 90% by mass, more preferably 15 to 60% by mass, and particularly preferably 20 to 50% by mass.
前記含有量が、 5質量％となると、テント膜の強度が低下することがあり、 90質量％ を超えると、保存時のエッジフュージョン（ロール端部力 のしみだし故障）が悪化す ることがある。  If the content is 5% by mass, the strength of the tent film may be reduced, and if it exceeds 90% by mass, edge fusion during storage (extruding failure of the roll end force) may be deteriorated. is there.
また、前記第一感光層と前記第二感光層とを有する態様において、感度調整のた めに、上記の範囲内で、前記第二感光層のモノマー含有率を前記第一感光層のモ ノマー含有率よりも高くするなどの調整をおこなってもよい。  In the embodiment having the first photosensitive layer and the second photosensitive layer, the monomer content of the second photosensitive layer is adjusted within the above range to adjust the sensitivity. Adjustment, such as making it higher than a content rate, may be performed.
[0064] 前記重合性化合物中に前記重合性基を 2個以上有する多官能モノマーの含有量 としては、 5〜： L00質量％が好ましぐ 20〜： L00質量％がより好ましぐ 40〜： L00質量 %が特に好ましい。 [0064] The content of the polyfunctional monomer having two or more of the polymerizable groups in the polymerizable compound is preferably 5 to: L00 mass% is preferable 20 to: L00 mass% is more preferable 40 to 40 : L00% by mass is particularly preferable.
[0065] 一光重合開始剤 [0065] One-photopolymerization initiator
前記光重合開始剤としては、前記重合性化合物の重合を開始する能力を有する限 り、特に制限はなぐ公知の光重合開始剤の中から適宜選択することができるが、例 えば、特開 2005— 258431号公報の段落 0286から 0310に記載されたィ匕合物など が挙げられる。 The photopolymerization initiator can be appropriately selected from known photopolymerization initiators that are not particularly limited as long as they have the ability to initiate polymerization of the polymerizable compound. For example, the compound described in paragraphs 0286 to 0310 of JP-A-2005-258431 can be mentioned.
[0066] 前記感光層における光重合開始剤の含有量としては、 0. 1〜30質量％が好ましく 、0. 5〜20質量％がより好ましぐ 0. 5〜15質量％が特に好ましい。  [0066] The content of the photopolymerization initiator in the photosensitive layer is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and particularly preferably 0.5 to 15% by mass.
前記第一感光層と前記第二感光層とを有する態様において、前記第一感光層と前 記第二感光層との感度差を光重合開始剤の含有量で調整する場合には、前記第二 感光層に含有されて!、る光重合開始剤の量を、前記第一感光層に含有されて!ヽる 光重合性開始剤の量よりも多くすればよい。前記第二感光層の光重合開始剤含有 量は、前記第一感光層の光重合開始剤の含有量に対して 1. 5〜： L00倍の量とする ことが好ましぐさらに 1.8倍〜 50倍の量が好ましぐ特に 2〜20倍の量とすることが 好ましい。  In an embodiment having the first photosensitive layer and the second photosensitive layer, when the sensitivity difference between the first photosensitive layer and the second photosensitive layer is adjusted by the content of the photopolymerization initiator, (2) The amount of the photopolymerization initiator contained in the photosensitive layer may be larger than the amount of the photopolymerization initiator contained in the first photosensitive layer. The photopolymerization initiator content of the second photosensitive layer is preferably 1.5 to L00 times the content of the photopolymerization initiator of the first photosensitive layer, and more preferably 1.8 times to A 50-fold amount is preferable, and a 2 to 20-fold amount is particularly preferable.
[0067] その他の成分  [0067] Other ingredients
前記その他の成分としては、例えば、増感剤、熱重合禁止剤、可塑剤、発色剤、着 色剤などが挙げられ、更に基体表面への密着促進剤及びその他の助剤類 (例えば、 顔料、導電性粒子、充填剤、消泡剤、難燃剤、レべリング剤、剥離促進剤、酸化防止 剤、香料、熱架橋剤、表面張力調整剤、連鎖移動剤等)を併用してもよい。これらの ィ匕合物としては、 ί列えば、特開 2005— 258431号公報の段落 0312力ら 0336に記 載された化合物などが挙げられ、適宜含有させることにより、目的とするパターン形成 材料の安定性、写真性、焼きだし性、膜物性等の性質を調整することができる。  Examples of the other components include sensitizers, thermal polymerization inhibitors, plasticizers, color formers, colorants, and the like, and adhesion promoters to the substrate surface and other auxiliary agents (for example, pigments). , Conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, release accelerators, antioxidants, fragrances, thermal crosslinking agents, surface tension modifiers, chain transfer agents, etc.) . Examples of these compounds include, for example, compounds described in JP-A-2005-258431, paragraphs 0312 and 0336, and the like. Properties such as stability, photographic properties, print-out properties, film properties, etc. can be adjusted.
[0068] <バリア層 >  [0068] <Barrier layer>
前記バリア層は、物質の移動を抑制可能である限り、特に制限はなぐ目的に応じ て適宜選択することができ、水溶性乃至水分散性であってもよぐアルカリ性液に対 して可溶性であってもよぐ不溶性であってもよい。なお、前記物質の移動を抑制可 能とは、前記バリア層を有しない場合と比較して、前記バリア層と隣接する前記第一 の層及び前記第二の層における目的物質の含有量の増加又は減少が、抑制されて いることを意味する。  The barrier layer can be appropriately selected according to the purpose without particular limitation as long as the movement of the substance can be suppressed, and is soluble in an alkaline liquid which may be water-soluble or water-dispersible. It may be insoluble. Note that the ability to suppress the movement of the substance means that the content of the target substance in the first layer and the second layer adjacent to the barrier layer is increased compared to the case where the barrier layer is not provided. Or it means that the decrease is suppressed.
[0069] 前記物質としては、特に制限はなぐ目的に応じて適宜選択することができるが、例 えば、酸素、水、前記第一の層及び前記第二の層の少なくともいずれかに含まれる 物質が挙げられる。 [0069] The substance can be appropriately selected depending on the purpose for which there is no particular limitation. For example, the substance is included in at least one of oxygen, water, the first layer, and the second layer. Substances.
[0070] 前記バリア層が、水溶性乃至水分散性である場合には、水溶性乃至水分散性の榭 脂を含むことが好ましぐアルカリ性液に対して可溶性である場合には、アルカリ性液 に対して可溶性の榭脂を含むことが好ましい。なお、前記水溶性の程度としては、例 えば、 25°Cの水に対し、 0. 1質量％以上溶解するものが好ましぐ 1質量％以上溶 解するものがより好ましい。  [0070] When the barrier layer is water-soluble or water-dispersible, when the barrier layer is soluble in an alkaline liquid that preferably contains a water-soluble or water-dispersible resin, the alkaline liquid It is preferable to contain soluble greaves. The water solubility is preferably, for example, preferably 0.1% by mass or more, and more preferably 1% by mass or more, with respect to 25 ° C. water.
[0071] 前記榭脂としては、特に制限はなぐ目的に応じて適宜選択することができるが、例 えば、各種のアルコール可溶性榭脂、水溶性榭脂、アルコール分散性榭脂、水分散 性榭脂、乳化性榭脂、アルカリ性液に対して可溶性の榭脂などが挙げられ、具体的 には、ビュル重合体（例えば、ポリビュルアルコール（変性ポリビュルアルコール類も 含む）、ポリビニルピロリドン等）、上述のビニル共重合体、水溶性ポリアミド、ゼラチン 、セルロース、これらの誘導体などが挙げられる。また、特許 2794242号に記載の熱 可塑性榭脂ゃ中間層に使用されている化合物、前記バインダーなどを使用すること もできる。これらは、 1種単独で使用してもよぐ 2種以上を併用してもよい。  [0071] The resin can be appropriately selected according to the purpose for which there is no particular limitation. For example, various alcohol-soluble resins, water-soluble resins, alcohol-dispersible resins, water-dispersible resins Examples include fats, emulsifiable fats, and fats that are soluble in alkaline liquids. Specific examples include bulle polymers (for example, polybulal alcohol (including modified polybulal alcohols), polyvinylpyrrolidone, etc.), Examples thereof include the above-mentioned vinyl copolymers, water-soluble polyamides, gelatin, cellulose, and derivatives thereof. Further, the thermoplastic resin described in Japanese Patent No. 2794242 and the compounds 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.
[0072] 前記バリア層が、アルカリ性液に対して不溶性である場合には、アルカリ性液に対 して不溶性の榭脂を含むことが好まし 、。  [0072] In the case where the barrier layer is insoluble in the alkaline liquid, it is preferable that the barrier layer contains a resin insoluble in the alkaline liquid.
前記アルカリ性液に対して不溶性の榭脂としては、例えば、主成分がエチレンを必 須の共重合成分とする共重合体が挙げられる。  Examples of the resin insoluble in the alkaline liquid include a copolymer whose main component is ethylene as a necessary copolymer component.
前記エチレンを必須の共重合成分とする共重合体としては、特に制限はなぐ目的 に応じて適宜選択することができる力 例えば、エチレン 酢酸ビニル共重合体 (EV A)、エチレン—ェチルアタリレート共重合体 (EEA)などが挙げられる。  The copolymer having ethylene as an essential copolymer component is a force that can be appropriately selected according to the purpose without any particular limitation. For example, ethylene vinyl acetate copolymer (EV A), ethylene-ethyl acrylate. Copolymer (EEA) and the like.
[0073] 前記バリア層の厚みとしては、特に制限はなぐ目的に応じて適宜選択することが できるが、例えば、 10 μ m未満が好ましぐ 0. 1〜6 μ mがより好ましぐ 1〜5 μ mが 特に好ましい。  [0073] The thickness of the barrier layer can be appropriately selected according to the purpose for which there is no particular limitation. For example, it is preferably less than 10 μm, more preferably 0.1 to 6 μm 1 ˜5 μm is particularly preferred.
前記厚みが、 10 /z m以上となると、露光の際、前記バリア層で光散乱が生じ、解像 度及び密着性の少なくともいずれかが悪ィ匕することがある。  When the thickness is 10 / z m or more, light scattering occurs in the barrier layer during exposure, and at least one of resolution and adhesion may be deteriorated.
[0074] <支持体及び保護フィルム > [0074] <Support and protective film>
前記支持体としては、特に制限はなぐ目的に応じて適宜選択することができるが、 光の透過性が良好であるものが好ましぐ更に表面の平滑性が良好であることがより 好ましい。 The support can be appropriately selected according to the purpose without particular limitation, Those having good light transmittance are preferred, and the surface smoothness is more preferred.
[0075] 前記支持体は、合成樹脂製で、かつ透明であるものが好ましぐ例えば、ポリエチレ ンテレフタレート、ポリエチレンナフタレート、ポリプロピレン、ポリエチレン、三酢酸セ ルロース、二酢酸セルロース、ポリ（メタ）アクリル酸アルキルエステル、ポリ（メタ）アタリ ル酸エステル共重合体、ポリ塩化ビュル、ポリビュルアルコール、ポリカーボネート、 ポリスチレン、セロファン、ポリ塩ィ匕ビユリデン共重合体、ポリアミド、ポリイミド、塩ィ匕ビ -ル '酢酸ビュル共重合体、ポリテトラフロロエチレン、ポリトリフロロエチレン、セル口 ース系フィルム、ナイロンフィルム等の各種のプラスチックフィルムが挙げられ、これら の中でも、ポリエチレンテレフタレートが特に好ましい。これらは、 1種単独で使用して もよぐ 2種以上を併用してもよい。  [0075] The support is preferably made of a synthetic resin and transparent, for example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic. Alkyl ester, poly (meth) acrylate ester copolymer, polychlorinated butyl, polybulal alcohol, polycarbonate, polystyrene, cellophane, polysalt-vinylidene copolymer, polyamide, polyimide, salt-vinyl '' Various plastic films such as butyl acetate copolymer, polytetrafluoroethylene, polytrifluoroethylene, 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.
[0076] 前記支持体の厚みとしては、特に制限はなぐ 目的に応じて適宜選択することがで さる力 f列; tは、、 2- 150 μ m力 S女子ましく、 5〜： LOO μ m力 S Jり女子ましく、 8〜50 μ m力 S 特に好ましい。  [0076] The thickness of the support is not particularly limited, and can be appropriately selected according to the purpose. F column; t is 2-150 μm force S girlish, 5-: LOO μ m force SJ-like girls, 8-50 μm force S Particularly preferred.
[0077] 前記支持体の形状としては、特に制限はなぐ 目的に応じて適宜選択することがで きるが、長尺状が好ましい。前記長尺状の支持体の長さとしては、特に制限はなぐ 例えば、 10m〜20000mの長さのものが挙げられる。  [0077] The shape of the support is not particularly limited and may be appropriately selected depending on the purpose, but is preferably long. The length of the long support is not particularly limited, and examples thereof include a length of 10 m to 20000 m.
[0078] 前記パターン形成材料は、前記第二の層 (感光層）上に保護フィルムを形成しても よい。  The pattern forming material may form a protective film on the second layer (photosensitive layer).
前記保護フィルムとしては、例えば、前記支持体に使用されるもの、紙、ポリエチレ ン、ポリプロピレン力ラミネートされた紙、などが挙げられ、これらの中でも、ポリエチレ ンフィルム、ポリプロピレンフィルムが好ましい。  Examples of the protective film include those used for the support, paper, polyethylene, paper laminated with polypropylene, and the like. Among these, a polyethylene film and a polypropylene film are preferable.
前記保護フィルムの厚みとしては、特に制限はなぐ 目的に応じて適宜選択するこ とができる力 例えば、 5〜： LOO /z m力好ましく、 8〜50 111カょり好ましく、 10〜30 /z mが特に好ましい。  The thickness of the protective film is not particularly limited and can be appropriately selected according to the purpose. For example, 5 to: LOO / zm force is preferable, 8 to 50 111 is preferable, and 10 to 30 / zm is preferable. Particularly preferred.
前記保護フィルムを用いる場合、該保護フィルムと前記第二の層 (感光層）との層間 接着力は、他の各層の層間接着力の中で、最も小さいことが好ましい。  When the protective film is used, the interlayer adhesive force between the protective film and the second layer (photosensitive layer) is preferably the smallest among the interlayer adhesive forces of the other layers.
前記支持体と保護フィルムとの組合せ (支持体 Z保護フィルム）としては、例えば、 ポリエチレンテレフタレート zポリプロピレン、ポリエチレンテレフタレート zポリエチレ ン、ポリ塩化ビュル Zセロファン、ポリイミド Zポリプロピレン、ポリエチレンテレフタレ ート zポリエチレンテレフタレートなどが挙げられる。また、支持体及び保護フィルム の少なくとも 、ずれかを表面処理することにより、上述のような接着力の関係を満たす ことができる。前記支持体の表面処理は、前記第一の層（クッション層又は第一感光 層）との接着力を高めるために施されてもよぐ例えば、下塗層の塗設、コロナ放電処 理、火炎処理、紫外線照射処理、高周波照射処理、グロ一放電照射処理、活性ブラ ズマ照射処理、レーザ光線照射処理などを挙げることができる。 As a combination of the support and the protective film (support Z protective film), for example, Examples include polyethylene terephthalate z polypropylene, polyethylene terephthalate z polyethylene, polychlorinated bur Z cellophane, polyimide Z polypropylene, polyethylene terephthalate z polyethylene terephthalate, and the like. In addition, the above-described adhesive force relationship can be satisfied by surface-treating at least one of the support and the protective film. The surface treatment of the support may be performed in order to increase the adhesive force with the first layer (cushion layer or first photosensitive layer). For example, coating of an undercoat layer, corona discharge treatment, Examples thereof include flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow discharge irradiation treatment, active plasma irradiation treatment, and laser beam irradiation treatment.
[0079] また、前記支持体と前記保護フィルムとの静摩擦係数としては、 0. 3〜1. 4が好ま しく、 0. 5〜1. 2力より好まし!/ヽ。  [0079] The coefficient of static friction between the support and the protective film is preferably 0.3 to 1.4, more preferably 0.5 to 1.2 force! / !.
前記静摩擦係数が、 0. 3未満であると、滑り過ぎるため、ロール状にした場合に卷 ズレが発生することがあり、 1. 4を超えると、良好なロール状に巻くことが困難となるこ とがある。  If the coefficient of static friction is less than 0.3, slipping may occur excessively, so that a deviation may occur when the roll is formed, and if it exceeds 1.4, it is difficult to wind in a good roll. Sometimes.
[0080] 前記パターン形成材料は、例えば、円筒状の卷芯に巻き取って、長尺状でロール 状に巻かれて保管されることが好ましい。前記長尺状のパターン形成材料の長さとし ては、特に制限はなぐ例えば、 10m〜20, OOOmの範囲力 適宜選択することがで きる。また、ユーザーが使いやすいようにスリット加工し、 100m〜l, OOOmの範囲の 長尺体をロール状にしてもよい。なお、この場合には、前記支持体が一番外側になる ように巻き取られることが好ましい。また、前記ロール状のパターン形成材料をシート 状にスリットしてもよい。保管の際、端面の保護、エッジフュージョンを防止する観点か ら、端面にはセパレーター (特に防湿性のもの、乾燥剤入りのもの）を設置することが 好ましぐまた梱包も透湿性の低 、素材を用いる事が好ま 、。  [0080] The pattern forming material is preferably stored, for example, wound around a cylindrical core and wound into a long roll. The length of the long pattern forming material is not particularly limited, and can be appropriately selected, for example, a range force of 10 m to 20, OOOm. In addition, slitting may be performed so that it is easy for the user to use, and a long body in the range of 100 m to l, OOOm may be rolled. In this case, it is preferable that the support is wound up so as to be the outermost side. The roll-shaped pattern forming material may be slit into a sheet shape. In order to protect the end face and prevent edge fusion during storage, it is preferable to install a separator (especially moisture-proof and desiccant-containing) on the end face, and the packaging has low moisture permeability. I prefer to use materials.
[0081] 前記保護フィルムは、前記保護フィルムと前記第二の層 (感光層）との接着性を調 整するために表面処理してもよい。前記表面処理は、例えば、前記保護フィルムの表 面に、ポリオルガノシロキサン、弗素化ポリオレフイン、ポリフルォロエチレン、ポリビ- ルアルコール等のポリマー力もなる下塗層を形成させる。該下塗層の形成は、前記 ポリマーの塗布液を前記保護フィルムの表面に塗布した後、 30〜150°C (特に 50〜 120°C)で 1〜30分間乾燥させることにより形成させることができる。 また、前記基体に接触する層のガラス転移点が最も高くなる限り、前記クッション層 、前記感光層、前記バリア層、前記支持体、及び前記保護フィルムの他に、剥離層、 接着層、光吸収層、表面保護層などの層を有してもよい。また、前記各層は、 1層有 していてもよぐ 2層以上有していてもよい。 [0081] The protective film may be surface-treated in order to adjust the adhesion between the protective film and the second layer (photosensitive layer). In the surface treatment, for example, an undercoat layer having a polymer strength such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, polyvinyl alcohol or the like 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. it can. In addition to the cushion layer, the photosensitive layer, the barrier layer, the support, and the protective film, in addition to the cushion layer, the photosensitive layer, the barrier layer, the support, and the protective film, as long as the glass transition point of the layer that contacts the substrate is the highest. You may have layers, such as a layer and a surface protective layer. Each of the layers may have one layer or two or more layers.
[0082] [パターン形成材料の製造]  [0082] [Production of pattern forming material]
前記パターン形成材料は、例えば、次のようにして製造することができる。 まず、前記第一の層、前記第二の層、及びバリア層に含まれる材料を、水又は溶剤 に溶解、乳化又は分散させて、塗布液を調製する。  The pattern forming material can be manufactured, for example, as follows. First, the materials contained in the first layer, the second layer, and the barrier layer are dissolved, emulsified or dispersed in water or a solvent to prepare a coating solution.
[0083] 前記塗布液の溶剤としては、特に制限はなぐ目的に応じて適宜選択することがで き、例えば、メタノール、エタノール、 n—プロパノール、イソプロパノール、 n—ブタノ ール、 sec ブタノール、 n—へキサノール等のアルコール類；アセトン、メチルェチル ケトン、メチルイソブチルケトン、シクロへキサノン、ジイソプチルケトンなどのケトン類； 酢酸ェチル、酢酸ブチル、酢酸 n—ァミル、硫酸メチル、プロピオン酸ェチル、フタ ル酸ジメチル、安息香酸ェチル、及びメトキシプロピルアセテートなどのエステル類； トルエン、キシレン、ベンゼン、ェチルベンゼンなどの芳香族炭化水素類；四塩ィ匕炭 素、トリクロロエチレン、クロ口ホルム、 1, 1, 1—トリクロロェタン、塩化メチレン、モノク ロロベンゼンなどのハロゲン化炭化水素類；テトラヒドロフラン、ジェチルエーテル、ェ チレングリコーノレモノメチノレエーテノレ、エチレングリコーノレモノェチノレエーテノレ、 1ーメ トキシ 2—プロパノールなどのエーテル類；ジメチルホルムアミド、ジメチルァセトアミ ド、ジメチルスルホオキサイド、スルホランなどが挙げられる。これらは、 1種単独で使 用してもよぐ 2種以上を併用してもよい。また、公知の界面活性剤を添加してもよい。  [0083] The solvent of the coating solution can be appropriately selected according to the purpose without any particular limitation. 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, diisoptyl ketone; Ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl ethyl propionate, phthalic acid Esters such as dimethyl, ethyl benzoate, and methoxypropyl acetate; aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene; tetrasalt carbon, trichloroethylene, chloroform, 1, 1, 1-trichloro Halogenation of ethane, methylene chloride, monochlorobenzene, etc. Hydrogen fluorides; ethers such as tetrahydrofuran, jetyl ether, ethylenic glycolenomonoethylenoateol, ethyleneglycolenomonoethylenotenole, 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide , Dimethyl sulfoxide, sulfolane and the like. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.
[0084] 次に、前記支持体上に前記第一の層用塗布液 (クッション層用塗布液、又は第一 感光層用塗布液)を塗布し、乾燥させて前記第一の層を形成し、前記バリア層を形 成する場合には、前記ノリア層用塗布液を塗布し、乾燥させてノリア層を形成し、該 バリア層上に前記第二の層用塗布液 (感光層用塗布液、又は第二感光層用塗布液 )を塗布し、乾燥させて前記第二の層を形成し、パターン形成材料を製造することが できる。  Next, the first layer coating solution (cushion layer coating solution or first photosensitive layer coating solution) is applied onto the support and dried to form the first layer. In the case of forming the barrier layer, the noria layer coating solution is applied and dried to form a noria layer, and the second layer coating solution (photosensitive layer coating solution) is formed on the barrier layer. Or a coating solution for the second photosensitive layer) and dried to form the second layer, whereby a pattern forming material can be produced.
[0085] 前記塗布液の塗布方法としては、特に制限はなぐ目的に応じて適宜選択すること ができる力 例えば、スプレー法、ロールコート法、回転塗布法、スリットコート法、エタ ストルージョンコート法、カーテンコート法、ダイコート法、グラビアコート法、ワイヤー バーコート法、ナイフコート法等の各種の塗布方法が挙げられる。 [0085] The method of applying the coating solution is appropriately selected according to the purpose for which there is no particular limitation. For example, spray coating, roll coating, spin coating, slit coating, etching coating, curtain coating, die coating, gravure coating, wire bar coating, knife coating, etc. A method is mentioned.
前記乾燥の条件としては、各成分、溶媒の種類、使用割合等によっても異なるが、 通常 60〜 110°Cの温度で 30秒間〜 15分間程度である。  The drying conditions vary depending on each component, the type of solvent, the ratio of use, etc., but are usually 60 to 110 ° C. for 30 seconds to 15 minutes.
[0086] 本発明のパターン形成材料は、基体表面の凹凸追従性に優れ、かつ、テント性及 びエッチングの均一性に優れた高精細なパターンを形成可能であるため、各種パタ ーンの形成用、配線パターン等の永久パターンの形成用、カラーフィルタ、柱材、リ ブ材、スぺーサ一、隔壁等の液晶構造部材の製造用、ホログラム、マイクロマシン、 プルーフなどのパターン形成用などに好適に用いることができ、特に本発明のパター ン形成方法及びパターン形成装置に好適に用いることができる。 [0086] Since the pattern forming material of the present invention is capable of forming a high-definition pattern excellent in uneven surface followability on the substrate surface and excellent in tent property and etching uniformity, various pattern formations are possible. Suitable for forming permanent patterns such as wiring patterns, color filters, column materials, rib materials, spacers, liquid crystal structural members such as partition walls, and forming patterns for holograms, micromachines, proofs, etc. In particular, it can be suitably used in the pattern forming method and pattern forming apparatus of the present invention.
[0087] (パターン形成装置及びパターン形成方法） (Pattern forming apparatus and pattern forming method)
本発明のパターン形成装置は、本発明の前記パターン形成材料を備えており、光 照射手段と光変調手段とを少なくとも有する。  The pattern forming apparatus of the present invention includes the pattern forming material of the present invention, and has at least light irradiation means and light modulation means.
[0088] 本発明のパターン形成方法は、露光工程を少なくとも含み、適宜選択したその他の 工程を含む。 [0088] The pattern forming method of the present invention includes at least an exposure step, and includes other steps appropriately selected.
なお、本発明の前記パターン形成装置は、本発明の前記パターン形成方法の説明 を通じて明らかにする。  In addition, the said pattern formation apparatus of this invention is clarified through description of the said pattern formation method of this invention.
[0089] [露光工程] [0089] [Exposure process]
前記露光工程は、本発明のパターン形成材料における感光層に対し、露光を行う 工程である。本発明の前記パターン形成材料については上述の通りである。  The said exposure process is a process of exposing with respect to the photosensitive layer in the pattern formation material of this invention. The pattern forming material of the present invention is as described above.
[0090] 前記露光の対象としては、前記パターン形成材料における感光層である限り、特に 制限はなぐ 目的に応じて適宜選択することができるが、例えば、基体上に前記バタ ーン形成材料を形成してなる積層体に対して行われることが好ましい。  [0090] The exposure target is not particularly limited as long as it is a photosensitive layer in the pattern forming material, and can be appropriately selected according to the purpose. For example, the pattern forming material is formed on a substrate. It is preferable to be performed on the laminated body.
[0091] 前記基体としては、特に制限はなぐ公知の材料の中力 表面平滑性の高いもの 力 凸凹のある表面を有するものまで適宜選択することができるが、板状の基体 (基 板)が好ましぐ具体的には、公知のプリント配線板形成用基板 (例えば、銅張積層板 )、ガラス板 (例えば、ソーダガラス板等）、合成樹脂性のフィルム、紙、金属板などが 挙げられる。 [0091] The substrate may be appropriately selected from known materials having no particular limitation, medium strength, high surface smoothness, force, and a surface having an uneven surface, but a plate-shaped substrate (substrate) may be used. Specifically, a known printed wiring board forming substrate (for example, copper-clad laminate), glass plate (for example, soda glass plate), synthetic resin film, paper, metal plate, etc. Can be mentioned.
[0092] 前記積層体における層構成としては、基体上に少なくとも前記第二の層と前記第一 の層とをこの順に有し、例えば、（1)前記基体、前記感光層、前記クッション層、及び 前記支持体をこの順に有する層構成、（2)前記基体、前記第二感光層、前記第一感 光層、及び前記支持体とをこの順に有する層構成、（3)前記基体、前記感光層、前 記バリア層、前記クッション層、及び前記支持体とをこの順に有する層構成、並びに（ 4)前記基体、前記第二感光層、前記バリア層、前記第一感光層、及び前記支持体と をこの順に有する層構成が好ま 、。  [0092] The layer structure of the laminate includes at least the second layer and the first layer in this order on a substrate, for example, (1) the substrate, the photosensitive layer, the cushion layer, And (2) a layer configuration having the substrate, the second photosensitive layer, the first photosensitive layer, and the support in this order, and (3) the substrate, the photosensitive layer. A layer structure including the layer, the barrier layer, the cushion layer, and the support in this order; and (4) the base, the second photosensitive layer, the barrier layer, the first photosensitive layer, and the support. A layer structure having and in this order is preferred.
[0093] 前記積層体の形成方法としては、特に制限はなぐ目的に応じて適宜選択すること ができるが、前記基体上に前記パターン形成材料を加熱及び加圧の少なくともいず れかを行!、ながら積層することが好ま 、。  [0093] The method of forming the laminate can be appropriately selected according to the purpose without any particular limitation, but at least one of heating and pressurizing the pattern forming material on the substrate is performed! While preferred, laminating.
前記加熱温度としては、前記第二の層のガラス転移温度を超える温度である限り、 特に制限はなぐ適宜選択することができ、例えば、 40〜150°Cが好ましい。  The heating temperature can be appropriately selected without particular limitation as long as the temperature exceeds the glass transition temperature of the second layer, and is preferably 40 to 150 ° C., for example.
前記加圧の圧力としては、特に制限はなぐ目的に応じて適宜選択することができ る力 f列; tは、、 0. 1〜1. OMPa力好ましく、 0. 2〜0. 8MPa力 ^より好まし!/ヽ。  The pressure of the pressurization is a force that can be appropriately selected according to the purpose for which there is no particular limitation. F column; t is preferably 0.1 to 1. OMPa force, 0.2 to 0.8 MPa force ^ More preferred! / ヽ.
[0094] 前記加熱及び加圧の少なくともいずれかを行う装置としては、特に制限はなぐ目 的に応じて適宜選択することができ、例えば、ラミネーター、真空ラミネーターなどが 好適に挙げられる。  [0094] The apparatus for performing at least one of heating and pressurization can be appropriately selected according to the purpose of restriction, and examples thereof include a laminator and a vacuum laminator.
[0095] 前記加熱及び加圧の少なくともいずれかを行う装置としては、特に制限はなぐ目 的に応じて適宜選択することができ、例えば、ラミネーター（例えば、大成ラミネータ 社製、 VP— Π)などが好適に挙げられる。  [0095] The apparatus for performing at least one of the heating and pressurization can be appropriately selected according to the purpose of restriction, such as a laminator (for example, VP-— manufactured by Taisei Laminator Co., Ltd.) Are preferable.
[0096] 前記積層体への露光としては、特に制限はなぐ目的に応じて適宜選択することが でき、例えば、前記支持体、クッション層及びバリア層を介して前記感光層を露光し てもよぐ前記支持体、クッション層及びバリア層を剥離した後、前記感光層を露光し てもよい。  [0096] The exposure of the laminate can be appropriately selected according to the purpose without any particular limitation. For example, the photosensitive layer may be exposed through the support, the cushion layer, and the barrier layer. After the support, cushion layer and barrier layer are peeled off, the photosensitive layer may be exposed.
[0097] 前記露光としては、特に制限はなぐ目的に応じて適宜選択することができ、デジタ ル露光、アナログ露光等が挙げられる力 これらの中でもデジタル露光が好ましい。  [0097] The exposure can be appropriately selected according to the purpose for which there is no particular limitation, and powers such as digital exposure, analog exposure, etc. Among these, digital exposure is preferable.
[0098] 前記デジタル露光としては、特に制限はなぐ目的に応じて適宜選択することがで きるが、例えば、形成するパターン形成情報に基づいて制御信号を生成し、該制御 信号に応じて変調させた光を用いて行うことが好まし 、。 [0098] The digital exposure can be appropriately selected according to the purpose without particular limitation. For example, it is preferable to generate a control signal based on the pattern formation information to be formed, and to use light modulated in accordance with the control signal.
[0099] 前記デジタル露光の手段としては、特に制限はなぐ目的に応じて適宜選択するこ とができるが、例えば、光を照射する光照射手段、形成するパターン情報に基づいて 該光照射手段から照射される光を変調させる光変調手段などが挙げられる。  [0099] The digital exposure means can be appropriately selected according to the purpose without any particular limitation. For example, the light irradiation means for irradiating light, and the light irradiation means based on the pattern information to be formed. Examples thereof include a light modulation unit that modulates the irradiated light.
[0100] <光変調手段 >  [0100] <Light modulation means>
前記光変調手段としては、光を変調することができる限り、特に制限はなぐ目的に 応じて適宜選択することができ、例えば、 n個の描素部を有することが好ましい。 前記 n個の描素部を有する光変調手段としては、特に制限はなぐ目的に応じて適 宜選択することができるが、例えば、空間光変調素子が好ましい。  The light modulating means can be appropriately selected according to the purpose without any limitation as long as light can be modulated. For example, the light modulating means preferably has n pixel portions. The light modulation means having the n picture elements can be appropriately selected according to the purpose without any particular limitation, and for example, a spatial light modulation element is preferable.
[0101] 前記空間光変調素子としては、例えば、デジタル ·マイクロミラー ·デバイス (DMD) 、 MEMS (Micro Electro Mechanical Systems)タイプの空間光変調素子（S LM ; Special Light Modulator)、電気光学効果により透過光を変調する光学素 子（PLZT素子）、液晶光シャツタ（FLC)などが挙げられ、これらの中でも DMDが好 適に挙げられる。  [0101] Examples of the spatial light modulator include a digital micromirror device (DMD), a MEMS (Micro Electro Mechanical Systems) type spatial light modulator (SLM; Special Light Modulator), and transmission by an electro-optic effect. Examples include optical elements that modulate light (PLZT elements) and liquid crystal light shirts (FLC). Among these, DMD is preferred.
[0102] また、前記光変調手段は、形成するパターン情報に基づいて制御信号を生成する パターン信号生成手段を有することが好ましい。この場合、前記光変調手段は、前記 パターン信号生成手段が生成した制御信号に応じて光を変調させる。  [0102] Further, it is preferable that the light modulation means includes pattern signal generation means for generating a control signal based on pattern information to be formed. In this case, the light modulating means modulates light according to the control signal generated by the pattern signal generating means.
前記制御信号としては、特に制限はなぐ目的に応じて適宜選択することができ、 例えば、デジタル信号が好適に挙げられる。  The control signal can be appropriately selected according to the purpose for which there is no particular limitation. For example, a digital signal is preferably used.
[0103] 前記光変調手段は、特開 2005— 258431号公報の段落 0016から 0047に記載さ れて 、る手段などが挙げられる。  [0103] Examples of the light modulation means include those described in paragraphs 0016 to 0047 of JP-A-2005-258431.
[0104] <光照射手段 >  [0104] <Light irradiation means>
前記光照射手段としては、特に制限はなぐ目的に応じて適宜選択することができ 、例えば、（超)高圧水銀灯、キセノン灯、カーボンアーク灯、ハロゲンランプ、複写機 用などの蛍光管、 LED,半導体レーザ等の公知光源、又は 2以上の光を合成して照 射可能な手段が挙げられ、これらの中でも 2以上の光を合成して照射可能な手段が 好ましい。 前記光照射手段から照射される光としては、例えば、支持体を介して光照射を行う 場合には、該支持体を透過し、かつ用いられる光重合開始剤や増感剤を活性化す る電磁波、紫外から可視光線、電子線、 X線、レーザ光などが挙げられ、これらの中 でもレーザ光が好ましぐ 2以上の光を合成したレーザ (以下、「合波レーザ」と称する ことがある）がより好ましい。また支持体を剥離して力も光照射を行う場合でも、同様の 光を用いることができる。 The light irradiation means can be appropriately selected according to the purpose without any particular limitation. For example, (ultra) high pressure mercury lamp, xenon lamp, carbon arc lamp, halogen lamp, copier, etc. fluorescent tube, LED, A known light source such as a semiconductor laser or means capable of combining and irradiating two or more lights can be mentioned. Among these, means capable of combining and irradiating two or more lights are preferable. The light emitted from the light irradiation means is, for example, an electromagnetic wave that passes through the support and activates the photopolymerization initiator and sensitizer used when the light is irradiated through the support. In particular, ultraviolet to visible light, electron beams, X-rays, laser light, etc. are mentioned, and among these, laser light is preferred. Laser that combines two or more lights (hereinafter sometimes referred to as “combined laser”) ) Is more preferable. Even when the support is peeled off and the light is irradiated with light, the same light can be used.
[0105] 前記紫外力も可視光線の波長としては、例えば、 300〜1500nmが好ましぐ 320 〜800mn力より好ましく、 330ηπ！〜 650mn力 ^特に好まし!/、。 [0105] As the wavelength of the visible light, the ultraviolet power is preferably 300 to 1500 nm, more preferably 320 to 800 mn, and 330 ηπ! ~ 650mn force ^ especially preferred!
前記レーザ光の波長としては、例えば、 200〜1500nm力 S好ましく、 300〜800nm 力 Sより好ましく、 330ΠΠ！〜 500mn力更に好ましく、 400ηπ！〜 450mn力 ^特に好まし!/、  The wavelength of the laser beam is, for example, preferably 200 to 1500 nm force S, more preferably 300 to 800 nm force S, and 330 mm! ~ 500mn force more preferred, 400ηπ! ~ 450mn power ^ especially preferred! /,
[0106] 前記合波レーザを照射可能な手段としては、例えば、複数のレーザと、マルチモー ド光ファイバと、該複数のレーザ力 それぞれ照射したレーザ光を集光して前記マル チモード光ファイバに結合させる集合光学系とを有する手段が好ましい。 [0106] As means capable of irradiating the combined laser, for example, a plurality of lasers, a multimode optical fiber, and a laser beam irradiated with each of the plurality of laser forces are condensed and coupled to the multimode optical fiber. Means having a collective optical system to be used is preferable.
[0107] 前記合波レーザを照射可能な手段 (ファイバアレイ光源）としては、例えば、特開 20 05— 258431号公報の段落 0110から 0146に記載された手段などが挙げられる。 前記露光は、前記変調させた光を、マイクロレンズアレイを通して行うことが好ましく 、更にアパーチャアレイ、結像光学系等などを通して行ってもよい。  Examples of means (fiber array light source) that can irradiate the combined laser include means described in paragraphs 0110 to 0146 of JP-A No. 2005-258431. The exposure is preferably performed using the modulated light through a microlens array, and may be performed through an aperture array, an imaging optical system, or the like.
[0109] 前記マイクロレンズアレイとしては、特に制限はなぐ目的に応じて適宜選択するこ とができる力 例えば、前記描素部における出射面の歪みによる収差を補正可能な 非球面を有するマイクロレンズを配列したものが好適に挙げられる。  [0109] The microlens array is a force that can be appropriately selected according to the purpose without any particular limitation. For example, a microlens having an aspherical surface capable of correcting aberration due to distortion of the exit surface in the pixel portion. Preferred are those arranged.
[0110] 前記非球面としては、特に制限はなぐ目的に応じて適宜選択することができるが、 例えば、トーリック面が好ましい。  [0110] The aspherical surface can be appropriately selected according to the purpose for which there is no particular limitation. For example, a toric surface is preferable.
[0111] 前記マイクロレンズアレイ、前記アパーチャアレイ、及び前記結像光学系等の手段 としては、 f列えば、、特開 2005— 258431号公報の段落 0050力ら 0066に記載され た手段が挙げられる。  [0111] Examples of the means such as the microlens array, the aperture array, and the imaging optical system include the means described in Paragraph 0050 Force et al. .
[0112] 特開 2005— 258431号公報に記載された実施形態では、マイクロレンズ 55aの光 出射側の端面が非球面（トーリック面）とされているが、 2つの光通過端面の一方を球 面とし、他方をシリンドリカル面としたマイクロレンズからマイクロレンズアレイを構成し て、上記実施形態と同様の効果を得ることもできる。 [0112] In the embodiment described in Japanese Patent Laid-Open No. 2005-258431, the light of the microlens 55a is used. Although the end surface on the emission side is an aspheric surface (toric surface), a microlens array is configured by using microlenses in which one of the two light passing end surfaces is a spherical surface and the other is a cylindrical surface. Similar effects can be obtained.
[0113] さらに、以上説明した実施形態においては、マイクロレンズアレイのマイクロレンズ 力 マイクロミラーの反射面の歪みによる収差を補正する非球面形状とされて 、るが 、このような非球面形状を採用する代わりに、マイクロレンズアレイを構成する各マイク 口レンズに、マイクロミラーの反射面の歪みによる収差を補正する屈折率分布を持た せても、同様の効果を得ることができる。  Furthermore, in the embodiment described above, the microlens force of the microlens array is an aspherical shape that corrects aberration due to distortion of the reflecting surface of the micromirror, but such an aspherical shape is adopted. Instead, the same effect can be obtained by providing each microphone lens constituting the microlens array with a refractive index distribution that corrects aberration due to distortion of the reflection surface of the micromirror.
[0114] そのようなマイクロレンズの一例を図 1及び図 2に示す。図 1及び図 2はそれぞれ、こ のマイクロレンズ 155aの正面形状及び側面形状を示すものであり、図示の通りこの マイクロレンズ 155aの外形形状は平行平板状である。なお、同図における x、 y方向 は、既述した通りである。  [0114] An example of such a microlens is shown in Figs. FIG. 1 and FIG. 2 respectively show the front shape and the side shape of the micro lens 155a. As shown in the drawing, the external shape of the micro lens 155a is a parallel plate shape. The x and y directions in the figure are as described above.
[0115] また、図 1及び図 2は、このマイクロレンズ 155aによる上記 X方向及び y方向に平行 な断面内におけるレーザ光 Bの集光状態を概略的に示している。このマイクロレンズ 155aは、光軸 O力 外方に向かって次第に増大する屈折率分布を有するものであり 、同図においてマイクロレンズ 155a内に示す破線は、その屈折率が光軸 O力も所定 の等ピッチで変化した位置を示している。図示の通り、 X方向に平行な断面内と y方 向に平行な断面内とを比較すると、後者の断面内の方がマイクロレンズ 155aの屈折 率変化の割合がより大であって、焦点距離がより短くなつている。このような屈折率分 布型レンズから構成されるマイクロレンズアレイを用いても、前記マイクロレンズアレイ 55を用いる場合と同様の効果を得ることが可能である。  1 and 2 schematically show the condensing state of the laser beam B in the cross section parallel to the X direction and the y direction by the microlens 155a. The microlens 155a has a refractive index distribution that gradually increases toward the outside of the optical axis O force. The broken line shown in the microlens 155a in FIG. The position changed with the pitch is shown. As shown in the figure, 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 getting shorter. Even when a microlens array composed of such a refractive index distribution type lens is used, the same effect as in the case of using the microlens array 55 can be obtained.
[0116] なお、図 3〜6に示したマイクロレンズ 55aのように面形状を非球面としたマイクロレ ンズにおいて、併せて上述のような屈折率分布を与え、面形状と屈折率分布の双方 によって、マイクロミラー 62の反射面の歪みによる収差を補正するようにしてもょ 、。  [0116] In the microlens having the aspherical surface shape like the microlens 55a shown in Figs. 3 to 6, the above refractive index distribution is given together, and both the surface shape and the refractive index distribution are provided. However, it is possible to correct the aberration caused by distortion of the reflecting surface of the micromirror 62.
[0117] また、上記の実施形態では、 DMD50を構成するマイクロミラー 62の反射面の歪み による収差を補正しているが、 DMD以外の空間光変調素子を用いる本発明のバタ ーン形成方法においても、その空間光変調素子の描素部の面に歪みが存在する場 合は、本発明を適用してその歪みによる収差を補正し、ビーム形状に歪みが生じるこ とを防止可能である。 [0117] In the above embodiment, the aberration due to the distortion of the reflection surface of the micromirror 62 constituting the DMD 50 is corrected. However, in the pattern forming method of the present invention using a spatial light modulation element other than the DMD. However, if there is distortion on the surface of the pixel part of the spatial light modulator, the present invention is applied to correct the aberration caused by the distortion, and the beam shape may be distorted. Can be prevented.
[0118] 次に、前記結像光学系について更に説明する。  [0118] Next, the imaging optical system will be further described.
前記露光ヘッドでは、図 7に示すように、光照射手段 144からレーザ光が照射され ると、 DMD50によりオン方向に反射される光束線の断面積力 レンズ系 454、 458 により数倍 (例えば、 2倍）に拡大される。拡大されたレーザ光は、マイクロレンズァレ ィ 472の各マイクロレンズにより DMD50の各描素部に対応して集光され、ァパーチ ャアレイ 476の対応するアパーチャを通過する。アパーチャを通過したレーザ光は、 レンズ系 480、 482【こ Jり被露光面 56上【こ結像される。  In the exposure head, as shown in FIG. 7, when laser light is irradiated from the light irradiation means 144, the cross-sectional area force of the light beam reflected by the DMD 50 in the ON direction is several times by the lens systems 454 and 458 (for example, 2x). The expanded laser light is condensed by each microlens of the microlens array 472 so as to correspond to each pixel part of the DMD 50 and passes through a corresponding aperture of the aperture array 476. The laser beam that has passed through the aperture is imaged on the lens system 480, 482 [exposed surface 56].
[0119] この結像光学系では、 DMD50により反射されたレーザ光は、拡大レンズ 454、 45 8により数倍に拡大されて被露光面 56に投影されるので、全体の画像領域が広くな る。このとき、マイクロレンズアレイ 472及びアパーチャアレイ 476が配置されていなけ れば、図 8に示すように、被露光面 56に投影される各ビームスポット BSの 1描素サイ ズ (スポットサイズ）が露光エリア 468のサイズに応じて大きなものとなり、露光エリア 4 68の鮮鋭度を表す MTF (Modulation Transfer Function)特性が低下する。  In this imaging optical system, the laser beam reflected by the DMD 50 is magnified several times by the magnifying lenses 454 and 458 and projected onto the exposed surface 56, so that the entire image area is widened. . At this time, if the microlens array 472 and the aperture array 476 are not arranged, one pixel size (spot size) of each beam spot BS projected onto the exposure surface 56 is exposed as shown in FIG. The size increases according to the size of area 468, and the MTF (Modulation Transfer Function) characteristic representing the sharpness of exposure area 468 is degraded.
[0120] 一方、マイクロレンズアレイ 472及びアパーチャアレイ 476を配置した場合には、 D MD50により反射されたレーザ光は、マイクロレンズアレイ 472の各マイクロレンズに より DMD50の各描素部に対応して集光される。これにより、図 9に示すように、露光 エリアが拡大された場合でも、各ビームスポット BSのスポットサイズを所望の大きさ（ 例えば、 lO ^ mX lO ^ m)に縮小することができ、 MTF特性の低下を防止して高精 細な露光を行うことができる。なお、露光エリア 468が傾いているのは、描素間の隙間 を無くす為に DMD50を傾けて配置しているからである。  On the other hand, when the microlens array 472 and the aperture array 476 are arranged, the laser light reflected by the DMD50 corresponds to each pixel part of the DMD50 by each microlens of the microlens array 472. Focused. As a result, as shown in FIG. 9, even when the exposure area is enlarged, the spot size of each beam spot BS can be reduced to a desired size (for example, lO ^ mX lO ^ m). It is possible to perform high-precision exposure by preventing a decrease in the exposure time. The exposure area 468 is inclined because the DMD 50 is inclined to eliminate the gap between the pixels.
[0121] また、マイクロレンズの収差によるビームの太りがあっても、アパーチャアレイによつ て被露光面 56上でのスポットサイズが一定の大きさになるようにビームを整形するこ とができると共に、各描素に対応して設けられたアパーチャアレイを通過させることに より、隣接する描素間でのクロストークを防止することができる。  [0121] Even if the beam is thick due to the aberration of the microlens, the aperture array can shape the beam so that the spot size on the exposed surface 56 is constant. At the same time, by passing through an aperture array provided corresponding to each pixel, crosstalk between adjacent pixels can be prevented.
[0122] 更に、光照射手段 144に後述する高輝度光源を使用することにより、レンズ 458か らマイクロレンズアレイ 472の各マイクロレンズに入射する光束の角度が小さくなるの で、隣接する描素の光束の一部が入射するのを防止することができる。即ち、高消光 比を実現することができる。 [0122] Furthermore, by using a high-intensity light source, which will be described later, as the light irradiation means 144, the angle of the light beam incident on each microlens of the microlens array 472 from the lens 458 becomes small. It is possible to prevent a part of the light beam from entering. That is, high quenching Ratio can be realized.
[0123] <その他の光学系 >  [0123] <Other optical systems>
本発明のパターン形成方法では、公知の光学系の中から適宜選択したその他の光 学系と併用してもよぐ例えば、 1対の組合せレンズからなる光量分布補正光学系な どが挙げられる。  The pattern forming method of the present invention 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.
前記光量分布補正光学系は、光軸に近い中心部の光束幅に対する周辺部の光束 幅の比が入射側に比べて出射側の方が小さくなるように各出射位置における光束幅 を変化させて、光照射手段からの平行光束を DMDに照射するときに、被照射面で の光量分布が略均一になるように補正する。  The light quantity distribution correcting optical system changes the light flux width at each exit position so that the ratio of the light flux width in the peripheral portion to the light flux width in the central portion close to the optical axis is smaller on the exit side than on the entrance side. When the DMD is irradiated with the parallel light beam from the light irradiation means, the light amount distribution on the irradiated surface is corrected so as to be substantially uniform.
前記光量分布補正光学系としては、例えば、特開 2005— 258431号公報の段落 0090から 0105に記載された手段などが挙げられる。  Examples of the light quantity distribution correcting optical system include means described in paragraphs 0090 to 0105 of JP-A-2005-258431.
[0124] [その他工程] [0124] [Other processes]
前記その他の工程としては、特に制限はなぐ公知のパターン形成における工程の 中から適宜選択することが挙げられる力 例えば、現像工程、エッチング工程、メツキ 工程などが挙げられる。これらは、 1種単独で使用してもよぐ 2種以上を併用してもよ い。  As the other steps, there is a force that can be appropriately selected from known pattern formation steps without particular limitations. Examples thereof include a development step, an etching step, and a plating step. These may be used alone or in combination of two or more.
前記現像工程は、前記露光工程により前記パターン形成材料における感光層を露 光し、該感光層の露光した領域を硬化させた後、未硬化領域を除去することにより現 像し、ノターンを形成する工程である。  The developing step exposes the photosensitive layer in the pattern forming material in the exposing step, cures the exposed region of the photosensitive layer, and then removes the uncured region to form an image, thereby forming a no-turn. It is a process.
[0125] 前記現像工程は、例えば、現像手段により好適に実施することができる。 [0125] The development step can be preferably carried out, for example, by a developing means.
前記現像手段としては、現像液を用いて現像することができる限り特に制限はなぐ 目的に応じて適宜選択することができるが、例えば、前記現像液を噴霧する手段、前 記現像液を塗布する手段、前記現像液に浸漬させる手段などが挙げられる。これら は、 1種単独で使用してもよぐ 2種以上を併用してもよい。  The developing means is not particularly limited as long as it can be developed using a developer, and can be appropriately selected according to the purpose. For example, the means for spraying the developer, and applying the developer And means for immersing in the developer. These may be used alone or in combination of two or more.
また、前記現像手段は、前記現像液を交換する現像液交換手段、前記現像液を供 給する現像液供給手段などを有して ヽてもよ ヽ。  In addition, the developing unit may include a developing solution replacing unit that replaces the developing solution, a developing solution supply unit that supplies the developing solution, and the like.
[0126] 前記現像液としては、特に制限はなぐ目的に応じて適宜選択することができるが、 例えば、アルカリ性液、水系現像液、有機溶剤などが挙げられ、これらの中でも、弱 アルカリ性の水溶液が好ましい。該弱アルカリ性液の塩基成分としては、例えば、水 酸化リチウム、水酸化ナトリウム、水酸化カリウム、炭酸リチウム、炭酸ナトリウム、炭酸 カリウム、炭酸水素リチウム、炭酸水素ナトリウム、炭酸水素カリウム、リン酸ナトリウム 、リン酸カリウム、ピロリン酸ナトリウム、ピロリン酸カリウム、硼砂などが挙げられる。 [0126] The developer can be appropriately selected depending on the purpose without any particular limitation, and examples thereof include alkaline solutions, aqueous developers, organic solvents, and the like. Alkaline aqueous solutions are preferred. Examples of the basic component of the weak alkaline liquid 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.
[0127] 前記弱アルカリ性の水溶液の pHとしては、例えば、約 8〜12が好ましぐ約 9〜11 力 り好ましい。前記弱アルカリ性の水溶液としては、例えば、 0. 1〜5質量％の炭酸 ナトリウム水溶液又は炭酸カリウム水溶液などが挙げられる。  [0127] The pH of the weakly alkaline aqueous solution is more preferably about 9 to 11 force, for example, preferably about 8 to 12. Examples of the weak alkaline aqueous solution include 0.1 to 5% by mass of sodium carbonate aqueous solution or potassium carbonate aqueous solution.
前記現像液の温度としては、前記感光層の現像性に合わせて適宜選択することが できるが、例えば、約 25°C〜40°Cが好ましい。  The temperature of the developer can be appropriately selected according to the developability of the photosensitive layer, and for example, about 25 ° C. to 40 ° C. is preferable.
[0128] 前記現像液は、界面活性剤、消泡剤、有機塩基 (例えば、エチレンジァミン、ェタノ ールァミン、テトラメチルアンモ -ゥムハイドロキサイド、ジエチレントリァミン、トリェチ レンペンタミン、モルホリン、トリエタノールアミン等)や、現像を促進させるため有機溶 剤（例えば、アルコール類、ケトン類、エステル類、エーテル類、アミド類、ラタトン類 等)などと併用してもよい。また、前記現像液は、水又はアルカリ水溶液と有機溶剤を 混合した水系現像液であってもよぐ有機溶剤単独であってもよ 、。  [0128] The developer is a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.) In order to accelerate development, an organic solvent (for example, alcohols, ketones, esters, ethers, amides, latatones, etc.) may be used in combination. The developer may be an aqueous developer obtained by mixing water or an alkaline aqueous solution and an organic solvent, or may be an organic solvent alone.
[0129] 前記エッチング工程としては、公知のエッチング処理方法の中力 適宜選択した方 法により行うことができる。  [0129] The etching step can be performed by a method appropriately selected from among known etching methods.
前記エッチング処理に用いられるエッチング液としては、特に制限はなぐ 目的に 応じて適宜選択することができるが、例えば、前記金属層が銅で形成されている場合 には、塩化第二銅溶液、塩化第二鉄溶液、アルカリエッチング溶液、過酸化水素系 エッチング液などが挙げられ、これらの中でも、エッチングファクターの点力 塩ィ匕第 二鉄溶液が好ましい。  The etching solution used for the etching treatment can be appropriately selected according to the purpose without any particular limitation. For example, when the metal layer is formed of copper, a cupric chloride solution, Examples thereof include a ferric solution, an alkaline etching solution, and a hydrogen peroxide-based etching solution. Among these, a point strength of etching factor—a salty ferric solution is preferable.
前記エッチング工程によりエッチング処理した後に前記パターンを除去することによ り、前記基体の表面に永久パターンを形成することができる。  A permanent pattern can be formed on the surface of the substrate by removing the pattern after performing the etching process in the etching step.
前記永久パターンとしては、特に制限はなぐ 目的に応じて適宜選択することがで き、例えば、配線パターンなどが好適に挙げられる。  The permanent pattern is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include a wiring pattern.
[0130] 前記メツキ工程としては、公知のメツキ処理の中から適宜選択した適宜選択した方 法により行うことができる。 前記メツキ処理としては、例えば、硫酸銅メツキ、ピロリン酸銅メツキ等の銅メツキ、ハ ィフローはんだメツキ等のはんだメツキ、ワット浴 (硫酸ニッケル—塩ィ匕ニッケル)メツキ 、スルファミン酸ニッケル等のニッケルメツキ、ハード金メッキ、ソフト金メッキ等の金メッ キなど処理が挙げられる。 [0130] 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, nickel plating such as watt bath (nickel sulfate-salt nickel nickel) plating, and nickel sulfamate. And gold plating such as hard gold plating and soft gold plating.
前記メツキ工程によりメツキ処理した後に前記パターンを除去することにより、また更 に必要に応じて不要部をエッチング処理等で除去することにより、前記基体の表面に 永久パターンを形成することができる。  A permanent pattern can be formed on the surface of the substrate by removing the pattern after performing a plating process in the plating process, and further removing unnecessary portions by an etching process or the like as necessary.
[0131] 〔プリント配線板の製造方法〕  [Manufacturing Method of Printed Wiring Board]
本発明のパターン形成方法は、プリント配線板の製造、特にスルーホール又はビア ホールなどのホール部を有するプリント配線板の製造に好適に用いることができる。 以下、本発明のパターン形成方法を利用したプリント配線板の製造方法の一例につ いて説明する。  The pattern forming method of the present invention can be suitably used for the production of a printed wiring board, particularly for the production of a printed wiring board having a hole portion such as a through hole or a via hole. Hereinafter, an example of a method for producing a printed wiring board using the pattern forming method of the present invention will be described.
[0132] プリント配線板の製造方法  [0132] Method for manufacturing printed wiring board
特に、スルーホール又はビアホールなどのホール部を有するプリント配線板の製造 方法としては、（1)前記基体としてホール部を有するプリント配線板形成用基板上に 、前記パターン形成材料を、その第二の層 (感光層、又は第二感光層）が前記基体 側となる位置関係にて積層して積層体形成し、 (2)前記積層体の前記基体とは反対 の側から、所望の領域に光照射行い感光層を硬化させ、（3)前記積層体から前記パ ターン形成材料における支持体、及びクッション層を有する場合はクッション層を除 去し、（4)前記積層体における感光層を現像し、該積層体中の未硬化部分を除去す ることによりパターンを形成することができる。  In particular, as a method for producing a printed wiring board having a hole portion such as a through hole or a via hole, (1) the second pattern forming material is placed on the printed wiring board forming substrate having the hole portion as the base. Layers (photosensitive layer or second photosensitive layer) are laminated in a positional relationship to be on the substrate side, and (2) light is applied to a desired region from the side of the laminate opposite to the substrate. The photosensitive layer is cured by irradiation, (3) the support in the pattern forming material and the cushion layer are removed from the laminate when the cushion layer is provided, and (4) the photosensitive layer in the laminate is developed. The pattern can be formed by removing the uncured portion in the laminate.
[0133] なお、前記クッション層がアルカリ性液に対して膨潤性乃至可溶性である場合には 、前記クッション層の除去は、特に制限されず、前記（2)以降のどこで行っても良いが 、前記クッション層がアルカリ性液に不溶性である場合には、前記 (4)以前に除去さ れることが好ましい。  [0133] When the cushion layer is swellable or soluble in an alkaline liquid, the removal of the cushion layer is not particularly limited, and may be performed anywhere after (2). When the cushion layer is insoluble in the alkaline liquid, it is preferably removed before (4).
また、前記（3)における前記支持体の除去は、前記（2)と前記 (4)との間で行う代 わりに、前記（1)と前記（2)との間で行ってもよい。  Further, the removal of the support in (3) may be performed between (1) and (2) instead of between (2) and (4).
さらに、前記パターン形成材料力 Sクッション層とバリア層とを有する場合、該バリア層 は（3)において前記支持体とともに除去されてもよぐ（4)において現像時に除去さ れてもよい。 Further, when the pattern forming material force S has a cushion layer and a barrier layer, the barrier layer May be removed together with the support in (3) or may be removed during development in (4).
[0134] その後、プリント配線板を得るには、前記形成したパターンを用いて、前記プリント 配線板形成用基板をエッチング処理又はメツキ処理する方法 (例えば、公知のサブト ラタティブ法又はアディティブ法 (例えば、セミアディティブ法、フルアディティブ法)） により処理すればよい。これらの中でも、工業的に有利なテンティングでプリント配線 板を形成するためには、前記サブトラクティブ法が好ましい。前記処理後プリント配線 板形成用基板に残存する硬化榭脂は剥離させ、また、前記セミアディティブ法の場 合は、剥離後さらに銅薄膜部をエッチングすることにより、所望のプリント配線板を製 造することができる。また、多層プリント配線板も、前記プリント配線板の製造法と同様 に製造が可能である。  [0134] Thereafter, in order to obtain a printed wiring board, a method of etching or plating the printed wiring board forming substrate using the formed pattern (for example, a known subtractive method or additive method (for example, Semi-additive method and full additive method)). Among these, the subtractive method is preferable in order to form a printed wiring board with industrially advantageous tenting. After the treatment, the cured resin remaining on the printed wiring board forming substrate is peeled off. In the case of the semi-additive method, the copper thin film portion is further etched after the peeling to produce a desired printed wiring board. can do. A multilayer printed wiring board can also be manufactured in the same manner as the printed wiring board manufacturing method.
[0135] 次に、前記パターン形成材料を用いたスルーホールを有するプリント配線板の製造 方法について、更に説明する。  [0135] Next, a method for producing a printed wiring board having through holes using the pattern forming material will be further described.
[0136] まずスルーホールを有し、表面が金属メツキ層で覆われたプリント配線板形成用基 板を用意する。前記プリント配線板形成用基板としては、例えば、銅張積層基板及び ガラス一エポキシなどの絶縁基材に銅メツキ層を形成した基板、又はこれらの基板に 層間絶縁膜を積層し、銅メツキ層を形成した基板 (積層基板)を用いることができる。  [0136] First, a printed wiring board forming substrate having through holes and having a surface covered with a metal plating layer is prepared. As the printed wiring board forming substrate, for example, a copper clad laminated substrate and a substrate in which a copper plating layer is formed on an insulating base material such as glass-epoxy, or an interlayer insulating film is laminated on these substrates, and a copper plating layer is formed. A formed substrate (laminated substrate) can be used.
[0137] 次に、前記パターン形成材料上に保護フィルムを有する場合には、該保護フィルム を剥離して、前記パターン形成材料における第二の層 (感光層、又は第二感光層） が前記プリント配線板形成用基板の表面に接するようにして加圧ローラを用いて圧着 する (積層工程)。これにより、前記プリント配線板形成用基板と前記積層体とをこの 順に有する積層体が得られる。  [0137] Next, in the case where a protective film is provided on the pattern forming material, the protective film is peeled off, and the second layer (photosensitive layer or second photosensitive layer) in the pattern forming material becomes the print Pressure is applied using a pressure roller so as to be in contact with the surface of the wiring board forming substrate (lamination process). Thereby, the laminated body which has the said board | substrate for printed wiring board formation and the said laminated body in this order is obtained.
前記パターン形成材料の積層温度としては、前記第二の層のガラス転移温度を超 える限り特に制限はなぐ適宜選択することができる力 例えば、 40〜150°Cが好ま しい。  The lamination temperature of the pattern forming material is preferably a force that can be appropriately selected as long as it exceeds the glass transition temperature of the second layer. For example, 40 to 150 ° C. is preferable.
前記圧着ロールのロール圧としては、特に制限はなぐ適宜選択することができるが 、例えば、 0. 1〜： LMPaが好ましい。  The roll pressure of the pressure-bonding roll is not particularly limited and can be appropriately selected. For example, 0.1 to LMPa is preferable.
前記圧着の速度としては、特に制限はなぐ適宜選択することができるが、 l〜3m z分が好ましい。 The speed of the crimping can be selected as appropriate without any particular limitation. z minutes are preferred.
また、前記プリント配線板形成用基板を予備加熱しておいてもよぐまた、減圧下で 積層してちょい。  Alternatively, the printed wiring board forming substrate may be preheated or laminated under reduced pressure.
[0138] 次に、前記積層体の基体とは反対側の面から、光を照射して感光層を硬化させる。  Next, the photosensitive layer is cured by irradiating light from the surface of the laminate opposite to the substrate.
なおこの際、必要に応じて (例えば、支持体の光透過性が不十分な場合など)前記 支持体を剥離して力も露光を行ってもよい。このとき、支持体とともに、前記クッション 層、及び前記クッション層と前記感光層との間にバリア層を形成した場合には前記バ リア層を剥離して力も露光を行ってもよい。  At this time, if necessary (for example, when the light transmittance of the support is insufficient), the support may be peeled off and the force may be exposed. At this time, when a barrier layer is formed between the cushion layer and the cushion layer and the photosensitive layer together with the support, the barrier layer may be peeled off and the force may be exposed.
[0139] この時点で、前記支持体、前記クッション層、及び前記バリア層を未だ剥離して 、な い場合には、前記積層体から少なくとも前記支持体を剥離する (剥離工程)。  At this point, if the support, the cushion layer, and the barrier layer are not yet peeled, at least the support is peeled from the laminate (peeling step).
[0140] 次に、前記プリント配線板形成用基板上の感光層の未硬化領域を、適当な現像液 にて溶解除去して、配線パターン形成用の硬化層とスルーホールの金属層保護用 硬化層のパターンを形成し、前記プリント配線板形成用基板の表面に金属層を露出 させる（現像工程)。  [0140] Next, the uncured region of the photosensitive layer on the printed wiring board forming substrate is dissolved and removed with an appropriate developer, and the cured layer for forming the wiring pattern and the curing for protecting the metal layer of the through hole are performed. A layer pattern is formed to expose the metal layer on the surface of the printed wiring board forming substrate (development process).
[0141] また、現像後に必要に応じて後加熱処理や後露光処理によって、硬化部の硬化反 応を更に促進させる処理をおこなってもよ 、。現像は上記のようなウエット現像法であ つてもよく、ドライ現像法であってもよい。  [0141] Further, after the development, if necessary, a post-heating treatment or a post-exposure treatment may be performed to further accelerate the curing reaction of the cured portion. The development may be a wet development method as described above or a dry development method.
[0142] 次いで、前記プリント配線板形成用基板の表面に露出した金属層をエッチング液 で溶解除去する（エッチング工程)。スルーホールの開口部は、硬化榭脂組成物 (テ ント膜)で覆われているので、エッチング液がスルーホール内に入り込んでスルーホ ール内の金属メツキを腐食することなぐスルーホールの金属メツキは所定の形状で 残ることになる。これより、前記プリント配線板形成用基板に配線パターンが形成され る。  Next, the metal layer exposed on the surface of the printed wiring board forming substrate is dissolved and removed with an etching solution (etching step). Since the opening of the through hole is covered with a cured resin composition (tent film), the metal coating of the through hole prevents the etching solution from entering the through hole and corroding the metal plating in the through hole. Will remain in the prescribed shape. Thereby, a wiring pattern is formed on the printed wiring board forming substrate.
[0143] 前記エッチング液としては、特に制限はなぐ 目的に応じて適宜選択することができ る力 例えば、前記金属層が銅で形成されている場合には、塩化第二銅溶液、塩ィ匕 第二鉄溶液、アルカリエッチング溶液、過酸ィ匕水素系エッチング液などが挙げられ、 これらの中でも、エッチングファクターの点から塩ィ匕第二鉄溶液が好ましい。  [0143] The etching solution is not particularly limited and can be appropriately selected depending on the purpose. For example, when the metal layer is formed of copper, a cupric chloride solution, salt solution Examples thereof include a ferric solution, an alkaline etching solution, a hydrogen peroxide-based etching solution, and the like. Among these, a salty ferric solution is preferable from the viewpoint of an etching factor.
[0144] 次に、強アルカリ水溶液などにて前記硬化層を剥離片として、前記プリント配線板 形成用基板から除去する (硬化物除去工程)。 [0144] Next, the printed wiring board is formed by using the hardened layer as a release piece with a strong alkaline aqueous solution or the like. Remove from the forming substrate (cured product removal step).
前記強アルカリ水溶液における塩基成分としては、特に制限はなぐ例えば、水酸 化ナトリウム、水酸ィ匕カリウムなどが挙げられる。  The base component in the strong alkaline aqueous solution is not particularly limited, and examples thereof include sodium hydroxide and potassium hydroxide.
前記強アルカリ水溶液の pHとしては、例えば、約 12〜14が好ましぐ約 13〜14が より好まし 、。  The pH of the strong alkaline aqueous solution is, for example, preferably about 13-14, more preferably about 12-14.
前記強アルカリ水溶液としては、特に制限はなぐ例えば、 1〜10質量％の水酸ィ匕 ナトリウム水溶液又は水酸ィ匕カリウム水溶液などが挙げられる。  The strong alkaline aqueous solution is not particularly limited, and examples thereof include 1 to 10% by mass of sodium hydroxide aqueous solution or potassium hydroxide aqueous solution.
[0145] また、プリント配線板は、多層構成のプリント配線板であってもよ 、。 [0145] The printed wiring board may be a multilayer printed wiring board.
なお、前記パターン形成材料は上記のエッチングプロセスのみでなぐメツキプロセ スに使用してもよい。前記メツキ法としては、例えば、硫酸銅メツキ、ピロリン酸銅メツキ 等の銅メツキ、ハイスローはんだメツキ等のはんだメツキ、ワット浴 (硫酸ニッケル—塩 ィ匕ニッケル）メツキ、スルファミン酸ニッケル等のニッケルメツキ、ハード金メッキ、ソフト 金メッキ等の金メッキなどが挙げられる。  Note that the pattern forming material may be used in a Meki process that is performed only by the etching process. Examples of the plating method include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-throw solder plating, watt bath (nickel sulfate-salt nickel) plating, nickel plating such as nickel sulfamate, Examples include hard gold plating and gold plating such as soft gold plating.
[0146] 本発明の前記パターン形成方法は、本発明の前記パターン形成材料を用いるため 、各種パターンの形成、配線パターン等の永久パターンの形成、カラーフィルタ、柱 材、リブ材、スぺーサ一、隔壁等の液晶構造部材の製造、ホログラム、マイクロマシン 、プルーフなどの製造に好適に使用することができ、特に高精細な配線パターンの 形成に好適に使用することができる。本発明のパターン形成装置は、本発明の前記 パターン形成材料を備えているため、各種パターンの形成、配線パターン等の永久 パターンの形成、カラーフィルタ、柱材、リブ材、スぺーサ一、隔壁等の液晶構造部 材の製造、ホログラム、マイクロマシン、プルーフなどの製造に好適に使用することが でき、特に高精細な配線パターンの形成に好適に用いることができる。  [0146] Since the pattern forming method of the present invention uses the pattern forming material of the present invention, formation of various patterns, formation of permanent patterns such as wiring patterns, color filters, pillar materials, rib materials, spacers, etc. It can be suitably used for the production of liquid crystal structural members such as partition walls, holograms, micromachines, proofs, etc., and can be particularly suitably used for the formation of high-definition wiring patterns. Since the pattern forming apparatus of the present invention includes the pattern forming material of the present invention, it forms various patterns, forms permanent patterns such as wiring patterns, color filters, pillar materials, rib materials, spacers, partition walls It can be suitably used for the production of liquid crystal structure members such as holograms, micromachines, and proofs, and can be particularly suitably used for the formation of high-definition wiring patterns.
実施例  Example
[0147] 以下、実施例により本発明を更に具体的に説明するが、本発明はこれらに限定さ れるものではない。  [0147] Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto.
[0148] (実施例 1) [Example 1]
パターン形成材料の製造  Manufacturing of pattern forming materials
前記支持体としての 16 μ m厚のポリエチレンテレフタレートフィルム（16QS52、東 レ (株)製）に、下記の組成からなる第一の層（第一感光層）用塗布液を塗布し、乾燥 させて 25 μ m厚の第一の層（第一感光層）を形成した。 16 μm thick polyethylene terephthalate film (16QS52, East (Co., Ltd.) is coated with a coating solution for the first layer (first photosensitive layer) having the following composition and dried to form the first layer (first photosensitive layer) 25 μm thick did.
[0149] 「第一の層 (第一感光層) rn rn  [0149] "First layer (first photosensitive layer) rn rn
•メチルメタタリレート /2 -ェチルへキシルアタリレート/ベンジルメタタリレート/ メタクリル酸共重合体 (共重合体組成 (モル比） =55Zll. 7/4. 5/28. 8、 質量平均分子量 = 90, 000、Tg = 70°C) 15質量部 •ドデカポリプロピレングリコールジアタリレート 6. 5質量部  • Methyl metatalylate / 2-ethylhexyl talylate / benzyl metatalylate / methacrylic acid copolymer (copolymer composition (molar ratio) = 55Zll. 7/4. 5 / 28.8, mass average molecular weight = 90, 000, Tg = 70 ° C) 15 parts by massDodeca polypropylene glycol ditalylate 6.5 parts by mass
.テトラエチレングリコールジメタタリレート 1. 5質量部 .Tetraethylene glycol dimetatalylate 1.5 parts by mass
•4, 4' -ビス（ジェチルァミノ）ベンゾフエノン 0. 04質量部 • 4,4'-Bis (jetylamino) benzophenone 0.04 parts by mass
'ベンゾフエノン 1. 0質量部  'Benzophenone 1.0 parts by mass
• 4 トルエンスルホンアミド 0. 5質量部  • 4 Toluenesulfonamide 0.5 parts by mass
'マラカイトグリーンシユウ酸塩 0. 02質量部  'Malachite green oxalate 0.02 parts by mass
•1, 2, 4-トリアゾール 0. 01質量部  • 1, 2, 4-triazole 0.01 parts by mass
•ロイコクリスタルバイオレット 0. 2質量部  • Royco Crystal Violet 0.2 parts by weight
•トリブロモメチルフエニルスルホン 0. 1質量部  • Tribromomethyl phenyl sulfone 0.1 parts by mass
ルェチル处ン 30 き β  Ruetil treatment 30
[0150] 形成した前記第一の層（第一感光層）の上に、下記の組成からなる第二の層（第二 感光層）用塗布液を塗布し、乾燥させて、 5 m厚の第二の層（第二感光層）を形成 した。  [0150] On the formed first layer (first photosensitive layer), a coating solution for the second layer (second photosensitive layer) having the following composition was applied and dried to give a thickness of 5 m. A second layer (second photosensitive layer) was formed.
[0151] 「第二の層 (第二感光層) rnm  [0151] "Second layer (second photosensitive layer) rnm
•メチルメタタリレート /2 -ェチルへキシルアタリレート/ベンジルメタタリレート/ メタクリル酸共重合体 (共重合体組成 (モル比） =40Z26. 7/4. 5/28. 8、 質量平均分子量 = 90, 000、Tg = 50°C) 15質量部 •ドデカポリプロピレングリコールジアタリレート 6. 5質量部  • Methyl metatalylate / 2-ethylhexyl talylate / benzyl metatalylate / methacrylic acid copolymer (copolymer composition (molar ratio) = 40Z26. 7/4. 5 / 28.8, mass average molecular weight = 90, 000, Tg = 50 ° C) 15 parts by massDodeca polypropylene glycol ditalylate 6.5 parts by mass
.テトラエチレングリコールジメタタリレート 1. 5質量部 .Tetraethylene glycol dimetatalylate 1.5 parts by mass
•4, 4' -ビス（ジェチルァミノ）ベンゾフエノン 0. 4質量部 • 4,4'-bis (jetylamino) benzophenone 0.4 parts by mass
'ベンゾフエノン 3. 0質量部  'Benzophenone 3.0 parts by mass
• 4 トルエンスルホンアミド 0. 5質量部 'マラカイトグリーンシユウ酸塩 0. 02質量部• 4 Toluenesulfonamide 0.5 parts by mass 'Malachite green oxalate 0.02 parts by mass
2, 4-トリアゾール 0. 01質量部 2,4-triazole 0.01 parts by mass
'ロイコクリスタルバイオレット 0. 2質量部  'Royco Crystal Violet 0.2 parts by weight
'トリブロモメチルフエ-ルスルホン 0. 1質量部  'Tribromomethylphenol sulfone 0.1 parts by mass
•メチルェチルケトン 10質量部  • 10 parts by mass of methyl ethyl ketone
ーメトキシ 2—プロパノール 20質量部  -Methoxy 2-propanol 20 parts by mass
[0152] 形成した前記第二の層（第二感光層）の上に、保護フィルムとして 12 m厚のポリ プロピレンフィルム (E501、王子製紙 (株)製)を積層し、パターン形成材料を製造し た。  [0152] A 12 m thick polypropylene film (E501, manufactured by Oji Paper Co., Ltd.) was laminated as a protective film on the formed second layer (second photosensitive layer) to produce a pattern forming material. It was.
前記第一の層 (第一感光層)及び前記第二の層 (第二感光層）の膜厚ムラを接触 式膜厚計 (サーフコム 1400D、（株)東京精密製)で測定したところ、いずれも ± 5% 以内であった。  When the film thickness unevenness of the first layer (first photosensitive layer) and the second layer (second photosensitive layer) was measured with a contact-type film thickness meter (Surfcom 1400D, manufactured by Tokyo Seimitsu Co., Ltd.) Also within ± 5%.
前記第一の層及び前記第二の層のガラス転移温度 (Tg)、及び 60°Cにおける溶融 粘度を下記の方法により測定した。結果を表 3に示す。  The glass transition temperature (Tg) and the melt viscosity at 60 ° C. of the first layer and the second layer were measured by the following methods. The results are shown in Table 3.
[0153] <ガラス転移温度 (Tg)の測定 > [0153] <Measurement of glass transition temperature (Tg)>
前記調製したパターン形成材料から、測定用サンプルとして前記第一の層及び前 記第二の層を、それぞれミクロトームで 10mgずつ採取し、これらを室温から 20°CZ 分の割合で昇温させ、示差走査熱量計を用いて比熱を測定し、前記比熱の変動が 起こる温度をガラス転移温度 (Tg)とした。  From the prepared pattern forming material, 10 mg each of the first layer and the second layer as a measurement sample was collected with a microtome, and the temperature was raised from room temperature at a rate of 20 ° CZ to obtain a differential. Specific heat was measured using a scanning calorimeter, and the temperature at which the specific heat fluctuation occurred was defined as the glass transition temperature (Tg).
[0154] <溶融粘度の測定 > [0154] <Measurement of melt viscosity>
前記第一の層及び前記第二の層を、 1cmの厚みで形成した測定用サンプルをそ れぞれ調製した。前記測定用サンプルを、ソリキッドメーター MR300 (レオロジ社製） を用い、室温から 20°CZ分の割合で昇温させて粘度測定を行った。  Samples for measurement in which the first layer and the second layer were formed with a thickness of 1 cm were prepared. The viscosity of the sample for measurement was measured by increasing the temperature from room temperature at a rate of 20 ° CZ using a solid meter MR300 (manufactured by Rheology).
[0155] 一積層体の製造 [0155] Production of single laminate
前記基体として、表面を研磨し、水洗し、乾燥させた銅張積層板 (スルーホールなし 、銅厚み 12 /z m)を調製し、該銅張積層板上に、前記パターン形成材料の第二の層 (第二感光層）が前記銅張積層板に接するようにして前記保護フィルムを剥がしなが ら、ラミネーター（MODEL8B— 720— PH、大成ラミネーター (株)製）を用いて積層 し、前記銅張積層板と、前記第二の層 (第二感光層）と、前記第一の層 (第一感光層 )と、前記支持体とがこの順に積層された積層体を調製した。圧着条件は、圧着ロー ル温度 105°C、圧着ロール圧力 3kgZcm2、圧着速度 lmZ分とした。 As the substrate, a copper-clad laminate (no through hole, copper thickness 12 / zm) whose surface was polished, washed with water and dried was prepared, and on the copper-clad laminate, a second of the pattern forming material was prepared. Laminator (MODEL8B-720-PH, manufactured by Taisei Laminator Co., Ltd.) while peeling off the protective film so that the layer (second photosensitive layer) is in contact with the copper clad laminate Then, a laminate was prepared in which the copper-clad laminate, the second layer (second photosensitive layer), the first layer (first photosensitive layer), and the support were laminated in this order. . The crimping conditions were a crimping roll temperature of 105 ° C, a crimping roll pressure of 3 kgZcm 2 , and a crimping speed of lmZ.
なお、前記銅張積層板における前記感光層を積層した方の面について、 JIS B 0 601に規定の最大高さ (Rz)を測定したところ、該 Rzは 3 μ mであった。  When the maximum height (Rz) defined in JIS B 0 601 was measured on the surface of the copper clad laminate on which the photosensitive layer was laminated, the Rz was 3 μm.
[0156] 前記積層体について、下記の方法により、膜厚のバラツキ、感度、解像度、及びェ ツチング線幅のバラツキの測定を行った。結果を表 4に示す。  [0156] With respect to the laminate, the following methods were used to measure variations in film thickness, sensitivity, resolution, and etching line width. The results are shown in Table 4.
[0157] <膜厚のバラツキの測定 >  [0157] <Measurement of film thickness variation>
前記基体上に積層された前記第一の層及び前記第二の層からなる膜の厚みを、 触針式膜厚計 (サーフコム 1400D、（株)東京精密製)を用い、 510 X 610cmの面 積で、基板表面における任意の 50点を測定した。この結果、膜厚のバラツキは、 ±0 . 1 μ mであつ 7こ。  The thickness of the film composed of the first layer and the second layer laminated on the substrate was measured using a stylus type film thickness meter (Surfcom 1400D, manufactured by Tokyo Seimitsu Co., Ltd.), and a surface of 510 X 610 cm In product, 50 arbitrary points on the substrate surface were measured. As a result, the film thickness variation is ± 0.1 μm.
[0158] <感度及び解像度の測定 >  [0158] <Measurement of sensitivity and resolution>
(1)最短現像時間の測定方法  (1) Measuring method of shortest development time
前記積層体力 前記支持体を剥がし取り、銅張積層板上の前記第一感光層上力 全面に 30°Cの 1質量0 /0炭酸ナトリウム水溶液を 0. 15MPaの圧力にてスプレーし、 炭酸ナトリウム水溶液のスプレー開始から銅張積層板上の前記感光層が溶解除去さ れるまでに要した時間を測定し、これを最短現像時間とした。この結果、前記最短現 像時間は、 25秒であった。 The peeled off the laminate strength the support, it was sprayed at a pressure of 0. 15 MPa 1 mass 0/0 aqueous sodium carbonate 30 ° C to the first photosensitive layer over the force over the entire surface of the copper-clad laminates, sodium carbonate The time required from the start of spraying of the aqueous solution until the photosensitive layer on the copper clad laminate was dissolved and removed was measured, and this was taken as the shortest development time. As a result, the shortest image time was 25 seconds.
[0159] (2)感度の測定  [0159] (2) Sensitivity measurement
前記積層体におけるパターン形成材料の感光層に対し、前記支持体側から、前記 光照射手段としての 405nmのレーザ光源を有する下記のパターン形成装置を用い て、 0. lmj/cm2から 21/2倍間隔で 100mj/cm2までの光エネルギー量の異なる 光を照射して露光し、前記感光層の一部の領域を硬化させた。室温にて 10分間静 置した後、前記積層体から前記支持体を剥がし取り、銅張積層板上の前記第一感光 層上から全面に、炭酸ナトリウム水溶液（30°C、 1質量％)をスプレー圧 0. 15MPaに て前記（1)で求めた最短現像時間の 2倍の時間スプレーし、未硬化の領域を溶解除 去して、残った硬化領域の厚みを測定した。 次いで、光の照射量と、硬化層の厚さとの関係をプロットして感度曲線を得た。この 結果、前記硬化層の厚みが前記第二の層の厚み（5 μ m)となったときの光エネルギ 一量 S 1は 4mjZcm2であり、硬化層の厚みが前記第一の層と第二の層との厚み（30 μ m)となったときの光エネルギー量 S2は 40mjZcm2、硬化層の厚みが前記第二の 層の厚み（5 μ m)を超えたときの光エネルギー量 S3は 14mjZcm2であった。 With respect to the photosensitive layer of the pattern forming material in the laminate, from the support side, the following pattern forming apparatus having a 405 nm laser light source as the light irradiating means is used, from 0. lmj / cm 2 to 2 1/2 Exposure was performed by irradiating with different light energy amounts up to 100 mj / cm 2 at double intervals to cure a part of the photosensitive layer. After standing at room temperature for 10 minutes, the support was peeled off from the laminate, and an aqueous sodium carbonate solution (30 ° C, 1% by mass) was applied to the entire surface from the first photosensitive layer on the copper clad laminate. Spraying was performed at a spray pressure of 0.15 MPa for twice the minimum development time determined in (1) above, and the uncured area was dissolved and removed, and the thickness of the remaining cured area was measured. Subsequently, the relationship between the light irradiation amount and the thickness of the cured layer was plotted to obtain a sensitivity curve. As a result, when the thickness of the hardened layer becomes the thickness of the second layer (5 μm), the amount of light energy S 1 is 4 mjZcm 2 , and the thickness of the hardened layer is the same as that of the first layer and the second layer. The amount of light energy S2 when the thickness with the second layer (30 μm) is 40 mjZcm 2 , and the amount of light energy when the thickness of the hardened layer exceeds the thickness of the second layer (5 μm) S3 Was 14 mjZcm 2 .
前記 S1は前記第二感光層を硬化させるために必要な光エネルギー、前記 S2は第 一感光層を硬化させるために必要な光エネルギー、前記 S3は、第一感光層の硬化 が始まるまでに必要な光エネルギー量を示す。また、前記第一感光層の光感度を 1 としたとき、前記第二感光層の光感度は 10であった。  S1 is the light energy necessary to cure the second photosensitive layer, S2 is the light energy necessary to cure the first photosensitive layer, and S3 is necessary before the first photosensitive layer is cured. The amount of light energy. When the photosensitivity of the first photosensitive layer was 1, the photosensitivity of the second photosensitive layer was 10.
[0160] (3)解像度の測定 [0160] (3) Measurement of resolution
前記（1)の最短現像時間の評価方法と同じ方法及び条件で前記積層体を作成し、 室温（23°C、 55%RH)にて 10分間静置した。得られた積層体の支持体上から、下 記のパターン形成装置を用いて、ライン Zスペース = 1Z1でライン幅 10 /ζ πι〜50 /ζ mまで 5 m刻みで各線幅の露光を行った。この際の露光量は、前記（2)で測定した 第二の層（第二感光層）が硬化するのに必要な光エネルギー量である。室温にて 10 分間静置した後、前記積層体から前記支持体を剥がし取った。銅張積層板上の前 記第一感光層上から全面に、前記現像液として炭酸ナトリウム水溶液（30°C、 1質量 %)をスプレー圧 0. 15MPaにて前記（1)で求めた最短現像時間の 2倍の時間スプ レーし、未硬化領域を溶解除去した。この様にして得られた硬化榭脂パターン付き銅 張積層板の表面を光学顕微鏡で観察し、硬化榭脂パターンのラインにッマリ、ョレ等 の異常のない最小のライン幅を測定し、これを解像度とした。該解像度は数値が小さ いほど良好である。  The laminate was prepared under the same method and conditions as in the method (1) for evaluating the shortest development time, and allowed to stand at room temperature (23 ° C., 55% RH) for 10 minutes. From the support of the obtained laminate, exposure was performed for each line width in 5 m increments from 10 / ζ πι to 50 / ζ m with a line Z space = 1Z1 using the following pattern forming apparatus. . The exposure amount at this time is the amount of light energy required for curing the second layer (second photosensitive layer) measured in (2) above. After standing at room temperature for 10 minutes, the support was peeled off from the laminate. The shortest development obtained in (1) above with a sodium carbonate aqueous solution (30 ° C, 1% by mass) as the developer at a spray pressure of 0.15 MPa over the entire surface of the first photosensitive layer on the copper clad laminate. Spraying was performed twice the time, and the uncured area was dissolved and removed. The surface of the copper clad laminate with a cured resin pattern thus obtained was observed with an optical microscope, and the line width of the cured resin pattern was measured to determine the minimum line width without any abnormalities such as scumming or scouring. Was defined as the resolution. The smaller the numerical value, the better the resolution.
[0161] <ェツチング線幅の測定 > [0161] <Measurement of etching line width>
前記（3)において硬化榭脂パターンが形成された前記積層体の表面に、塩化鉄工 ッチャント (塩ィ匕第二鉄含有エッチング溶液)をスプレーし、硬化層パターンが形成さ れていない露出した銅層を溶解除去した。その後、 2質量％の水酸ィ匕ナトリウム水溶 液をスプレーし、硬化層パターンを除去し、銅層の線幅を 20点測定し、ノ ラツキを測 し 7こ。 [0162] < <パターン形成装置 > > On the surface of the laminate on which the cured resin pattern is formed in (3) above, an iron chloride etchant (salt-iron ferric-containing etching solution) is sprayed to expose the exposed copper on which the cured layer pattern is not formed. The layer was dissolved away. After that, spray 2% by weight sodium hydroxide aqueous solution, remove the hardened layer pattern, measure the line width of the copper layer at 20 points, and measure the roughness. [0162] <<Pattern forming device>>
前記光照射手段として図 10〜16に示す合波レーザ光源と、前記光変調手段とし て図 17及び図 18に示す主走査方向にマイクロミラーが 1024個配列されたマイクロミ ラー列が、副走査方向に 768組配列された前記光変調手段の内、 1024個 X 256列 のみを駆動するように制御された DMD50と、図 7に示した一方の面がトーリック面で あるマイクロレンズをアレイ状に配列したマイクロレンズアレイ 472及び該マイクロレン ズアレイを通した光を前記感光層に結像する光学系 480、 482とを有するパターン形 成装置を用いた。  The combined laser light source shown in FIGS. 10 to 16 as the light irradiating means, and the micromirror array in which 1024 micromirrors are arranged in the main scanning direction shown in FIGS. 17 and 18 as the light modulating means are in the sub-scanning direction. The DMD50 controlled to drive only 1024 x 256 rows among the 768 light modulation means arranged in a row and the microlens whose one surface is a toric surface shown in FIG. 7 are arranged in an array. The pattern forming apparatus including the microlens array 472 and the optical systems 480 and 482 for forming an image of the light passing through the microlens array on the photosensitive layer was used.
外観として図 19に示すパターン形成装置のステージ 152上に、前記積層体が格納 された真空焼枠 (図示せず)が配置され、前記積層体の感光層 150に対して露光が 行われる。  As an appearance, a vacuum frame (not shown) in which the laminate is stored is arranged on a stage 152 of the pattern forming apparatus shown in FIG. 19, and the photosensitive layer 150 of the laminate is exposed.
[0163] 前記マイクロレンズとしては、図 3〜6に示すように、トーリックレンズ 55aが用いられ ており、前記 X方向に光学的に対応する方向の曲率半径 Rx= 0. 125mm,前記 y 方向に対応する方向の曲率半径 Ry=—0. 1mmである。  As the microlens, a toric lens 55a is used as shown in FIGS. 3 to 6, and a radius of curvature Rx = 0.125 mm in a direction optically corresponding to the X direction, in the y direction. The radius of curvature in the corresponding direction is Ry = —0.1 mm.
[0164] また、マイクロレンズアレイ 55の集光位置近傍に配置されるアパーチャアレイ 59は 、その各アパーチャ 59aに、それと対応するマイクロレンズ 55aを経た光のみが入射 するように配置されている。  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.
[0165] プリント基板の製造  [0165] Manufacture of printed circuit boards
内壁に銅めつき層を備えた直径 3mmのスルーホールを有する銅張積層板の表面 を研磨し、水洗し、乾燥させて基体を調製した。該銅張積層板上に、前記パターン形 成材料の第二の層（第二感光層）が前記銅張積層板に接するようにして前記保護フ イルムを剥がしながら、ラミネーター（MODEL8B— 720— PH、大成ラミネーター（ 株)製)を用いて積層し、前記銅張積層板と、前記第二の層 (第二感光層）と、前記第 一の層 (第一感光層）と、前記支持体とがこの順に積層された積層体を調製した。圧 着条件は、圧着ロール温度 105°C、圧着ロール圧力 3kgZcm2、圧着速度 lmZ分 とした。 The surface of a copper clad laminate having a through hole with a diameter of 3 mm having a copper plating layer on the inner wall was polished, washed with water, and dried to prepare a substrate. A laminator (MODEL8B-720-PH) is formed on the copper clad laminate while peeling off the protective film so that the second layer (second photosensitive layer) of the pattern forming material is in contact with the copper clad laminate. The copper clad laminate, the second layer (second photosensitive layer), the first layer (first photosensitive layer), and the support are laminated using a Taisei Laminator Co., Ltd. A laminate was prepared in which and were laminated in this order. The pressing conditions were a pressure roll temperature of 105 ° C, a pressure roll pressure of 3 kgZcm 2 , and a pressure bonding speed of lmZ.
前記積層体を室温（23°C、 55%RH)にて 10分間静置した後、前記パターン形成 装置を用いて、配線パターン形成領域に前記第二感光層を硬化させるために必要 な光エネルギー SIを所定のパターン状に照射し、スルーホール開口部及びその周 辺領域に前記第一感光層を硬化させるために必要な光エネルギー S2を照射した。 露光後、室温にて 10分間静置した後、前記積層体から前記支持体を剥がし取り、 銅張積層板上の前記第一の層 (第一感光層）上力も全面に、炭酸ナトリウム水溶液（ 30°C、 1質量％)をスプレー圧 0. 15MPaにて前記（1)で求めた最短現像時間の 2 倍の時間スプレーし、未硬化の領域を溶解除去して、硬化層パターンを形成した。 Necessary for curing the second photosensitive layer in the wiring pattern forming area using the pattern forming apparatus after allowing the laminate to stand at room temperature (23 ° C, 55% RH) for 10 minutes. Light energy SI was irradiated in a predetermined pattern, and light energy S2 necessary to cure the first photosensitive layer was irradiated to the through-hole opening and its peripheral region. After the exposure, the substrate was allowed to stand at room temperature for 10 minutes, and then the support was peeled off from the laminate, and the upper force of the first layer (first photosensitive layer) on the copper-clad laminate was also applied to the entire surface with an aqueous sodium carbonate solution ( (30 ° C, 1% by mass) was sprayed at a spray pressure of 0.15 MPa for twice the minimum development time obtained in (1) above, and uncured areas were dissolved and removed to form a cured layer pattern. .
[0166] 前記硬化層パターンの厚みを測定した。また、パターンを顕微鏡で観察し、パター ン欠陥の有無を観察した。この結果、硬化層の厚みは 5 μ m±0. 05 μであり、パタ ーン欠陥は観察されな力つた。  [0166] The thickness of the cured layer pattern was measured. In addition, the pattern was observed with a microscope to observe the presence or absence of pattern defects. As a result, the thickness of the hardened layer was 5 μm ± 0.05 μm, and no pattern defects were observed.
[0167] 次いで、前記硬化層パターンが形成された前記積層体の表面に、塩化鉄工ッチヤ ント (塩化第二鉄含有エッチング溶液)をスプレーし、硬化層パターンが形成されて 、 ない露出した銅層を溶解除去した。その後、 2質量％の水酸ィ匕ナトリウム水溶液をス プレーし、硬化層パターンを除去し、プリント配線板を得た。  [0167] Next, an iron chloride etchant (ferric chloride-containing etching solution) is sprayed on the surface of the laminate on which the hardened layer pattern is formed, and the hardened layer pattern is not formed and the exposed copper layer is not exposed. Was dissolved and removed. Thereafter, a 2% by mass aqueous solution of sodium hydroxide and sodium hydroxide was sprayed to remove the hardened layer pattern to obtain a printed wiring board.
[0168] (実施例 2)  [Example 2]
実施例 1において、第一の層用塗布液における 4, 4 ビス (ジェチルァミノ)ベンゾ フエノン、及びべンゾフエノンを添加せず、クッション層用塗布液とした以外は、実施 例 1と同様にして、支持体、第一の層 (クッション層）、第二の層 (感光層）、及び保護 フィルムをこの順に有するパターン形成材料を製造した。また、実施例 1と同様にして 、基体、第二の層 (感光層）、第一の層 (クッション層）、及び支持体をこの順に有する 積層体、並びにプリント配線板を製造した。  In Example 1, support was conducted in the same manner as in Example 1 except that the coating solution for the cushion layer was not added without adding 4,4 bis (jetylamino) benzophenone and benzophenone in the coating solution for the first layer. A pattern forming material having a body, a first layer (cushion layer), a second layer (photosensitive layer), and a protective film in this order was produced. In the same manner as in Example 1, a laminate having a substrate, a second layer (photosensitive layer), a first layer (cushion layer), and a support in this order, and a printed wiring board were produced.
前記パターン形成材料における前記第一の層及び前記第二の層のガラス転移温 度 (Tg)、及び 60°Cにおける溶融粘度を表 3に示す。また、前記積層体における膜 厚のバラツキ、感度、解像度、及びエッチング線幅のバラツキを表 4に示す。  Table 3 shows the glass transition temperatures (Tg) of the first layer and the second layer in the pattern forming material and the melt viscosity at 60 ° C. Table 4 shows the film thickness variation, sensitivity, resolution, and etching line width variation in the laminate.
[0169] (実施例 3) [Example 3]
実施例 1において、前記第一の層上に、下記の組成力 なるノ リア層用塗布液を 塗布、乾燥し、 1. 6 m厚のノ リア層を形成した以外は、実施例 1と同様にして、支 持体、第一の層 (第一感光層）、バリア層、第二の層 (第二感光層）、及び保護フィル ムをこの順に有するパターン形成材料を製造した。また、実施例 1と同様にして、基 体、第二の層 (第二感光層）、バリア層、第一の層 (第一感光層）、及び支持体をこの 順に有する積層体、並びにプリント配線板を製造した。 In Example 1, a coating solution for the NORA layer having the following composition was applied on the first layer and dried to form a 1.6 m thick NORA layer. Thus, a pattern forming material having a support, a first layer (first photosensitive layer), a barrier layer, a second layer (second photosensitive layer), and a protective film in this order was produced. In the same manner as in Example 1, A laminate having a substrate, a second layer (second photosensitive layer), a barrier layer, a first layer (first photosensitive layer), and a support in this order, and a printed wiring board were produced.
前記パターン形成材料における前記第一の層及び前記第二の層のガラス転移温 度 (Tg)、及び 60°Cにおける溶融粘度を表 3に示す。また、前記積層体における膜 厚のバラツキ、感度、解像度、及びエッチング線幅のバラツキを表 4に示す。  Table 3 shows the glass transition temperatures (Tg) of the first layer and the second layer in the pattern forming material and the melt viscosity at 60 ° C. Table 4 shows the film thickness variation, sensitivity, resolution, and etching line width variation in the laminate.
また、プリント配線板における硬化層のパターン欠陥の有無を観察した結果、欠陥 や異常はみられなかった。  In addition, as a result of observing the presence or absence of pattern defects in the cured layer on the printed wiring board, no defects or abnormalities were found.
ただし、前記感度の測定において、前記第一感光層を硬化させるのに必要な光ェ ネルギー量 S2は、硬化層の厚みが 31. 6 μ mとなった時の光エネルギー量とした。  However, in the sensitivity measurement, the amount of light energy S2 required to cure the first photosensitive layer was the amount of light energy when the thickness of the cured layer reached 31.6 μm.
[0170] 「バリア ffl、途 夜 Ί [0170] "Barrier ffl
'ポリビュルアルコール（ポパール PVA205、（株）クラレ製） 10g  'Polybulol alcohol (Popard PVA205, Kuraray Co., Ltd.) 10g
'ポリビュルアルコール（ポパール PVA505、（株）クラレ製） 5g 'Polybule alcohol (Popard PVA505, Kuraray Co., Ltd.) 5g
Figure imgf000045_0001
Figure imgf000045_0001
[0171] (実施例 4)  [Example 4]
実施例 1において、実施例 3と同様のバリア層用塗布液を塗布、乾燥し、 1. 6 μ ηι 厚のノ リア層を形成した以外は、実施例 1と同様にして、支持体、第一の層（クッショ ン層）、バリア層、第二の層 (感光層）、及び保護フィルムをこの順に有するパターン 形成材料を製造した。また、実施例 1と同様にして、基体、第二の層 (感光層）、バリ ァ層、第一の層（クッション層）、及び支持体をこの順に有する積層体、並びにプリント 配線板を製造した。  In Example 1, the same procedure as in Example 1 was applied, except that a barrier layer coating solution similar to that in Example 3 was applied and dried to form a 1.6 μηι-thick noria layer. A pattern forming material having one layer (a cushion layer), a barrier layer, a second layer (photosensitive layer), and a protective film in this order was produced. Further, in the same manner as in Example 1, a laminated body having a substrate, a second layer (photosensitive layer), a barrier layer, a first layer (cushion layer), and a support in this order, and a printed wiring board were produced. did.
前記パターン形成材料における前記第一の層及び前記第二の層のガラス転移温 度 (Tg)、及び 60°Cにおける溶融粘度を表 3に示す。また、前記積層体における膜 厚のバラツキ、感度、解像度、及びエッチング線幅のバラツキを表 4に示す。  Table 3 shows the glass transition temperatures (Tg) of the first layer and the second layer in the pattern forming material and the melt viscosity at 60 ° C. Table 4 shows the film thickness variation, sensitivity, resolution, and etching line width variation in the laminate.
また、プリント配線板における硬化層のパターン欠陥の有無を観察した結果、欠陥 や異常はみられなかった。  In addition, as a result of observing the presence or absence of pattern defects in the cured layer on the printed wiring board, no defects or abnormalities were found.
[0172] (比較例 1) [0172] (Comparative Example 1)
実施例 1において、前記第一の層（第一感光層）用塗布液におけるドデカポリプロ ピレングリコールジアタリレートの配合量を 3. 5質量部とし、テトラエチレンダリコール ジメタタリレートの配合量を 0. 5質量部とした以外は、実施例 1と同様にして、支持体 、第一の層 (第一感光層）、第二の層 (第二感光層）、及び保護フィルムをこの順に有 するパターン形成材料を製造した。また、実施例 1と同様にして、基体、第二の層（第 二感光層）、第一の層 (第一感光層）、及び支持体をこの順に有する積層体、並びに プリント配線板を製造した。 In Example 1, the blending amount of dodecapropylene glycol ditalylate in the coating solution for the first layer (first photosensitive layer) was 3.5 parts by mass, A support, a first layer (first photosensitive layer), a second layer (second photosensitive layer), the same as in Example 1 except that the blending amount of dimetatalylate was 0.5 parts by mass, And the pattern formation material which has a protective film in this order was manufactured. Further, in the same manner as in Example 1, a laminated body having a substrate, a second layer (second photosensitive layer), a first layer (first photosensitive layer), and a support in this order, and a printed wiring board are manufactured. did.
前記パターン形成材料における前記第一の層及び前記第二の層のガラス転移温 度 (Tg)、及び 60°Cにおける溶融粘度を表 3に示す。また、前記積層体における膜 厚のバラツキ、感度、解像度、及びエッチング線幅のバラツキを表 4に示す。  Table 3 shows the glass transition temperatures (Tg) of the first layer and the second layer in the pattern forming material and the melt viscosity at 60 ° C. Table 4 shows the film thickness variation, sensitivity, resolution, and etching line width variation in the laminate.
[0173] (比較例 2) [0173] (Comparative Example 2)
実施例 2において、前記第一の層（クッション層）用塗布液におけるドデカポリプロピ レングリコールジアタリレートの配合量を 3. 5質量部とし、テトラエチレングリコールジ メタタリレートの配合量を 0. 5質量部とした以外は、実施例 2と同様にして、支持体、 第一の層（クッション層）、第二の層 (感光層）、及び保護フィルムをこの順に有するパ ターン形成材料を製造した。また、実施例 2と同様にして、基体、第二の層 (感光層） 、第一の層（クッション層）、及び支持体をこの順に有する積層体、並びにプリント配 線板を製造した。  In Example 2, the blending amount of dodecapolypropylene glycol diatalylate in the coating solution for the first layer (cushion layer) is 3.5 parts by mass, and the blending amount of tetraethylene glycol dimetatalylate is 0.5 parts by mass. A pattern forming material having a support, a first layer (cushion layer), a second layer (photosensitive layer), and a protective film in this order was produced in the same manner as in Example 2 except that. In the same manner as in Example 2, a laminate having a substrate, a second layer (photosensitive layer), a first layer (cushion layer), and a support in this order, and a printed wiring board were produced.
前記パターン形成材料における前記第一の層及び前記第二の層のガラス転移温 度 (Tg)、及び 60°Cにおける溶融粘度を表 3に示す。また、前記積層体における膜 厚のバラツキ、感度、解像度、及びエッチング線幅のバラツキを表 4に示す。  Table 3 shows the glass transition temperatures (Tg) of the first layer and the second layer in the pattern forming material and the melt viscosity at 60 ° C. Table 4 shows the film thickness variation, sensitivity, resolution, and etching line width variation in the laminate.
[0174] (比較例 3) [0174] (Comparative Example 3)
実施例 3において、前記第一の層（第一感光層）用塗布液におけるドデカポリプロ ピレングリコールジアタリレートの配合量を 3. 5質量部とし、テトラエチレンダリコール ジメタタリレートの配合量を 0. 5質量部とした以外は、実施例 3と同様にして、支持体 、第一の層 (第一感光層）、バリア層、第二の層 (第二感光層）、及び保護フィルムを この順に有するパターン形成材料を製造した。また、実施例 3と同様にして、基体、第 二の層 (第二感光層）、バリア層、第一の層 (第一感光層）、及び支持体をこの順に有 する積層体、並びにプリント配線板を製造した。  In Example 3, the blending amount of dodecapropylene glycol ditalarirate in the coating solution for the first layer (first photosensitive layer) is 3.5 parts by mass, and the blending amount of tetraethylenedaricol dimetatalylate is 0. A support, a first layer (first photosensitive layer), a barrier layer, a second layer (second photosensitive layer), and a protective film were prepared in the same manner as in Example 3 except that the content was 5 parts by mass. The pattern formation material which has in order was manufactured. Further, in the same manner as in Example 3, a laminate having a substrate, a second layer (second photosensitive layer), a barrier layer, a first layer (first photosensitive layer), and a support in this order, and a print A wiring board was manufactured.
前記パターン形成材料における前記第一の層及び前記第二の層のガラス転移温 度 (Tg)、及び 60°Cにおける溶融粘度を表 3に示す。また、前記積層体における膜 厚のバラツキ、感度、解像度、及びエッチング線幅のバラツキを表 4に示す。 Glass transition temperature of the first layer and the second layer in the pattern forming material Table 3 shows the temperature (Tg) and melt viscosity at 60 ° C. Table 4 shows the film thickness variation, sensitivity, resolution, and etching line width variation in the laminate.
[0175] (比較例 4) [0175] (Comparative Example 4)
実施例 4において、前記第一の層（クッション層）用塗布液におけるドデカポリプロピ レングリコールジアタリレートの配合量を 3. 5質量部とし、テトラエチレングリコールジ メタタリレートの配合量を 0. 5質量部とした以外は、実施例 4と同様にして、支持体、 第一の層（クッション層）、バリア層、第二の層（感光層）、及び保護フィルムをこの順 に有するパターン形成材料を製造した。また、実施例 1と同様にして、基体、第二の 層 (感光層）、バリア層、第一の層（クッション層）、及び支持体をこの順に有する積層 体、並びにプリント配線板を製造した。  In Example 4, the blending amount of dodecapolypropylene glycol diatalylate in the coating solution for the first layer (cushion layer) is 3.5 parts by mass, and the blending amount of tetraethylene glycol dimetatalylate is 0.5 parts by mass. A pattern forming material having a support, a first layer (cushion layer), a barrier layer, a second layer (photosensitive layer), and a protective film in this order was produced in the same manner as in Example 4. did. Further, in the same manner as in Example 1, a laminate having a substrate, a second layer (photosensitive layer), a barrier layer, a first layer (cushion layer), and a support in this order, and a printed wiring board were produced. .
前記パターン形成材料における前記第一の層及び前記第二の層のガラス転移温 度 (Tg)、及び 60°Cにおける溶融粘度を表 1に示す。また、前記積層体における膜 厚のバラツキ、感度、解像度、及びエッチング線幅のバラツキを表 2に示す。  Table 1 shows the glass transition temperatures (Tg) of the first layer and the second layer in the pattern forming material and the melt viscosity at 60 ° C. Table 2 shows the variation in film thickness, sensitivity, resolution, and etching line width in the laminate.
[0176] [表 1] [0176] [Table 1]
Figure imgf000047_0001
Figure imgf000047_0001
[0177] [表 2] ぐ 、、 / -V- 感度（mJZcm2:^ エッチング線幅の[0177] [Table 2] ,, / -V- sensitivity (mJZcm 2 : ^ Etching line width
Jl旲〗旱ひリ /ヽノノ 解像度 Jl 旲〗 旱 ひ り / ヽ ノ ノ Resolution
S1 S2 S3 バラツキ 実施例 1 ±0. 1 ji m 4 40 14 ^o^ m ±0. 1 jU m 実施例 2 ±0. 1 ji m 4 ^o^ m ±0. 1 jU m 実施例 3 ±0. 1 U m 4 40 14 1 OjU m ±0. 111 m 実施例 4 ±0. 1 U m 4 1 OjU m ±0. 111 m 比較例 1 ± 1 m 4 50 18 1 OjU m ±1 m 比較例 2 ± 1 jU m 4 1 OjU m ±1 m 比較例 3 ± 1 jU m 4 50 18 1 OjU m ±1 m 比較例 4 ± 1 m 4 ^o^ m ±1 m  S1 S2 S3 Variation Example 1 ± 0. 1 ji m 4 40 14 ^ o ^ m ± 0. 1 jU m Example 2 ± 0. 1 ji m 4 ^ o ^ m ± 0. 1 jU m Example 3 ± 0. 1 U m 4 40 14 1 OjU m ± 0. 111 m Example 4 ± 0. 1 U m 4 1 OjU m ± 0. 111 m Comparative example 1 ± 1 m 4 50 18 1 OjU m ± 1 m Comparison Example 2 ± 1 jU m 4 1 OjU m ± 1 m Comparative example 3 ± 1 jU m 4 50 18 1 OjU m ± 1 m Comparative example 4 ± 1 m 4 ^ o ^ m ± 1 m
※ 丄：第二の層（第二感光層、又は感光層）を硬化させるために必要な光エネルギ * 丄: Light energy required to cure the second layer (second photosensitive layer or photosensitive layer)
52：第一の層（第一感光層）を硬化させるために必要な光エネルギー量52: Amount of light energy required to cure the first layer (first photosensitive layer)
53：第一の層（第一感光層）の硬化が始まるまでに必要な光エネルギー量 [0178] 表 1及び表 2の結果より、ガラス転移温度及び溶融粘度が、第一の層よりも第二の 層の方が高い実施例 1〜4のパターン形成材料は、積層後の膜厚の均一性に優れ、 形成されたパターンの解像度に優れ、エッチング線幅も均一であることがわ力つた。 産業上の利用可能性 53: Amount of light energy required until the first layer (first photosensitive layer) is cured [0178] From the results in Table 1 and Table 2, the glass transition temperature and the melt viscosity are higher than those of the first layer. The pattern forming material of Examples 1 to 4 has higher uniformity of the film thickness after lamination, excellent resolution of the formed pattern, and uniform etching line width. . Industrial applicability
[0179] 本発明のパターン形成材料は、基体表面の凹凸追従性に優れ、かつ、テント性及 びエッチングの均一性に優れた高精細なパターンを形成可能なパターンを形成可能 であるため、各種パターンの形成、配線パターン等の永久パターンの形成、カラーフ ィルタ、柱材、リブ材、スぺーサ一、隔壁等の液晶構造部材の製造、ホログラム、マイ クロマシン、プルーフの製造などに好適に用いることができ、特に高精細な配線パタ ーンの形成に好適に用いることができる。本発明のパターン形成装置は、本発明の 前記パターン形成材料を備えているため、各種パターンの形成、配線パターン等の 永久パターンの形成、カラーフィルタ、柱材、リブ材、スぺーサ一、隔壁等の液晶構 造部材の製造、ホログラム、マイクロマシン、プルーフの製造などに好適に用いること ができ、特に高精細な配線パターンの形成に好適に用いることができる。本発明のパ ターン形成方法は、本発明の前記パターン形成材料を用いるため、各種パターンの 形成、配線パターン等の永久パターンの形成、カラーフィルタ、柱材、リブ材、スぺー サー、隔壁等の液晶構造部材の製造、ホログラム、マイクロマシン、プルーフの製造 などに好適に用いることができ、特に高精細な配線パターンの形成に好適に使用す ることがでさる。 [0179] The pattern forming material of the present invention is capable of forming a pattern capable of forming a high-definition pattern excellent in uneven surface followability on the substrate surface and excellent in tent properties and etching uniformity. Suitable for pattern formation, formation of permanent patterns such as wiring patterns, manufacturing of liquid crystal structural members such as color filters, pillars, ribs, spacers, partition walls, holograms, micromachines, proofs, etc. In particular, it can be suitably used for forming a high-definition wiring pattern. Since the pattern forming apparatus of the present invention includes the pattern forming material of the present invention, it forms various patterns, forms permanent patterns such as wiring patterns, color filters, pillar materials, rib materials, spacers, partition walls It can be suitably used for the production of liquid crystal structural members such as holograms, micromachines, and proofs, and can be particularly suitably used for the formation of high-definition wiring patterns. Since the pattern forming method of the present invention uses the pattern forming material of the present invention, the formation of various patterns, the formation of permanent patterns such as wiring patterns, color filters, pillar materials, rib materials, and spacers. It can be suitably used for the production of liquid crystal structural members such as sir and partition walls, the production of holograms, micromachines, and proofs, and is particularly suitable for the formation of high-definition wiring patterns.

Claims

請求の範囲 The scope of the claims
[I] 支持体上に、第一の層と第二の層とをこの順に有し、該第一の層のガラス転移温度  [I] On a support, it has a first layer and a second layer in this order, and the glass transition temperature of the first layer
(Tg)を A、該第二の層のガラス転移温度 (Tg)を Bとしたとき、 B≥ Aであることを特徴 とするパターン形成材料。  A pattern forming material characterized in that B≥A where (Tg) is A and the glass transition temperature (Tg) of the second layer is B.
[2] 第一の層のガラス転移温度 Aが— 20〜30°Cであり、第二の層のガラス転移温度 B が 10〜40°Cである請求項 1に記載のパターン形成材料。  [2] The pattern forming material according to claim 1, wherein the glass transition temperature A of the first layer is −20 to 30 ° C., and the glass transition temperature B of the second layer is 10 to 40 ° C.
[3] 第二の層の溶融粘度が、 40〜： L00°Cの範囲において、 500〜30000 (Pa' S)であ る請求項 1から 2のいずれかに記載のパターン形成材料。 [3] The pattern forming material according to any one of claims 1 to 2, wherein the melt viscosity of the second layer is in the range of 40 to: L00 ° C, and is 500 to 30000 (Pa'S).
[4] 第一の層の厚みが 5〜30 μ m、第二の層の厚みが 2〜15 μ mである請求項 1から[4] The thickness of the first layer is 5 to 30 μm, and the thickness of the second layer is 2 to 15 μm.
3の!、ずれかに記載のパターン形成材料。 3 !, Pattern forming material as described in any of the above.
[5] 第一の層がクッション層であり、第二の層が感光層である請求項 1から 4のいずれか に記載のパターン形成材料。 5. The pattern forming material according to any one of claims 1 to 4, wherein the first layer is a cushion layer and the second layer is a photosensitive layer.
[6] 第一の層が第一感光層であり、第二の層が第二感光層である請求項 1から 4のい ずれかに記載のパターン形成材料。 6. The pattern forming material according to any one of claims 1 to 4, wherein the first layer is a first photosensitive layer and the second layer is a second photosensitive layer.
[7] 405nmの波長の光を照射した際において、第一感光層のパターン形成可能な最 小露光量が、第二感光層のパターン形成可能な最小露光量よりも大きい請求項 6に 記載のパターン形成材料。 [7] The minimum exposure amount capable of pattern formation of the first photosensitive layer is larger than the minimum exposure amount capable of pattern formation of the second photosensitive layer when irradiated with light having a wavelength of 405 nm. Pattern forming material.
[8] 感光層が、バインダーと、重合性化合物と、光重合開始剤とを含む請求項 5から 7 の!、ずれかに記載のパターン形成材料。 8. The pattern forming material according to any one of claims 5 to 7, wherein the photosensitive layer contains a binder, a polymerizable compound, and a photopolymerization initiator.
[9] 第一の層と第二の層との間に、物質の移動を制御可能なバリア層を有する請求項[9] The barrier layer capable of controlling the movement of the substance between the first layer and the second layer.
1から 8のいずれかに記載のパターン形成材料。 The pattern forming material according to any one of 1 to 8.
[10] 請求項 1から 9のいずれかに記載のパターン形成材料を備えており、 [10] The pattern forming material according to any one of claims 1 to 9,
光を照射可能な光照射手段と、該光照射手段からの光を変調し、前記パターン形 成材料における感光層に対して露光を行う光変調手段とを少なくとも有することを特 徴とするパターン形成装置。  Pattern formation characterized by comprising at least light irradiation means capable of irradiating light and light modulation means for modulating light from the light irradiation means and exposing the photosensitive layer in the pattern forming material. apparatus.
[II] 請求項 1から 9のいずれかに記載のパターン形成材料における該感光層に対し、 露光を行うことを少なくとも含むことを特徴とするパターン形成方法。  [II] A pattern forming method comprising at least exposing the photosensitive layer in the pattern forming material according to any one of claims 1 to 9.
[12] 露光が、形成するパターン情報に基づいて制御信号を生成し、該制御信号に応じ て変調させた光を用いて行われる請求項 11に記載のパターン形成方法。 [12] The exposure generates a control signal based on the pattern information to be formed, and according to the control signal The pattern forming method according to claim 11, wherein the pattern forming method is performed using light modulated by the step.
[13] 露光が、光変調手段により光を変調させた後、前記光変調手段における描素部の 出射面の歪みによる収差を補正可能な非球面を有するマイクロレンズを配列したマイ クロレンズアレイを通して行われる請求項 11から 12のいずれかに記載のパターン形 成方法。 [13] After the exposure, the light is modulated by the light modulation means, and then passes through a microlens array in which microlenses having aspherical surfaces capable of correcting aberration due to distortion of the exit surface of the picture element portion in the light modulation means are arranged. 13. The pattern forming method according to claim 11, which is performed.
[14] 非球面が、トーリック面である請求項 13に記載のパターン形成方法。  14. The pattern forming method according to claim 13, wherein the aspherical surface is a toric surface.
[15] 露光が行われた後、感光層の現像を行う請求項 11から 14のいずれかに記載のパ ターン形成方法。 15. The pattern forming method according to claim 11, wherein the photosensitive layer is developed after the exposure.
[16] 現像が行われた後、永久パターンの形成を行う請求項 15に記載のパターン形成方 法。  16. The pattern forming method according to claim 15, wherein a permanent pattern is formed after the development.
PCT/JP2006/303404 2005-03-04 2006-02-24 Pattern forming material, pattern forming apparatus and pattern forming method WO2006093040A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2005061407A JP2006243546A (en) 2005-03-04 2005-03-04 Pattern forming material, pattern forming apparatus, and pattern forming method
JP2005-061407 2005-03-04

Publications (1)

Publication Number Publication Date
WO2006093040A1 true WO2006093040A1 (en) 2006-09-08

Family

ID=36941071

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2006/303404 WO2006093040A1 (en) 2005-03-04 2006-02-24 Pattern forming material, pattern forming apparatus and pattern forming method

Country Status (3)

Country Link
JP (1) JP2006243546A (en)
TW (1) TW200702930A (en)
WO (1) WO2006093040A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022215283A1 (en) * 2021-04-06 2022-10-13 株式会社 ムラカミ Layered film for pattern formation, non-photosensitive screen printing plate, and method for manufacturing same

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5068603B2 (en) * 2007-08-22 2012-11-07 富士フイルム株式会社 Photosensitive transfer material, partition wall and method for forming the same, color filter and method for manufacturing the same, and display device
KR101396621B1 (en) * 2012-10-15 2014-05-16 삼성전기주식회사 Dry film and method for manufacturing circuit board with the same
JP2016080803A (en) * 2014-10-14 2016-05-16 太陽インキ製造株式会社 Dry film and flexible printed wiring board
JP6018664B2 (en) * 2015-04-13 2016-11-02 三菱製紙株式会社 Photosensitive film for sandblasting
JP6812556B2 (en) * 2017-07-28 2021-01-13 富士フイルム株式会社 Photosensitive resin composition, photosensitive transfer material, circuit wiring manufacturing method, and touch panel manufacturing method
CN111684359A (en) * 2018-02-05 2020-09-18 富士胶片株式会社 Photosensitive transfer material, method for manufacturing circuit wiring, and method for manufacturing touch panel
WO2019151534A1 (en) * 2018-02-05 2019-08-08 富士フイルム株式会社 Photosensitive transfer material, manufacturing method for circuit wiring, and manufacturing method for touch panel

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01221735A (en) * 1988-02-29 1989-09-05 Nippon Synthetic Chem Ind Co Ltd:The Image forming method
JPH05241333A (en) * 1992-02-28 1993-09-21 Dainippon Printing Co Ltd Photosensitive recording medium
JPH0728232A (en) * 1993-07-08 1995-01-31 Fuji Photo Film Co Ltd Photosensitive transfer material
JPH0854732A (en) * 1994-08-12 1996-02-27 Toagosei Co Ltd Etching resist sheet and production of printed wiring board
JPH095992A (en) * 1995-04-28 1997-01-10 E I Du Pont De Nemours & Co Durable multilayer coating material capable of being processed aqueously and capable of being changed into optical image for printed circuit
JPH1069090A (en) * 1996-08-29 1998-03-10 Hitachi Chem Co Ltd Photosensitive film and production of color filter using the same
JP2003098675A (en) * 2001-09-26 2003-04-04 Fuji Photo Film Co Ltd Photosensitive transfer material and image forming method
JP2003114528A (en) * 2001-10-02 2003-04-18 Fuji Photo Film Co Ltd Photosensitive resin composition, photosensitive transfer material, member for liquid crystal display element and liquid crystal display element
JP2003307845A (en) * 2002-04-17 2003-10-31 Hitachi Chem Co Ltd Photosensitive film for forming circuit and method for manufacturing printed-wiring board
JP2004012564A (en) * 2002-06-04 2004-01-15 Fuji Photo Film Co Ltd Method for forming image
JP2004062156A (en) * 2002-06-07 2004-02-26 Fuji Photo Film Co Ltd Exposure head and exposure apparatus
US20050024477A1 (en) * 2003-07-31 2005-02-03 Fuji Photo Film Co., Ltd. Exposure head
JP2005055656A (en) * 2003-08-04 2005-03-03 Fuji Photo Film Co Ltd Photosensitive transfer sheet

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06122280A (en) * 1992-08-27 1994-05-06 Konica Corp Recording material, image receiving material, and recording method in light to heat converted heat mode

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01221735A (en) * 1988-02-29 1989-09-05 Nippon Synthetic Chem Ind Co Ltd:The Image forming method
JPH05241333A (en) * 1992-02-28 1993-09-21 Dainippon Printing Co Ltd Photosensitive recording medium
JPH0728232A (en) * 1993-07-08 1995-01-31 Fuji Photo Film Co Ltd Photosensitive transfer material
JPH0854732A (en) * 1994-08-12 1996-02-27 Toagosei Co Ltd Etching resist sheet and production of printed wiring board
JPH095992A (en) * 1995-04-28 1997-01-10 E I Du Pont De Nemours & Co Durable multilayer coating material capable of being processed aqueously and capable of being changed into optical image for printed circuit
JPH1069090A (en) * 1996-08-29 1998-03-10 Hitachi Chem Co Ltd Photosensitive film and production of color filter using the same
JP2003098675A (en) * 2001-09-26 2003-04-04 Fuji Photo Film Co Ltd Photosensitive transfer material and image forming method
JP2003114528A (en) * 2001-10-02 2003-04-18 Fuji Photo Film Co Ltd Photosensitive resin composition, photosensitive transfer material, member for liquid crystal display element and liquid crystal display element
JP2003307845A (en) * 2002-04-17 2003-10-31 Hitachi Chem Co Ltd Photosensitive film for forming circuit and method for manufacturing printed-wiring board
JP2004012564A (en) * 2002-06-04 2004-01-15 Fuji Photo Film Co Ltd Method for forming image
JP2004062156A (en) * 2002-06-07 2004-02-26 Fuji Photo Film Co Ltd Exposure head and exposure apparatus
US20050024477A1 (en) * 2003-07-31 2005-02-03 Fuji Photo Film Co., Ltd. Exposure head
JP2005055656A (en) * 2003-08-04 2005-03-03 Fuji Photo Film Co Ltd Photosensitive transfer sheet

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022215283A1 (en) * 2021-04-06 2022-10-13 株式会社 ムラカミ Layered film for pattern formation, non-photosensitive screen printing plate, and method for manufacturing same

Also Published As

Publication number Publication date
TW200702930A (en) 2007-01-16
JP2006243546A (en) 2006-09-14

Similar Documents

Publication Publication Date Title
WO2006093040A1 (en) Pattern forming material, pattern forming apparatus and pattern forming method
WO2006006671A1 (en) Photosensitive composition, pattern forming material, photosensitive laminate, pattern forming apparatus and method of pattern formation
WO2006019089A1 (en) Photosensitive transfer material and pattern forming method and pattern
WO2007108171A1 (en) Photosensitive composition, photosensitive film, photosensitive layered product, method of forming permanent pattern, and printed wiring board
WO2007000885A1 (en) Permanent patterning method
WO2005116774A1 (en) Pattern formation method
WO2007102289A1 (en) Photosensitive composition, photosensitive film, method for permanent pattern formation using said photosensitive composition, and printed board
WO2006059532A1 (en) Material for pattern formation, apparatus for pattern formation, and method for pattern formation
WO2007010748A1 (en) Patterning method
JP2010009913A (en) Photopolymerizable resin laminate, and method of manufacturing pattern using the same
JP2009223142A (en) Surface roughening and treating method for photosensitive film, and photosensitive film
JP2008003558A (en) Pattern forming material, pattern forming method and pattern
JP2008009404A (en) Pattern forming material, pattern forming apparatus and pattern forming method
JP2008251918A (en) Permanent pattern forming method and printed circuit board
JP2005249970A (en) Pattern forming material, pattern forming apparatus and pattern forming method
WO2006025389A1 (en) Pattern-forming material, pattern-forming apparatus and pattern-forming method
WO2006075633A1 (en) Pattern forming material, pattern forming apparatus and permanent pattern forming method
JP2007286480A (en) Pattern forming method
WO2021193297A1 (en) Method for manufacturing master plate, master plate, transferred object, and article
JP2008015364A (en) Photosensitive composition, photosensitive film, permanent pattern forming method, and printed circuit board
JP2006048031A (en) Photosensitive film, process for producing the same and process for forming permanent pattern
WO2006109721A1 (en) Material for pattern formation, apparatus for pattern formation, and method for pattern formation
JP2008250246A (en) Method for manufacturing photosensitive laminate, and printed wiring board and method for manufacturing the same
WO2007032246A1 (en) Material for pattern formation, apparatus for pattern formation, and method for pattern formation
JP2006023406A (en) Photosensitive film for permanent pattern formation, method for producing the same and permanent pattern forming method

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

NENP Non-entry into the national phase

Ref country code: RU

122 Ep: pct application non-entry in european phase

Ref document number: 06714543

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP