WO2022209307A1 - 積層体及び積層体の製造方法 - Google Patents

積層体及び積層体の製造方法 Download PDF

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Publication number
WO2022209307A1
WO2022209307A1 PCT/JP2022/004743 JP2022004743W WO2022209307A1 WO 2022209307 A1 WO2022209307 A1 WO 2022209307A1 JP 2022004743 W JP2022004743 W JP 2022004743W WO 2022209307 A1 WO2022209307 A1 WO 2022209307A1
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WO
WIPO (PCT)
Prior art keywords
mass
resin pattern
group
meth
photosensitive layer
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Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2022/004743
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English (en)
French (fr)
Japanese (ja)
Inventor
陽平 有年
健太郎 豊岡
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Fujifilm Corp
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Fujifilm Corp
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Priority to JP2023510585A priority Critical patent/JP7812843B2/ja
Publication of WO2022209307A1 publication Critical patent/WO2022209307A1/ja
Priority to US18/475,635 priority patent/US20240027897A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers

Definitions

  • the present disclosure relates to a laminate and a method for manufacturing the laminate.
  • a resin pattern formed using a photosensitive composition is used, for example, as a protective film for electrodes such as touch panel electrodes and as a protective film against chemical reactions such as etching.
  • a cured product of a photosensitive composition is preferably used.
  • Patent Document 1 discloses a method for forming a cured resin film pattern. Specifically, Patent Document 1 describes a photosensitive resin composition containing a binder polymer having a carboxyl group having an acid value of 75 mgKOH/g or more, a photopolymerizable compound, and a photopolymerization initiator on a substrate.
  • Patent Document 1 International Publication No. 2013/084886
  • the resin pattern used as a protective film is less susceptible to damage such as scratches.
  • Edge quality is defined, for example, by factors such as the shape, size and surface texture of the edge of the resin pattern. In particular, as edge quality, suppression of the phenomenon that the edge of the resin pattern is lifted from the base material (referring to the edge of the resin pattern being separated from the base material; hereinafter sometimes referred to as "edge lifting") is required.
  • An object of one embodiment of the present disclosure is to provide a laminate including a resin pattern that has excellent scratch resistance and prevents or reduces edge lifting.
  • Another embodiment of the present disclosure aims to provide a method of manufacturing a laminate including a resin pattern that has excellent scratch resistance and prevents or reduces edge lifting.
  • the present disclosure includes the following aspects. ⁇ 1> A base material and a resin pattern are included, and the surface of the resin pattern is detected based on a depth direction analysis of the resin pattern performed along a direction from the resin pattern toward the base material.
  • the strength of at least one component selected from the group consisting of sodium ions and potassium ions is defined as 100%
  • at least one component selected from the group consisting of sodium ions and potassium ions is removed from the surface of the resin pattern.
  • the presence depth of at least one component selected from the group consisting of sodium ions and potassium ions in the resin pattern defined by the distance to the point where the intensity of the seed component first reaches 90% is 0 .3 ⁇ m to 3.0 ⁇ m laminate.
  • ⁇ 2> The laminate according to ⁇ 1>, wherein the ratio of the existing depth to the thickness of the resin pattern is 0.1 to 0.9.
  • ⁇ 3> The laminate according to ⁇ 1> or ⁇ 2>, wherein the resin pattern is a cured product of a photosensitive composition.
  • the photosensitive composition contains a polymerizable compound and a polymerization initiator.
  • ⁇ 5> The laminate according to ⁇ 3> or ⁇ 4>, wherein the photosensitive composition contains a polymer.
  • ⁇ 6> The laminate according to ⁇ 5>, wherein the polymer has a polymerizable group.
  • ⁇ 7> The laminate according to any one of ⁇ 1> to ⁇ 6>, including a transparent electrode between the substrate and the resin pattern.
  • ⁇ 8> The laminate according to any one of ⁇ 1> to ⁇ 7>, which is a touch panel.
  • ⁇ 9> Disposing a photosensitive layer on a substrate, exposing the photosensitive layer in a pattern, and providing a developer containing at least one component selected from the group consisting of sodium ions and potassium ions. removing the exposed portion or the non-exposed portion of the photosensitive layer using water to form a resin pattern; washing the resin pattern using water; and allowing the base material and the resin pattern to stand still.
  • the intensity of at least one component selected from the group consisting of sodium ions and potassium ions detected on the surface of the resin pattern is defined as 100%
  • the surface of the resin pattern consists of sodium ions and potassium ions.
  • at least one component selected from the group consisting of sodium ions and potassium ions in said resin pattern defined by the distance to the point where the intensity of at least one component selected from the group first reaches 90%; is 0.3 ⁇ m to 3.0 ⁇ m.
  • a laminate including a resin pattern that has excellent scratch resistance and prevents or reduces edge lifting According to another embodiment of the present disclosure, there is provided a method of manufacturing a laminate including a resin pattern having excellent scratch resistance and preventing or reducing edge lifting.
  • FIG. 1 is a schematic cross-sectional view showing the structure of a laminate according to one embodiment.
  • FIG. 2 is a schematic cross-sectional view showing the structure of a laminate according to another embodiment.
  • a numerical range indicated using "-" indicates a range that includes the numerical values described before and after "-" as the minimum and maximum values, respectively.
  • upper or lower limits described in a certain numerical range may be replaced with upper or lower limits of other numerical ranges described step by step.
  • upper or lower limits described in a certain numerical range may be replaced with values shown in Examples.
  • the amount of each component in the composition means the total amount of the multiple substances present in the composition unless otherwise specified when there are multiple substances corresponding to each component in the composition. do.
  • process is not only an independent process, but even if it cannot be clearly distinguished from other processes, it is included in the term as long as the intended purpose of the process is achieved. .
  • transparent means that the average transmittance of visible light with a wavelength of 400 nm to 700 nm is 80% or more.
  • the average transmittance is measured using a spectrophotometer (for example, spectrophotometer U-3310 manufactured by Hitachi, Ltd.).
  • (meth)acrylic means acrylic, methacrylic, or both acrylic and methacrylic.
  • (meth)acrylate means acrylate, methacrylate, or both acrylate and methacrylate.
  • (meth)acryloyl means acryloyl, methacryloyl, or both acryloyl and methacryloyl.
  • the notation of groups (atomic groups) without “substituted” and “unsubstituted” includes groups having no substituents and groups having substituents.
  • an "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • exposure includes not only exposure using light, but also writing using particle beams such as electron beams and ion beams, unless otherwise specified.
  • the light used for exposure generally includes the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and active rays (active energy rays) such as electron beams. mentioned.
  • the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in the present disclosure are obtained by gel permeation using columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by Tosoh Corporation). It is a molecular weight obtained by detection using a solvent THF (tetrahydrofuran) and a differential refractometer using an ion chromatography (GPC) analyzer, and converted using polystyrene as a standard substance.
  • THF tetrahydrofuran
  • GPC ion chromatography
  • the numerical value attached to each structural unit of the polymer represents mol %.
  • the refractive index is a value measured using an ellipsometer at a wavelength of 550 nm.
  • hue is a value measured using a color difference meter (CR-221, manufactured by Minolta Co., Ltd.).
  • alkali-soluble means that the solubility in 100 g of a 1% by mass aqueous solution of sodium carbonate at a liquid temperature of 22°C is 0.1 g or more.
  • solid content means all components excluding solvent.
  • a laminate according to an embodiment of the present disclosure includes a base material and a resin pattern. Furthermore, at least one selected from the group consisting of sodium ions and potassium ions detected on the surface of the resin pattern based on depth direction analysis of the resin pattern performed along the direction from the resin pattern toward the substrate.
  • the intensity of the component is defined as 100%
  • the distance from the surface of the resin pattern to the point where the intensity of at least one component selected from the group consisting of sodium ions and potassium ions first reaches 90%
  • the presence depth of at least one component selected from the group consisting of sodium ions and potassium ions in the resin pattern defined by is 0.3 ⁇ m to 3.0 ⁇ m.
  • the depth of presence of a specific component in the resin pattern is measured by depth profile analysis using time-of-flight secondary ion mass spectrometry (TOF-SIMS), as described later, and is determined from the "surface of the resin pattern" to " It is represented by the distance to "the point where the intensity of at least one component selected from the group consisting of sodium ions and potassium ions reaches a reference value.”
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • a laminate including a resin pattern that has excellent scratch resistance and prevents or reduces edge lifting.
  • a laminate according to one embodiment of the present disclosure includes a substrate.
  • base materials include resin base materials, glass base materials, and semiconductor base materials.
  • the substrate is preferably a resin substrate.
  • resin substrates include cycloolefin polymer films, polypropylene films, polyethylene terephthalate films (e.g., biaxially oriented polyethylene terephthalate films), polymethyl methacrylate films, cellulose triacetate films, polystyrene films, polyimide films, and polycarbonate films. be done.
  • the substrate preferably contains a polymer, more preferably at least one selected from the group consisting of a cycloolefin polymer and a polyimide, and still more preferably a cycloolefin polymer.
  • the thickness of the substrate is preferably 5 ⁇ m to 200 ⁇ m, more preferably 10 ⁇ m to 100 ⁇ m.
  • the thickness of the substrate is represented by the arithmetic mean of five thicknesses measured by cross-sectional observation using a scanning electron microscope (SEM).
  • a laminate according to an embodiment of the present disclosure includes a resin pattern.
  • the resin pattern may be placed in contact with the substrate.
  • Other components may be arranged between the substrate and the resin pattern.
  • the shape, width and spacing of the resin pattern are determined according to the application, for example.
  • the width of the resin pattern is preferably in the range of 5 ⁇ m to 1,000 ⁇ m.
  • the distance between the resin patterns is preferably in the range of 5 ⁇ m to 1,000 ⁇ m.
  • the thickness of the resin pattern is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, even more preferably 3 ⁇ m or more, and particularly preferably 5 ⁇ m or more.
  • the upper limit of the thickness of the resin pattern may be 40 ⁇ m, 30 ⁇ m, 20 ⁇ m or 10 ⁇ m.
  • the thickness of the resin pattern is represented by the arithmetic mean of five thicknesses measured by cross-sectional observation using a scanning electron microscope (SEM).
  • the presence depth of at least one component selected from the group consisting of sodium ions and potassium ions in the resin pattern is 0.3 ⁇ m to 3.0 ⁇ m.
  • the aspect that "the presence depth of at least one component selected from the group consisting of sodium ions and potassium ions in the resin pattern is 0.3 ⁇ m to 3.0 ⁇ m" includes the following (1) to (3) is included.
  • the presence depth of either the sodium ion or the potassium ion component may be defined. That is, in the present disclosure, the presence depth of sodium ions in the resin pattern may be 0.3 ⁇ m to 3.0 ⁇ m, or the presence depth of potassium ions in the resin pattern may be 0.3 ⁇ m to 3.0 ⁇ m. good too.
  • the presence depth of sodium ions in the resin pattern is 0.3 ⁇ m or more and 3.0 ⁇ m or less, and the presence depth of potassium ions in the resin pattern is 0.3 ⁇ m or more and 3.0 ⁇ m or less.
  • the presence depth of sodium ions in the resin pattern is 0.3 ⁇ m or more and 3.0 ⁇ m or less, and the presence depth of potassium ions in the resin pattern is less than 0.3 ⁇ m or more than 3.0 ⁇ m.
  • the presence depth of sodium ions in the resin pattern is less than 0.3 ⁇ m or more than 3.0 ⁇ m, and the presence depth of potassium ions in the resin pattern is 0.3 ⁇ m or more and 3.0 ⁇ m or less.
  • the depth of presence of at least one component selected from the group consisting of sodium ions and potassium ions in the resin pattern is preferably 0.5 ⁇ m or more, and preferably 1.0 ⁇ m or more. It is more preferable that the thickness is 1.5 ⁇ m or more. From the viewpoint of reducing edge floating, the depth of presence of at least one component selected from the group consisting of sodium ions and potassium ions in the resin pattern is preferably 2.8 ⁇ m or less, and is 2.5 ⁇ m or less. is more preferably 2.2 ⁇ m or less.
  • the presence depth of at least one component selected from the group consisting of sodium ions and potassium ions in the resin pattern is measured by depth profile analysis using time-of-flight secondary ion mass spectrometry (TOF-SIMS).
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • the target component that is, sodium ion or potassium ion
  • Depth profile analysis is performed along the direction from the resin pattern toward the substrate. Specifically, sodium ions or potassium ions are detected by TOF-SIMS while sputtering the object to be measured with an Ar 2 + cluster sputtering gun.
  • the sputtering time when the intensity of the target component first reaches 90% is determined by the depth ( That is, the distance from the surface of the resin pattern to the point where the intensity of the target component first reaches 90%).
  • the depth That is, the distance from the surface of the resin pattern to the point where the intensity of the target component first reaches 90%.
  • the sodium ion or potassium ion is detected by TOF-SIMS while sputtering including the other layer.
  • OCA Optical Clear Adhesive
  • the interface between the resin pattern and another layer is determined based on the thickness of each layer, the sputtering rate, and the components detected in each layer. For example, at the interface between the resin pattern and another layer that does not contain sodium ions or potassium ions, the peak of sodium ions or potassium ions rises, so the portion where the peak of sodium ions or potassium ions rises can be regarded as the surface of the resin pattern. .
  • the depth of presence of the specific component (that is, at least one component selected from the group consisting of sodium ions and potassium ions) in the resin pattern is adjusted, for example, by the manufacturing conditions of the resin pattern.
  • the manufacturing conditions of the resin pattern For example, as described in the section "Laminate manufacturing method" below, when a developer containing a specific component is used in the process of manufacturing a resin pattern, the depth at which the specific component exists in the resin pattern It changes according to the degree of permeation of the components of the developer into the pattern. For example, when the degree of permeation of the components of the developer into the resin pattern increases, the presence depth of the specific component in the resin pattern increases.
  • the degree of permeation of the components of the developer into the resin pattern decreases, the presence depth of the specific component in the resin pattern decreases.
  • the degree of permeation of the components of the developer into the resin pattern depends, for example, on the development conditions (e.g., the temperature and processing time of the developer), and on the cleaning conditions. It is adjusted by the conditions (eg water temperature and treatment time) and the standing time after washing.
  • the method of adjusting the existence depth of the specific component in the resin pattern is not limited to the above specific examples.
  • the ratio of the depth of presence of the specific component in the resin pattern to the thickness of the resin pattern is preferably 0.1 to 0.9. It is preferably 0.2 to 0.7, even more preferably 0.3 to 0.5.
  • the absolute value of the difference between the thickness of the resin pattern and the depth of existence of the specific component in the resin pattern is 0.5 ⁇ m to 10 ⁇ m. It is preferably 1 ⁇ m to 6 ⁇ m, more preferably 2 ⁇ m to 4 ⁇ m.
  • the moisture permeability of the resin pattern with a thickness of 40 ⁇ m is preferably 500 g/(m 2 24 hr) or less, more preferably 300 g/(m 2 24 hr) or less, and 100 g/(m 2 24 hr). ) or less. Specific preferred values include, for example, 80 g/(m 2 ⁇ 24 hr), 150 g/(m 2 ⁇ 24 hr) and 220 g/(m 2 ⁇ 24 hr).
  • the moisture permeability is measured according to "JIS Z 0208 (1976)" (cup method). The above moisture permeability is preferable under any of the test conditions of 40° C. and 90% humidity, 65° C. and 90% humidity, and 80° C. and 95% humidity.
  • a polymer can be used as a component of the resin pattern.
  • the polymer include the polymers described as components of the photosensitive layer in the section "Laminate production method” below.
  • examples of the polymer also include polymers of polymerizable compounds described as components of the photosensitive layer in the section "Method for producing laminate” below.
  • the resin pattern is preferably a cured product of a photosensitive composition.
  • the photosensitive composition preferably contains a polymer.
  • the photosensitive composition also preferably contains a polymerizable compound and a polymerization initiator.
  • the photosensitive composition also preferably contains a polymer, a polymerizable compound and a polymerization initiator.
  • the polymer preferably has a polymerizable group, more preferably a radically polymerizable group.
  • Embodiments of the photosensitive composition are described in the section "Laminate Production Method" below.
  • the method of curing the photosensitive composition is determined, for example, according to the components of the photosensitive composition.
  • Preferred curing methods for the photosensitive composition include, for example, the exposure described in the section "Laminate production method” below.
  • a laminate according to an embodiment of the present disclosure may further include other components as necessary.
  • the type, arrangement and number of other components are determined according to the purpose, for example.
  • Other components include, for example, transparent electrodes and lead wiring.
  • a laminate according to an embodiment of the present disclosure preferably includes a transparent electrode.
  • the laminate according to an embodiment of the present disclosure preferably includes a transparent electrode between the substrate and the resin pattern. That is, the laminate according to an embodiment of the present disclosure preferably includes a substrate, a transparent electrode, and a resin pattern in this order.
  • a laminate according to an embodiment of the present disclosure preferably includes a resin pattern, a transparent electrode, a substrate, a transparent electrode, and a resin pattern in this order.
  • Components of the transparent electrode include, for example, metal oxides. Metal oxides include, for example, indium tin oxide (ITO) and indium zinc oxide (IZO).
  • the transparent electrode may be composed of thin metal wires such as metal nanowires. Metal thin wires include, for example, silver thin wires and copper thin wires.
  • the transparent electrode may be composed of a metal mesh. Silver conductive materials such as silver mesh and silver nanowires are preferred.
  • the transparent electrode may be a transparent electrode pattern.
  • a laminate according to an embodiment of the present disclosure preferably includes routing wiring.
  • the lead-out wiring is preferably arranged between the base material and the resin pattern.
  • the routing wiring is electrically connected to the transparent electrode.
  • a metal is mentioned as a component of a routing wiring. Metals include, for example, gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc and manganese. The metal may be an alloy.
  • the component of the routing wiring is preferably copper, molybdenum, aluminum or titanium, more preferably copper.
  • refractive index adjustment layer examples include the refractive index adjusting layer described as a component of the transfer film in the section "Method for producing laminate" below.
  • FIG. 1 is a schematic cross-sectional view showing the structure of a laminate according to one embodiment.
  • FIG. 2 is a schematic cross-sectional view showing the structure of a laminate according to another embodiment.
  • the structure of the laminate is not limited to the structure shown in each drawing.
  • the laminate 90 shown in FIG. 1 has an image display area 74 and an image non-display area 75 (that is, frame portion).
  • the laminate 90 has touch panel electrodes on both sides of the substrate 32 .
  • the laminate 90 comprises a first metallic conductive material 70 on one side of the substrate 32 and a second metallic conductive material 72 on the other side of the substrate 32 .
  • the routing wiring 56 is connected to each of the first metal conductive material 70 and the second metal conductive material 72 . Examples of the routing wiring 56 include copper wiring and silver wiring.
  • the routing wiring 56 is surrounded by the resin pattern 18 and the first metal conductive material 70 or the second metal conductive material 72 .
  • the resin pattern 18 is formed on one surface of the base material 32 so as to cover the first transparent electrode pattern 70 and the lead wiring 56, and the other surface of the base material 32 is formed with the second resin pattern 18.
  • a resin pattern 18 is formed to cover the metal conductive material 72 and the routing wiring 56 .
  • a laminate 100 shown in FIG. 2 includes a substrate 10, a first wiring portion 20B, a second island electrode portion 30A, a second wiring portion 30B, a resin pattern 60 and a transparent layer 80.
  • the first wiring portions 20B are alternately arranged with the first island-shaped electrode portions (not shown) from the front to the back in FIG. properly connected.
  • the second wiring portion 30B electrically connects two adjacent second island electrode portions 30A.
  • the first island-shaped electrode portion 20B and the second island-shaped electrode portion 30A are covered with the resin pattern 60 .
  • the resin pattern 60 and the second wiring portion 30B are covered with a transparent layer 80.
  • Examples of the transparent layer 80 include OCA.
  • a laminate according to an embodiment of the present disclosure is applied to applications such as a touch panel, for example.
  • a laminate according to an embodiment of the present disclosure is preferably a touch panel, and more preferably a capacitive touch panel.
  • the resin pattern preferably functions as a protective film for touch panel electrodes or touch panel wiring.
  • a laminate according to an embodiment of the present disclosure can be used for precision microfabrication by photolithography.
  • the resin pattern preferably functions as an etching resist.
  • the laminate according to one embodiment of the present disclosure preferably includes a conductive layer between the substrate and the resin pattern.
  • Conductive layers include, for example, layers containing metal layers, metal oxide layers, and metal wires. Materials for the metal layer, the metal oxide layer, and the layer containing the fine metal wires include the substances described in the above section "Other components".
  • the laminate is formed by the steps of forming a photosensitive layer on a conductive layer disposed on a substrate, pattern-exposing the photosensitive layer, and exposing the photosensitive layer to light. It is preferably formed through a step of removing an unnecessary portion from the photosensitive layer and a step of removing the conductive layer in the portion where the photosensitive layer has been removed to obtain a conductive pattern.
  • a laminate according to an embodiment of the present disclosure is a semiconductor package, a printed circuit board, various wiring formation applications for a sensor substrate, an electromagnetic wave shielding material, a conductive film such as a film heater, a liquid crystal sealing material, a structure in the micromachine or microelectronics field It can be applied to the formation of objects and the like.
  • a method for manufacturing a laminate according to an embodiment of the present disclosure includes disposing a photosensitive layer on a base material (hereinafter referred to as an “arrangement step”) and pattern-exposing the photosensitive layer (hereinafter , referred to as an “exposure step”), and a developer containing at least one component selected from the group consisting of sodium ions and potassium ions to remove the exposed or unexposed areas of the photosensitive layer, and forming a pattern (hereinafter referred to as "development step”); washing the resin pattern with water (hereinafter referred to as “washing step”); (hereinafter referred to as a “stilling step”), and is carried out along the direction from the resin pattern that has passed through the standing of the base material and the resin pattern to the base material.
  • the intensity of at least one component selected from the group consisting of sodium ions and potassium ions detected on the surface of the resin pattern is defined as 100%
  • the above Sodium ions and potassium in the resin pattern defined by the distance from the surface of the resin pattern to the point where the intensity of at least one component selected from the group consisting of sodium ions and potassium ions first reaches 90%.
  • the existence depth of at least one component selected from the group consisting of ions is preferably 0.3 ⁇ m to 3.0 ⁇ m.
  • the series of steps including the developing step, washing step, and standing step in the present disclosure is the presence depth of the specific component (i.e., at least one component selected from the group consisting of sodium ions and potassium ions) in the resin pattern.
  • the stationary step greatly contributes to the purpose of adjusting the existence depth of the specific component in the resin pattern to a specific range.
  • the degree of permeation of the component of the developer into the resin pattern changes, and the existence depth of the specific component in the resin pattern is 0.3 ⁇ m to 0.3 ⁇ m. Adjusted to 3.0 ⁇ m. Therefore, according to one embodiment of the present disclosure, there is provided a method for manufacturing a laminate including a resin pattern that has excellent scratch resistance and prevents or reduces edge lifting.
  • the photosensitive layer is disposed on the substrate.
  • the photosensitive layer may be placed in contact with the substrate.
  • Other components may be placed between the substrate and the photosensitive layer.
  • a method for manufacturing a laminate including a base material, a transparent electrode, and a resin pattern in this order includes preparing a substrate including a base material and a transparent electrode in this order before the placement step. is preferred.
  • the aspect of the base material is described in the "Laminate” section above. Preferred aspects of the base material are the same as the preferred aspects of the base material described in the section “Laminate” above.
  • the photosensitive layer is preferably a negative photosensitive layer.
  • the negative photosensitive layer has the property that the exposed area is less soluble in a developer than the unexposed area.
  • the thickness of the photosensitive layer is determined, for example, according to the thickness of the desired resin pattern.
  • the preferred embodiment of the thickness of the resin pattern described in the above section of "Laminate” applies mutatis mutandis to the preferred embodiment of the thickness of the photosensitive layer.
  • the thickness of the photosensitive layer may be 30 ⁇ m or less. From the viewpoint of improving developability, the thickness of the photosensitive layer is preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, even more preferably 10 ⁇ m or less, and 5.0 ⁇ m or less. Especially preferred. From the viewpoint of improving the strength of the resin pattern, the thickness of the photosensitive layer is preferably 0.60 ⁇ m or more, more preferably 1.5 ⁇ m or more.
  • the thickness of the photosensitive layer is represented by the arithmetic mean of 5 thicknesses measured by cross-sectional observation using a scanning electron microscope (SEM).
  • the refractive index of the photosensitive layer is preferably from 1.41 to 1.59, more preferably from 1.47 to 1.56.
  • the photosensitive layer is preferably achromatic.
  • the L * value is found to be between 10 and 90.
  • the a * value is -1.0 to 1.0 and the b * value is preferably -1.0 to 1.0.
  • the visible light transmittance per 1.0 ⁇ m thickness of the photosensitive layer is preferably 80% or more, more preferably 90% or more. More preferably, it is 95% or more, most preferably.
  • the visible light transmittance all of the average transmittance at a wavelength of 400 nm to 800 nm, the minimum transmittance at a wavelength of 400 nm to 800 nm, and the transmittance at a wavelength of 400 nm are preferably 80% or more.
  • Preferred values for transmittance include, for example, 87%, 92% and 98%.
  • the dissolution rate of the photosensitive layer in a 1.0% by mass sodium carbonate aqueous solution is preferably 0.01 ⁇ m/sec or more, more preferably 0.10 ⁇ m/sec or more. It is preferably 0.20 ⁇ m/second or more, and more preferably 0.20 ⁇ m/second or more. From the viewpoint of the edge shape of the pattern, the dissolution rate of the photosensitive layer in a 1.0% by mass sodium carbonate aqueous solution is preferably 5.0 ⁇ m/sec or less, more preferably 4.0 ⁇ m/sec or less. , 3.0 ⁇ m/sec or less.
  • Specific preferred numerical values include, for example, 1.8 ⁇ m/second, 1.0 ⁇ m/second and 0.7 ⁇ m/second.
  • the dissolution rate of the photosensitive layer in a 1.0 mass % sodium carbonate aqueous solution is measured by the following method.
  • the photosensitive layer (thickness: within the range of 1.0 ⁇ m to 10 ⁇ m) from which the solvent has been sufficiently removed is showered with a 1.0% by mass sodium carbonate aqueous solution at 25° C. until the photosensitive layer is completely dissolved.
  • the upper limit of the shower development time is 2 minutes.
  • the shower nozzle used for development is 1/4 MINJJX030PP manufactured by Ikeuchi Co., Ltd.
  • the spray pressure of the shower is 0.08 MPa.
  • the shower flow rate per unit time is 1,800 mL/min.
  • the dissolution rate is calculated by dividing the thickness of the photosensitive layer by the time required for the photosensitive layer to completely dissolve. If the photosensitive layer is not completely melted in 2 minutes, the amount of film thickness change is calculated in the same manner.
  • the swelling rate of the photosensitive layer after exposure to a 1.0% by mass sodium carbonate aqueous solution is preferably 100% or less, more preferably 50% or less, and more preferably 30%. More preferably: Specific preferred values include, for example, 4%, 13% and 25%.
  • the swelling rate of the photosensitive layer after exposure to a 1.0% by weight sodium carbonate aqueous solution is measured by the following method.
  • the photosensitive layer (thickness: within the range of 1.0 ⁇ m to 10 ⁇ m) from which the solvent has been sufficiently removed is exposed with an ultra-high pressure mercury lamp at 500 mj/cm 2 (i-line measurement).
  • the photosensitive layer is immersed in a 1.0% by weight sodium carbonate aqueous solution, and the thickness of the photosensitive layer is measured after 30 seconds. The percentage increase in the thickness of the photosensitive layer after immersion relative to the thickness of the photosensitive layer before immersion is calculated.
  • the number of foreign substances having a diameter of 1.0 ⁇ m or more in the photosensitive layer is preferably 10/mm 2 or less, more preferably 5/mm 2 or less. Specific preferred values include, for example, 0/mm 2 , 1/mm 2 , 4/mm 2 and 8/mm 2 .
  • the number of foreign objects is measured by the following method. Any five regions (1 mm ⁇ 1 mm) on the surface of the photosensitive layer from the normal direction of the surface of the photosensitive layer are visually observed using an optical microscope, and a diameter of 1 in each region Measure the number of foreign matter of 0 ⁇ m or more, and calculate the number of foreign matter by arithmetically averaging them.
  • the haze of a solution obtained by dissolving 1.0 cm 3 of a photosensitive layer in 1.0 L (liter) of a 1.0% by weight sodium carbonate aqueous solution at 30° C. is It is preferably 60% or less, more preferably 30% or less, even more preferably 10% or less, and particularly preferably 1% or less. Specific preferred values include, for example, 0.4%, 1%, 9% and 24%.
  • Haze is measured by the following method. First, a 1.0% by mass sodium carbonate aqueous solution is prepared and the liquid temperature is adjusted to 30°C. 1.0 cm 3 of photosensitive layer is placed in 1.0 L of sodium carbonate aqueous solution. Stir at 30° C.
  • haze of the solution in which the photosensitive layer is dissolved is measured. Haze is measured using a haze meter (product name “NDH4000”, manufactured by Nippon Denshoku Industries Co., Ltd.) using a liquid measurement unit and a liquid measurement dedicated cell with an optical path length of 20 mm.
  • Components of the photosensitive layer include, for example, polymers, polymerizable compounds, polymerization initiators, heterocyclic compounds, aliphatic thiol compounds, thermal crosslinkable compounds, surfactants, polymerization inhibitors and hydrogen donating compounds. .
  • the photosensitive layer preferably contains a polymer.
  • the polymer will be described below.
  • polymers examples include (meth)acrylic resins, styrene resins, epoxy resins, amide resins, amidoepoxy resins, alkyd resins, phenolic resins, ester resins, urethane resins, and reactions between epoxy resins and (meth)acrylic acid.
  • Acid-modified epoxy acrylate resins obtained by reacting epoxy acrylate resins obtained and epoxy acrylate resins with acid anhydrides are exemplified.
  • a (meth)acrylic resin is one of the preferred embodiments of the polymer because of its excellent alkali developability and film formability.
  • the (meth)acrylic resin means a resin having structural units derived from a (meth)acrylic compound.
  • the content of structural units derived from the (meth)acrylic compound is preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 90% by mass, based on all structural units of the (meth)acrylic resin % by mass or more is more preferable.
  • the (meth)acrylic resin may be composed only of structural units derived from the (meth)acrylic compound, or may have structural units derived from polymerizable monomers other than the (meth)acrylic compound. . That is, the upper limit of the content of structural units derived from the (meth)acrylic compound is 100% by mass with respect to all structural units of the (meth)acrylic resin.
  • (Meth)acrylic compounds include, for example, (meth)acrylic acid, (meth)acrylic acid esters, (meth)acrylamides and (meth)acrylonitrile.
  • (meth)acrylic acid esters examples include (meth)acrylic acid alkyl ester, (meth)acrylic acid tetrahydrofurfuryl ester, (meth)acrylic acid dimethylaminoethyl ester, (meth)acrylic acid diethylaminoethyl ester, (meth) ) acrylic acid glycidyl ester, (meth)acrylic acid benzyl ester, 2,2,2-trifluoroethyl (meth)acrylate and 2,2,3,3-tetrafluoropropyl (meth)acrylate, (meth) Acrylic acid alkyl esters are preferred.
  • the alkyl group of the (meth)acrylic acid alkyl ester may be linear or branched.
  • (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, and (meth)acrylate.
  • the (meth)acrylic acid ester is preferably a (meth)acrylic acid alkyl ester having an alkyl group having 1 to 12 carbon atoms, and is a (meth)acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms. is more preferred, and methyl (meth)acrylate or ethyl (meth)acrylate is even more preferred.
  • (Meth)acrylamides include, for example, acrylamides such as diacetone acrylamide.
  • the (meth)acrylic resin may have structural units other than the structural units derived from the (meth)acrylic compound.
  • the polymerizable monomer forming the structural unit is not particularly limited as long as it is a compound other than the (meth)acrylic compound copolymerizable with the (meth)acrylic compound.
  • Examples include styrene, vinyl toluene, and ⁇ - Styrene compounds optionally having a substituent at the ⁇ -position or aromatic ring such as methylstyrene, vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether, maleic acid, maleic anhydride, monomethyl maleate, maleic acid Maleic acid monoesters such as monoethyl and monoisopropyl maleate, fumaric acid, cinnamic acid, ⁇ -cyanocinnamic acid, itaconic acid and crotonic acid. These polymerizable monomers may be used singly or in combination of two or more.
  • the (meth)acrylic resin preferably has a structural unit having an acid group from the viewpoint of improving alkali developability.
  • Acid groups include, for example, carboxy groups, sulfo groups, phosphoric acid groups, and phosphonic acid groups.
  • the (meth)acrylic resin more preferably has a structural unit having a carboxy group, and more preferably has a structural unit derived from the above (meth)acrylic acid.
  • the content of the structural unit having an acid group (preferably a structural unit derived from (meth)acrylic acid) in the (meth)acrylic resin is excellent in developability, relative to the total mass of the (meth)acrylic resin, It is preferably 10% by mass or more.
  • the upper limit is not particularly limited, it is preferably 50% by mass or less, more preferably 40% by mass or less, from the viewpoint of excellent alkali resistance.
  • the (meth)acrylic resin more preferably has structural units derived from the (meth)acrylic acid alkyl ester described above.
  • the content of the structural unit derived from the (meth)acrylic acid alkyl ester in the (meth)acrylic resin is preferably 50% by mass to 90% by mass, based on the total structural units of the (meth)acrylic resin. It is more preferably in the range of 90% by mass and even more preferably in the range of 65% by mass to 90% by mass.
  • the (meth)acrylic resin a resin having both a structural unit derived from (meth)acrylic acid and a structural unit derived from a (meth)acrylic acid alkyl ester is preferable, and a structural unit derived from (meth)acrylic acid and A resin composed only of structural units derived from a (meth)acrylic acid alkyl ester is more preferable.
  • an acrylic resin having a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from ethyl acrylate is also preferable.
  • the (meth)acrylic resin preferably has at least one selected from the group consisting of structural units derived from methacrylic acid and structural units derived from methacrylic acid alkyl esters. It is more preferable to have both structural units derived from an alkyl ester.
  • the total content of structural units derived from methacrylic acid and structural units derived from methacrylic acid alkyl esters in the (meth)acrylic resin is 40% by mass or more with respect to all structural units of the (meth)acrylic resin. Preferably, it is more preferably 60% by mass or more.
  • the upper limit is not particularly limited, and may be 100% by mass or less, preferably 80% by mass or less.
  • the (meth)acrylic resin is derived from at least one selected from the group consisting of structural units derived from methacrylic acid and structural units derived from methacrylic acid alkyl esters, and structural units derived from acrylic acid and acrylic acid alkyl esters. It is also preferable to have at least one selected from the group consisting of structural units that The total content of methacrylic acid-derived structural units and methacrylic acid alkyl ester-derived structural units is the mass ratio to the total content of acrylic acid-derived structural units and acrylate alkyl ester-derived structural units. is preferably 60/40 to 80/20.
  • the (meth)acrylic resin preferably has an ester group at its end in terms of excellent developability of the photosensitive layer.
  • the terminal portion of the (meth)acrylic resin is composed of a site derived from the polymerization initiator used in the synthesis.
  • a (meth)acrylic resin having an ester group at its terminal can be synthesized by using a polymerization initiator that generates a radical having an ester group.
  • the polymer is preferably, for example, a polymer having an acid value of 60 mgKOH/g or more from the viewpoint of developability. Further, the polymer is, for example, a resin having a carboxy group with an acid value of 60 mgKOH/g or more (so-called carboxy group-containing resin) because it is thermally crosslinked with a cross-linking component by heating and easily forms a strong film. More preferably, it is a (meth)acrylic resin having a carboxy group with an acid value of 60 mgKOH/g or more (so-called carboxy group-containing (meth)acrylic resin).
  • the three-dimensional crosslink density can be increased by, for example, adding a thermally crosslinkable compound such as a blocked isocyanate compound to thermally crosslink.
  • a thermally crosslinkable compound such as a blocked isocyanate compound
  • the carboxy group of the resin having a carboxy group is dehydrated and hydrophobized, the wet heat resistance can be improved.
  • the carboxy group-containing (meth)acrylic resin having an acid value of 60 mgKOH/g or more is not particularly limited as long as it satisfies the above acid value conditions, and can be appropriately selected from known (meth)acrylic resins.
  • a carboxy group-containing acrylic resin having an acid value of 60 mgKOH/g or more paragraphs [0033] to [0052] of JP-A-2010-237589
  • carboxy group-containing acrylic resins having an acid value of 60 mgKOH/g or more can be preferably used.
  • the polymer is a styrene-acrylic copolymer.
  • the styrene-acrylic copolymer refers to a resin having a structural unit derived from a styrene compound and a structural unit derived from a (meth)acrylic compound, and the structural unit derived from the styrene compound and the (meth)
  • the total content of structural units derived from acrylic compounds is preferably 30% by mass or more, more preferably 50% by mass or more, based on all the structural units of the copolymer.
  • the content of structural units derived from a styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, and 5% by mass, based on the total structural units of the copolymer. More preferably, it is up to 80% by mass.
  • the content of the structural unit derived from the (meth)acrylic compound is preferably 5% by mass or more, more preferably 10% by mass or more, based on the total structural units of the copolymer. , more preferably 20% by mass to 95% by mass.
  • the polymer preferably has an aromatic ring structure, and more preferably has a structural unit having an aromatic ring structure.
  • Monomers that form structural units having an aromatic ring structure include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid , styrene dimers, and styrene trimers).
  • a monomer having an aralkyl group or styrene is preferable.
  • the aralkyl group includes a substituted or unsubstituted phenylalkyl group (excluding a benzyl group), a substituted or unsubstituted benzyl group, and the like, and a substituted or unsubstituted benzyl group is preferred.
  • Examples of monomers having a phenylalkyl group include phenylethyl (meth)acrylate.
  • Examples of monomers having a benzyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate; vinyl monomers having a benzyl group, such as vinylbenzyl chloride, and vinyl benzyl alcohol and the like. Among them, benzyl (meth)acrylate is preferred.
  • the polymer more preferably has a structural unit represented by the following formula (S) (a structural unit derived from styrene).
  • the content of the structural unit having an aromatic ring structure is preferably 5% by mass to 90% by mass with respect to the total structural units of the polymer, and 10 It is more preferably from 70% by mass, and even more preferably from 20% by mass to 60% by mass.
  • the content of structural units having an aromatic ring structure in the polymer is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 60 mol%, based on the total structural units of the polymer. Preferably, it is more preferably 20 mol % to 60 mol %.
  • the content of the structural unit represented by the above formula (S) in the polymer is preferably 5 mol% to 70 mol%, preferably 10 mol% to 60 mol%, based on the total structural units of the polymer. More preferably 20 mol % to 60 mol %, particularly preferably 20 mol % to 50 mol %.
  • the "structural unit” when the content of the "structural unit” is defined by the molar ratio, the "structural unit” is synonymous with the “monomer unit”.
  • the "monomer unit” may be modified after polymerization by a polymer reaction or the like. The same applies to the following.
  • the polymer preferably has an aliphatic hydrocarbon ring structure.
  • the polymer preferably has structural units having an aliphatic hydrocarbon ring structure.
  • the aliphatic hydrocarbon ring structure may be monocyclic or polycyclic.
  • the polymer more preferably has a ring structure in which two or more aliphatic hydrocarbon rings are condensed.
  • rings constituting the aliphatic hydrocarbon ring structure in the constituent unit having the aliphatic hydrocarbon ring structure include tricyclodecane ring, cyclohexane ring, cyclopentane ring, norbornane ring, and isoboron ring.
  • a ring in which two or more aliphatic hydrocarbon rings are condensed is preferable, and a tetrahydrodicyclopentadiene ring (tricyclo[5.2.1.0 2,6 ]decane ring) is more preferable.
  • Examples of monomers forming structural units having an aliphatic hydrocarbon ring structure include dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate.
  • the polymer more preferably has a structural unit represented by the following formula (Cy), and a structural unit represented by the above formula (S) and a structure represented by the following formula (Cy) It is more preferable to have units.
  • RM represents a hydrogen atom or a methyl group
  • R Cy represents a monovalent group having an aliphatic hydrocarbon ring structure
  • RM in formula ( Cy ) is preferably a methyl group.
  • R Cy in formula (Cy) is preferably a monovalent group having an aliphatic hydrocarbon ring structure having 5 to 20 carbon atoms, and a monovalent group having an aliphatic hydrocarbon ring structure having 6 to 16 carbon atoms. is more preferably a group, more preferably a monovalent group having an aliphatic hydrocarbon ring structure with 8 to 14 carbon atoms.
  • the aliphatic hydrocarbon ring structure in R Cy of formula (Cy) is preferably a cyclopentane ring structure, a cyclohexane ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornane ring structure, or an isoboron ring structure, and a cyclohexane ring structure. or a tetrahydrodicyclopentadiene ring structure, more preferably a tetrahydrodicyclopentadiene ring structure.
  • the aliphatic hydrocarbon ring structure in R Cy of the formula (Cy) is preferably a ring structure in which two or more aliphatic hydrocarbon rings are condensed, and two to four aliphatic hydrocarbon rings are condensed. It is more preferable that the ring is a rounded ring.
  • the polymer may have one type of structural unit having an aliphatic hydrocarbon ring structure, or may have two or more types.
  • the content of the structural unit having an aliphatic hydrocarbon ring structure is 5% by mass to 90% by mass based on the total structural units of the polymer. preferably 10% by mass to 80% by mass, even more preferably 20% by mass to 70% by mass.
  • the content of structural units having an aliphatic hydrocarbon ring structure in the polymer is preferably 5 mol% to 70 mol%, and 10 mol% to 60 mol%, based on the total structural units of the polymer. is more preferable, and 20 mol % to 50 mol % is even more preferable.
  • the content of the structural unit represented by the above formula (Cy) in the polymer is preferably 5 mol% to 70 mol%, preferably 10 mol% to 60 mol%, based on the total structural units of the polymer. more preferably 20 mol % to 50 mol %.
  • the total content of structural units having an aromatic ring structure and structural units having an aliphatic hydrocarbon ring structure is It is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and even more preferably 40% by mass to 75% by mass, based on the total structural units of the coalescence.
  • the total content of the constituent units having an aromatic ring structure and the constituent units having an aliphatic hydrocarbon ring structure in the polymer is preferably 10 mol% to 80 mol% with respect to the total constituent units of the polymer, It is more preferably 20 mol % to 70 mol %, even more preferably 40 mol % to 60 mol %.
  • the total content of the structural unit represented by the formula (S) and the structural unit represented by the formula (Cy) in the polymer is 10 mol% to 80 mol% with respect to the total structural units of the polymer. preferably 20 mol % to 70 mol %, even more preferably 40 mol % to 60 mol %.
  • the molar amount nS of the structural unit represented by the formula (S) and the molar amount nCy of the structural unit represented by the formula (Cy) in the polymer preferably satisfy the relationship represented by the following formula (SCy), It more preferably satisfies the following formula (SCy-1), and further preferably satisfies the following formula (SCy-2).
  • SCy 0.2 ⁇ nS/(nS+nCy) ⁇ 0.8: Formula (SCy) 0.30 ⁇ nS / (nS + nCy) ⁇ 0.75: formula (SCy-1) 0.40 ⁇ nS / (nS + nCy) ⁇ 0.70: formula (SCy-2)
  • the polymer preferably has a structural unit having an acid group.
  • the acid group includes a carboxy group, a sulfo group, a phosphonic acid group, and a phosphoric acid group, with the carboxy group being preferred.
  • a structural unit having an acid group a structural unit derived from (meth)acrylic acid shown below is preferable, and a structural unit derived from methacrylic acid is more preferable.
  • the polymer may have one type of structural unit having an acid group, or may have two or more types.
  • the content of the structural unit having an acid group is preferably 5% by mass to 50% by mass, based on the total structural units of the polymer, and 5% by mass. It is more preferably from 10 to 30% by mass, more preferably from 10 to 30% by mass.
  • the content of structural units having an acid group in the polymer is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 50 mol%, based on the total structural units of the polymer. , more preferably 20 mol % to 40 mol %.
  • the content of structural units derived from (meth)acrylic acid in the polymer is preferably 5 mol% to 70 mol%, and preferably 10 mol% to 50 mol%, based on the total structural units of the polymer. is more preferred, and 20 mol % to 40 mol % is even more preferred.
  • the polymer preferably has a reactive group, and more preferably has a structural unit having a reactive group.
  • the reactive group is preferably a polymerizable group, more preferably a radically polymerizable group, and still more preferably an ethylenically unsaturated group.
  • the polymer when the polymer has an ethylenically unsaturated group, the polymer preferably has a constitutional unit having an ethylenically unsaturated group in its side chain.
  • the "main chain” represents the relatively longest bond chain in the molecule of the polymer compound that constitutes the resin, and the "side chain” represents an atomic group branched from the main chain.
  • the ethylenically unsaturated group is more preferably an allyl group or a (meth)acryloxy group. Examples of structural units having a reactive group include, but are not limited to, those shown below.
  • the polymer may have one type of structural unit having a reactive group, or may have two or more types.
  • the content of the structural unit having a reactive group is preferably 5% by mass to 70% by mass with respect to the total structural units of the polymer, and 10 It is more preferably from 50% by mass, and even more preferably from 20% by mass to 40% by mass.
  • the content of the structural unit having a reactive group in the polymer is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 60 mol%, based on the total structural units of the polymer. is more preferred, and 20 mol % to 50 mol % is even more preferred.
  • a reactive group into a polymer functional groups such as a hydroxyl group, a carboxy group, a primary amino group, a secondary amino group, an acetoacetyl group, and a sulfo group may be added to an epoxy compound, a blocked isocyanate, or the like.
  • functional groups such as a hydroxyl group, a carboxy group, a primary amino group, a secondary amino group, an acetoacetyl group, and a sulfo group may be added to an epoxy compound, a blocked isocyanate, or the like.
  • compounds, isocyanate compounds, vinylsulfone compounds, aldehyde compounds, methylol compounds, and carboxylic acid anhydrides may be added to an epoxy compound, a blocked isocyanate, or the like.
  • glycidyl (meth)acrylate is added to a part of the carboxy group of the obtained polymer by a polymer reaction. to introduce a (meth)acryloxy group into the polymer.
  • a polymer having (meth)acryloxy groups in side chains can be obtained.
  • the polymerization reaction is preferably carried out under temperature conditions of 70°C to 100°C, more preferably under temperature conditions of 80°C to 90°C.
  • an azo initiator is preferable, and for example, V-601 (trade name) or V-65 (trade name) manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. is more preferable.
  • the polymer reaction is preferably carried out under temperature conditions of 80°C to 110°C. In the polymer reaction, it is preferable to use a catalyst such as an ammonium salt.
  • the polymer the following polymers are preferred.
  • the content ratio (a to d) of each structural unit shown below and the weight average molecular weight Mw can be appropriately changed depending on the purpose.
  • the polymer may contain a polymer having a structural unit having a carboxylic anhydride structure (hereinafter also referred to as "polymer X").
  • the carboxylic anhydride structure may be either a linear carboxylic anhydride structure or a cyclic carboxylic anhydride structure, but is preferably a cyclic carboxylic anhydride structure.
  • the ring of the cyclic carboxylic anhydride structure is preferably a 5- to 7-membered ring, more preferably a 5- or 6-membered ring, and even more preferably a 5-membered ring.
  • a structural unit having a carboxylic anhydride structure is a structural unit containing in the main chain a divalent group obtained by removing two hydrogen atoms from a compound represented by the following formula P-1, or a structural unit represented by the following formula P-1 It is preferably a structural unit in which a monovalent group obtained by removing one hydrogen atom from the represented compound is bonded to the main chain directly or via a divalent linking group.
  • R A1a represents a substituent
  • n 1a R A1a may be the same or different
  • Examples of the substituent represented by RA1a include an alkyl group.
  • Z 1a is preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, and still more preferably an alkylene group having 2 carbon atoms.
  • n1a represents an integer of 0 or more.
  • Z 1a represents an alkylene group having 2 to 4 carbon atoms
  • n 1a is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, even more preferably 0.
  • n1a represents an integer of 2 or more
  • multiple R A1a may be the same or different.
  • two or more RA1a groups may combine with each other to form a ring, but preferably do not combine with each other to form a ring.
  • the structural unit having a carboxylic anhydride structure is preferably a structural unit derived from an unsaturated carboxylic anhydride, more preferably a structural unit derived from an unsaturated cyclic carboxylic anhydride, and an unsaturated aliphatic cyclic carboxylic acid anhydride.
  • Structural units derived from acid anhydride are more preferred, structural units derived from maleic anhydride or itaconic anhydride are particularly preferred, and structural units derived from maleic anhydride are most preferred.
  • Rx represents a hydrogen atom, a methyl group, a CH2OH group, or a CF3 group
  • Me represents a methyl group
  • the structural unit having a carboxylic anhydride structure in the polymer X may be of one type alone, or may be of two or more types.
  • the total content of structural units having a carboxylic anhydride structure is preferably 0 mol% to 60 mol%, preferably 5 mol% to 40 mol%, relative to all structural units of polymer X. More preferably, it is still more preferably 10 mol % to 35 mol %.
  • the photosensitive layer may contain only one type of polymer X, or may contain two or more types.
  • the content of the polymer X is preferably 0.1% by mass to 30% by mass, and 0.2% by mass to It is more preferably 20% by mass, even more preferably 0.5% to 20% by mass, and particularly preferably 1% to 20% by mass.
  • the weight average molecular weight (Mw) of the polymer is preferably 5,000 or more, more preferably 10,000 or more, still more preferably 10,000 to 50,000, and 20,000 to 30,000. is particularly preferred.
  • the acid value of the polymer is preferably 10 mgKOH/g to 200 mgKOH/g, more preferably 60 mg to 200 mgKOH/g, still more preferably 60 mgKOH/g to 150 mgKOH/g, and 70 mgKOH/g to 125 mg KOH/g is particularly preferred.
  • the acid value of a polymer is a value measured according to the method described in "JIS K 0070:1992".
  • the degree of dispersion of the polymer is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, and 1.0 to 4.0. is more preferred, and 1.0 to 3.0 is particularly preferred.
  • the photosensitive layer may contain only one type of polymer, or may contain two or more types.
  • the content of the polymer is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and 30% by mass to 70% by mass, based on the total mass of the photosensitive layer. % is more preferred.
  • the photosensitive layer preferably contains a polymerizable compound.
  • the polymerizable compound will be described below.
  • a polymerizable compound is a compound having a polymerizable group.
  • the polymerizable group include radically polymerizable groups and cationic polymerizable groups, with radically polymerizable groups being preferred.
  • the polymerizable compound preferably contains a radically polymerizable compound having an ethylenically unsaturated group (hereinafter also simply referred to as "ethylenically unsaturated compound").
  • a (meth)acryloxy group is preferred as the ethylenically unsaturated group.
  • the ethylenically unsaturated compound in the present specification is a compound other than the above polymer, and preferably has a molecular weight of less than 5,000.
  • One preferred embodiment of the polymerizable compound is a compound represented by the following formula (M) (also simply referred to as "compound M”).
  • Q 2 -R 1 -Q 1 Formula (M)
  • Q 1 and Q 2 each independently represent a (meth)acryloyloxy group
  • R 1 represents a divalent linking group having a chain structure.
  • Q 1 and Q 2 in formula (M) are preferably the same group from the viewpoint of ease of synthesis. From the viewpoint of reactivity, Q 1 and Q 2 in formula (M) are preferably acryloyloxy groups.
  • R 1 in formula (M) is an alkylene group, an alkyleneoxyalkylene group (-L 1 -OL 1 -), or a polyalkyleneoxyalkylene group (-(L 1 -O) p -L 1 -).
  • a hydrocarbon group having 2 to 20 carbon atoms or a polyalkyleneoxyalkylene group is more preferred, an alkylene group having 4 to 20 carbon atoms is even more preferred, and a linear alkylene group having 6 to 18 carbon atoms is particularly preferred.
  • the hydrocarbon group only needs to have a chain structure in at least a part thereof, and the part other than the chain structure is not particularly limited.
  • Each L 1 independently represents an alkylene group, preferably an ethylene group, a propylene group or a butylene group, more preferably an ethylene group or a 1,2-propylene group.
  • p represents an integer of 2 or more, preferably an integer of 2-10.
  • the number of atoms in the shortest linking chain linking Q 1 and Q 2 in compound M is preferably 3 to 50, more preferably 4 to 40, even more preferably 6 to 20, and 8 1 to 12 are particularly preferred.
  • “the number of atoms in the shortest linking chain linking between Q1 and Q2 ” means the shortest is the number of atoms in
  • compound M examples include 1,3-butanediol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, hydrogenation bisphenol A di(meth)acrylate, hydrogenated bisphenol F di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, poly(ethylene glycol/propylene glycol) di(meth)acrylate, and polybutylene glycol di(meth)acrylate.
  • ester monomers can also be used as a mixture.
  • 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate.
  • ) is preferably at least one compound selected from the group consisting of acrylates, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,10- More preferably, at least one compound selected from the group consisting of decanediol di(meth)acrylates, 1,9-nonanediol di(meth)acrylate and 1,10-decanediol di(meth) More preferably, it is at least one compound selected from the group consisting of acrylates.
  • a preferred embodiment of the polymerizable compound is a bifunctional or higher ethylenically unsaturated compound.
  • "difunctional or higher ethylenically unsaturated compound” means a compound having two or more ethylenically unsaturated groups in one molecule.
  • a (meth)acryloyl group is preferred as the ethylenically unsaturated group in the ethylenically unsaturated compound.
  • a (meth)acrylate compound is preferable as the ethylenically unsaturated compound.
  • bifunctional ethylenically unsaturated compound is not particularly limited and can be appropriately selected from known compounds.
  • Bifunctional ethylenically unsaturated compounds other than compound M include tricyclodecanedimethanol di(meth)acrylate and 1,4-cyclohexanediol di(meth)acrylate.
  • bifunctional ethylenically unsaturated compounds include tricyclodecanedimethanol diacrylate (trade name: NK Ester A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecanedimethanol dimethacrylate (trade name : NK Ester DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (trade name: NK Ester A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), and 1,6-hexane Diol diacrylate (trade name: NK Ester A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.) can be mentioned.
  • the trifunctional or higher ethylenically unsaturated compound is not particularly limited and can be appropriately selected from known compounds.
  • Examples of tri- or higher ethylenically unsaturated compounds include dipentaerythritol (tri/tetra/penta/hexa) (meth)acrylate, pentaerythritol (tri/tetra) (meth)acrylate, trimethylolpropane tri(meth)acrylate, Ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds having a glycerin tri(meth)acrylate skeleton can be mentioned.
  • (tri/tetra/penta/hexa) (meth)acrylate is a concept that includes tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate.
  • (tri/tetra)(meth)acrylate” is a concept that includes tri(meth)acrylate and tetra(meth)acrylate.
  • caprolactone-modified compounds of (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), (meth)acrylates Alkylene oxide-modified compounds of compounds (KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel Allnex, etc.) and ethoxylated glycerin triacrylate (NK Ester A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd., etc.).
  • a urethane (meth)acrylate compound can also be mentioned as a polymerizable compound.
  • Urethane (meth)acrylates include urethane di(meth)acrylates, such as propylene oxide-modified urethane di(meth)acrylates, and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates.
  • Urethane (meth)acrylates also include trifunctional or higher urethane (meth)acrylates.
  • the lower limit of the number of functional groups is more preferably hexafunctional or more, and still more preferably octafunctional or more.
  • the upper limit of the number of functional groups is preferably 20 or less.
  • Trifunctional or higher urethane (meth)acrylates include, for example, 8UX-015A (manufactured by Taisei Fine Chemicals Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and U-15HA (manufactured by Shin-Nakamura Chemical Co., Ltd.). , UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), AH-600 (trade name) manufactured by Kyoeisha Chemical Co., Ltd., and UA-306H, UA-306T, UA-306I, UA-510H, and UX-5000 (both manufactured by Nippon Kayaku Co., Ltd.) and the like.
  • One of the preferred embodiments of the polymerizable compound is an ethylenically unsaturated compound having an acid group.
  • Acid groups include phosphate groups, sulfo groups, and carboxy groups. Among these, a carboxy group is preferable as the acid group.
  • Examples of the ethylenically unsaturated compound having an acid group include tri- to tetra-functional ethylenically unsaturated compounds having an acid group [pentaerythritol tri- and tetraacrylate (PETA) having a carboxyl group introduced into its skeleton (acid value: 80- 120 mg KOH/g)], 5- to 6-functional ethylenically unsaturated compounds having acid groups (dipentaerythritol penta and hexaacrylate (DPHA) skeletons with carboxy groups introduced [acid value: 25-70 mg KOH/g)] etc. If necessary, these trifunctional or higher ethylenically unsaturated compounds having an acid group may be used in combination with a difunctional ethylenically unsaturated compound having an acid group.
  • PETA penentaerythritol tri- and tetraacrylate
  • DPHA dipentaerythritol penta and hex
  • the ethylenically unsaturated compound having an acid group is preferably at least one selected from the group consisting of bifunctional or higher ethylenically unsaturated compounds having a carboxy group and carboxylic acid anhydrides thereof.
  • the ethylenically unsaturated compound having an acid group is at least one selected from the group consisting of a bifunctional or higher ethylenically unsaturated compound having a carboxyl group and its carboxylic acid anhydride, the developability and film strength are improved. increase.
  • the bifunctional or higher ethylenically unsaturated compound having a carboxy group is not particularly limited and can be appropriately selected from known compounds.
  • Examples of bifunctional or higher ethylenically unsaturated compounds having a carboxyl group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.), and Aronix (registered trademark) M-510 (manufactured by Toagosei Co., Ltd.) can be mentioned.
  • the ethylenically unsaturated compound having an acid group is preferably a polymerizable compound having an acid group described in paragraphs [0025] to [0030] of JP-A-2004-239942. incorporated into the specification.
  • the polymerizable compound for example, a compound obtained by reacting a polyhydric alcohol with an ⁇ , ⁇ -unsaturated carboxylic acid, a compound obtained by reacting a glycidyl group-containing compound with an ⁇ , ⁇ -unsaturated carboxylic acid, urethane Urethane monomers such as (meth)acrylate compounds having bonds, ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ '-(meth)acryloyloxyethyl-o-phthalate, ⁇ -hydroxyethyl- ⁇ '-(meth)acryloyloxyethyl -o-phthalate, ⁇ -hydroxypropyl- ⁇ '-(meth)acryloyloxyethyl-o-phthalate and other phthalic acid compounds, and (meth)acrylic acid alkyl esters. These are used alone or in combination of two or more.
  • Compounds obtained by reacting a polyhydric alcohol with an ⁇ , ⁇ -unsaturated carboxylic acid include, for example, 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, 2,2-bis Bisphenol A-based (meth)acrylate compounds such as (4-((meth)acryloxypolypropoxy)phenyl)propane and 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane , polyethylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups, polypropylene glycol di(meth)acrylate having 2 to 14 propylene oxide groups, and 2 to 14 ethylene oxide groups.
  • 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane 2,2-bis Bisphenol A-based (meth)acrylate compounds such as (4-((meth)acryloxypolypropoxy)phenyl)propane and 2,2-bis(
  • an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferable, such as tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or Di(trimethylolpropane)tetraacrylate is more preferred.
  • the polymerizable compound particularly, an ethylenically unsaturated compound
  • one containing an ester bond is particularly preferable in terms of excellent developability of the photosensitive layer after transfer.
  • the ethylenically unsaturated compound containing an ester bond is not particularly limited as long as it contains an ester bond in the molecule, but an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferable, and tetramethylolmethanetri (Meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane)tetraacrylate are more preferred.
  • the ethylenically unsaturated compounds include an ethylenically unsaturated compound having an aliphatic group having 6 to 20 carbon atoms, and an ethylenically unsaturated compound having the above tetramethylolmethane structure or trimethylolpropane structure. It preferably contains a compound and Ethylenically unsaturated compounds having an aliphatic structure with 6 or more carbon atoms include 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and tricyclodecanedimethanol di(meth)acrylate. (Meth)acrylates are mentioned.
  • a preferred embodiment of the polymerizable compound is a polymerizable compound having an aliphatic hydrocarbon ring structure (preferably a bifunctional ethylenically unsaturated compound).
  • a polymerizable compound having a ring structure in which two or more aliphatic hydrocarbon rings are condensed preferably a structure selected from the group consisting of a tricyclodecane structure and a tricyclodecene structure.
  • Bifunctional ethylenically unsaturated compounds having a ring structure in which two or more aliphatic hydrocarbon rings are condensed are preferred, and tricyclodecanedimethanol di(meth)acrylate is even more preferred.
  • a cyclopentane structure As the aliphatic hydrocarbon ring structure, a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornane structure, or an isoboron structure is preferable.
  • the molecular weight of the polymerizable compound is preferably 200 to 3,000, more preferably 250 to 2,600, even more preferably 280 to 2,200, and 300 to 2,200. is particularly preferred.
  • the content ratio of polymerizable compounds having a molecular weight of 300 or less is 30% by mass or less with respect to the content of all polymerizable compounds contained in the photosensitive layer. is preferably 25% by mass or less, and even more preferably 20% by mass or less.
  • the photosensitive layer preferably contains a bifunctional or higher ethylenically unsaturated compound, and more preferably contains a trifunctional or higher ethylenically unsaturated compound. More preferably, it contains a tetrafunctional ethylenically unsaturated compound.
  • the photosensitive layer comprises a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and a polymer having a structural unit having an aliphatic hydrocarbon ring. preferably included.
  • the photosensitive layer preferably contains a compound represented by formula (M) and an ethylenically unsaturated compound having an acid group, and 1,9-nonane More preferably, it contains diol diacrylate, tricyclodecanedimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, and 1,9-nonanediol diacrylate and tricyclodecanedimethanol diacrylate. More preferably, it contains an acrylate and a succinic acid modified form of dipentaerythritol pentaacrylate.
  • M a compound represented by formula (M) and an ethylenically unsaturated compound having an acid group
  • 1,9-nonane More preferably, it contains diol diacrylate, tricyclodecanedimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, and 1,9-nonane
  • the photosensitive layer contains a compound represented by formula (M), an ethylenically unsaturated compound having an acid group, and a thermally crosslinkable compound described later. is preferable, and it is more preferable to contain a compound represented by formula (M), an ethylenically unsaturated compound having an acid group, and a blocked isocyanate compound described later.
  • the photosensitive layer is composed of a bifunctional ethylenically unsaturated compound (preferably, a bifunctional (meth) acrylate compound) and a tri- or more functional ethylenically unsaturated compound (preferably a tri- or more functional (meth)acrylate compound).
  • a bifunctional ethylenically unsaturated compound preferably, a bifunctional (meth) acrylate compound
  • a tri- or more functional ethylenically unsaturated compound preferably a tri- or more functional (meth)acrylate compound
  • the mass ratio of the contents of the difunctional ethylenically unsaturated compound and the trifunctional or higher ethylenically unsaturated compound is preferably 10:90 to 90:10, and 30:70 to 70:30. is more preferred.
  • the content of the bifunctional ethylenically unsaturated compound with respect to the total amount of all ethylenically unsaturated compounds is preferably 20% by mass to 80% by mass, more preferably 30% by mass to 70% by mass. preferable.
  • the content of the bifunctional ethylenically unsaturated compound in the photosensitive layer is preferably 10% by mass to 60% by mass, more preferably 15% by mass to 40% by mass.
  • the photosensitive layer preferably contains the compound M and a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure from the viewpoint of rust prevention.
  • the photosensitive layer contains the compound M and an ethylenically unsaturated compound having an acid group from the viewpoints of substrate adhesion, development residue suppression, and rust prevention.
  • compound M a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, and more preferably containing an ethylenically unsaturated compound having an acid group, compound M, an aliphatic hydrocarbon ring structure
  • the photosensitive layer has 1,9-nonanediol diacrylate and a carboxylic acid group from the viewpoints of substrate adhesion, development residue suppression, and rust prevention. It preferably contains a polyfunctional ethylenically unsaturated compound, preferably contains 1,9-nonanediol diacrylate, tricyclodecanedimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, 1,9-nonanediol diacrylate, tricyclodecanedimethanol diacrylate, dipentaerythritol hexaacrylate, and an ethylenically unsaturated compound having a carboxylic acid group are further preferred, and 1,9-nonanediol diacrylate , tricyclodecanedimethanol diacrylate, an ethylenically unsaturated compound having a carboxylic acid group, and a
  • the photosensitive layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound.
  • the content of bifunctional or higher ethylenically unsaturated compounds in the ethylenically unsaturated compounds is 60% by mass to 100% by mass with respect to the total content of all ethylenically unsaturated compounds contained in the photosensitive layer. is preferred, more preferably 80% by mass to 100% by mass, and even more preferably 90% by mass to 100% by mass.
  • the polymerizable compound preferably has a bisphenol structure from the viewpoint of improving the resolution by suppressing the swelling of the photosensitive layer due to the developer.
  • the bisphenol structure includes, for example, a bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane) and a bisphenol derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane). F structure and bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane) are included, and bisphenol A structure is preferred.
  • polymerizable compounds having a bisphenol structure examples include compounds having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure. Both ends of the bisphenol structure and the two polymerizable groups may be directly bonded or bonded via one or more alkyleneoxy groups.
  • the alkyleneoxy group added to both ends of the bisphenol structure is preferably an ethyleneoxy group or a propyleneoxy group, more preferably an ethyleneoxy group.
  • the number of alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16, more preferably 6 to 14 per molecule.
  • Polymerizable compounds having a bisphenol structure are described in paragraphs [0072] to [0080] of JP-A-2016-224162, and the contents described in this publication are incorporated herein.
  • polymerizable compound having a bisphenol structure a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferable, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is more preferable.
  • 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane examples include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, Showa Denko Materials Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, Shin-Nakamura Chemical Co., Ltd.) ), 2,2-bis(4-(methacryloxydodecaethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Showa Denko Materials), 2,2-bis(4-(methacryloxypentadecaethoxy) Phenyl) propane (BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl) propane (BPE
  • a compound represented by the following general formula (B1) is also preferable.
  • R 1 and R 2 each independently represent a hydrogen atom or a methyl group.
  • A represents C2H4 .
  • B represents C3H6 .
  • n1 and n3 are each independently an integer of 1-39, and n1+n3 is an integer of 2-40.
  • n2 and n4 are each independently an integer of 0-29, and n2+n4 is an integer of 0-30.
  • the arrangement of -(AO)- and -(B-O)- constitutional units may be random or block. In the case of a block, either -(AO)- or -(B-O)- may be on the side of the biphenyl group.
  • n1+n2+n3+n4 is preferably 2 to 20, more preferably 2 to 16, and even more preferably 4 to 12. Further, n2+n4 is preferably 0 to 10, more preferably 0 to 4, still more preferably 0 to 2, and particularly preferably 0.
  • the polymerizable compounds (especially ethylenically unsaturated compounds) may be used singly or in combination of two or more.
  • the content of the polymerizable compound (especially ethylenically unsaturated compound) in the photosensitive layer is preferably 1% by mass to 70% by mass, and 5% by mass to 70% by mass, based on the total mass of the photosensitive layer. %, more preferably 5% by mass to 60% by mass, and particularly preferably 5% by mass to 50% by mass.
  • the photosensitive layer preferably contains a polymerization initiator.
  • the polymerization initiator will be described below.
  • a photopolymerization initiator is preferable as the polymerization initiator.
  • the photopolymerization initiator is not particularly limited, and known photopolymerization initiators can be used.
  • a photopolymerization initiator having an oxime ester structure hereinafter also referred to as an “oxime photopolymerization initiator”
  • a photopolymerization initiator having an ⁇ -aminoalkylphenone structure hereinafter, “ ⁇ - Also referred to as "aminoalkylphenone-based photopolymerization initiator”.
  • ⁇ - also referred to as "aminoalkylphenone-based photopolymerization initiator”
  • a photopolymerization initiator having an ⁇ -hydroxyalkylphenone structure hereinafter also referred to as an " ⁇ -hydroxyalkylphenone-based polymerization initiator
  • an acylphosphine oxide structure A photopolymerization initiator having Also referred to as "agent”.
  • the photopolymerization initiator includes an oxime-based photopolymerization initiator, an ⁇ -aminoalkylphenone-based photopolymerization initiator, an ⁇ -hydroxyalkylphenone-based polymerization initiator, a biimidazole-based polymerization initiator, and an N-phenylglycine-based photopolymerization initiator. It preferably contains at least one selected from the group consisting of agents selected from the group consisting of oxime-based photopolymerization initiators, ⁇ -aminoalkylphenone-based photopolymerization initiators, and N-phenylglycine-based photopolymerization initiators. It is more preferable to include at least one of
  • photopolymerization initiator for example, paragraphs [0031] to [0042] of JP-A-2011-95716, and paragraphs [0064] to [0081] of JP-A-2015-014783 A polymerization initiator may be used.
  • photopolymerization initiators include 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyloxime) [trade name: IRGACURE (registered trademark) OXE-01, BASF company], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) [trade name: IRGACURE (registered trademark) OXE-02 , manufactured by BASF], IRGACURE (registered trademark) OXE03 (manufactured by BASF), IRGACURE (registered trademark) OXE04 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1 -[4-(4-morpholinyl)phenyl]-1-butanone [trade name: Omnirad (registered trademark) 379EG, IGM Resins B
  • oxime ester [trade name: Lunar (registered trademark) 6, manufactured by DKSH Japan], 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione- 2-(O-benzoyloxime) (trade name: TR-PBG-305, manufactured by Changzhou Power Electronics New Materials Co., Ltd.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2- Furanylcarbonyl)-9H-carbazol-3-yl]-,2-(O-acetyloxime) (trade name: TR-PBG-326, manufactured by Changzhou Tenryu Electric New Materials Co., Ltd.), 3-cyclohexyl-1-(6 -(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name:
  • a photoradical polymerization initiator which is one type of photopolymerization initiator, preferably contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof.
  • the two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and its derivative may be the same or different.
  • 2,4,5-triarylimidazole dimer examples include, for example, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di (Methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2- (p-Methoxyphenyl)-4,5-diphenylimidazole dimer.
  • the polymerization initiator may be used singly or in combination of two or more. When two or more are used in combination, an oxime photopolymerization initiator and at least one selected from ⁇ -aminoalkylphenone photopolymerization initiators and ⁇ -hydroxyalkylphenone polymerization initiators can be used. preferable.
  • the content of the polymerization initiator is preferably 0.1% by mass or more, and 0.5% by mass or more, relative to the total mass of the photosensitive layer. is more preferable, and 1.0% by mass or more is even more preferable.
  • the upper limit thereof is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the photosensitive layer.
  • the photosensitive layer may contain a heterocyclic compound.
  • the heterocyclic compound will be described below.
  • the heterocyclic ring possessed by the heterocyclic compound may be either monocyclic or polycyclic heterocyclic ring.
  • a nitrogen atom, an oxygen atom, and a sulfur atom are mentioned as a heteroatom which a heterocyclic compound has.
  • the heterocyclic compound preferably has at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably has a nitrogen atom.
  • heterocyclic compounds examples include triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, benzoxazole compounds, and pyrimidine compounds.
  • the heterocyclic compound is at least one selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzimidazole compounds, and benzoxazole compounds.
  • At least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, and benzoxazole compounds is more preferred.
  • heterocyclic compound Preferred specific examples of the heterocyclic compound are shown below.
  • triazole compounds and benzotriazole compounds include the following compounds.
  • the following compounds can be exemplified as thiadiazole compounds.
  • triazine compounds include the following compounds.
  • the following compounds can be exemplified as rhodanine compounds.
  • the following compounds can be exemplified as thiazole compounds.
  • the following compounds can be exemplified as benzimidazole compounds.
  • the heterocyclic compound may be used singly or in combination of two or more.
  • the content of the heterocyclic compound is preferably 0.01% by mass to 20.0% by mass, based on the total mass of the photosensitive layer, and 0.10% by mass. % to 10.0 mass %, more preferably 0.30 mass % to 8.0 mass %, and particularly preferably 0.50 mass % to 5.0 mass %.
  • the photosensitive layer may contain an aromatic thiol compound other than an aliphatic thiol compound or a heterocyclic compound.
  • aromatic thiol compound other than an aliphatic thiol compound or a heterocyclic compound.
  • the aliphatic thiol compound will be described below.
  • the photosensitive layer contains an aliphatic thiol compound
  • the en-thiol reaction between the aliphatic thiol compound and the radically polymerizable compound having an ethylenically unsaturated group suppresses curing shrinkage of the formed film. and stress is relieved.
  • aliphatic thiol compound a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (that is, a bifunctional or higher aliphatic thiol compound) is preferable.
  • polyfunctional aliphatic thiol compounds are preferable as the aliphatic thiol compound from the viewpoint of adhesion of the formed pattern (particularly, adhesion after exposure).
  • polyfunctional aliphatic thiol compound means an aliphatic compound having two or more thiol groups (also referred to as "mercapto groups”) in the molecule.
  • a low-molecular-weight compound having a molecular weight of 100 or more is preferable as the polyfunctional aliphatic thiol compound.
  • the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, still more preferably 150 to 1,000.
  • the number of functional groups of the polyfunctional aliphatic thiol compound is, for example, preferably 2 to 10, more preferably 2 to 8, and even more preferably 2 to 6, from the viewpoint of adhesion of the pattern to be formed.
  • polyfunctional aliphatic thiol compounds include trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolethane tris(3-mercaptobutyrate ), tris [(3-mercaptopropionyloxy) ethyl] isocyanurate, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate pionate), dipentaerythritol hexakis(3-mercaptopropionat
  • polyfunctional aliphatic thiol compounds include trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, and 1,3,5- At least one compound selected from the group consisting of tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione is preferred.
  • Examples of monofunctional aliphatic thiol compounds include 1-octanethiol, 1-dodecanethiol, ⁇ -mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n- Octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.
  • the photosensitive layer contains an aromatic thiol compound other than an aliphatic thiol compound or a heterocyclic compound, so that a layer containing silver is adjacent to the photosensitive layer (that is, a layer containing silver is adjacent to the resin pattern) ), and can suppress alteration and migration of silver.
  • the photosensitive layer may contain a single aliphatic thiol compound or an aromatic thiol compound other than a heterocyclic compound, or may contain two or more aliphatic thiol compounds.
  • the content of the aliphatic thiol compound is preferably 0.1% by mass or more with respect to the total mass of the photosensitive layer, and 0.1% by mass or more. It is more preferably 1% by mass to 30% by mass, even more preferably 0.2% by mass to 20% by mass, and particularly preferably 0.5% by mass to 10% by mass.
  • the photosensitive layer preferably contains a thermally crosslinkable compound from the viewpoint of the strength of the resulting cured film and the adhesiveness of the resulting uncured film.
  • the thermally crosslinkable compound will be described below.
  • a thermally crosslinkable compound having an ethylenically unsaturated group which will be described later, is not treated as an ethylenically unsaturated compound, but as a thermally crosslinkable compound.
  • thermally crosslinkable compounds examples include epoxy compounds, oxetane compounds, methylol compounds, and blocked isocyanate compounds. Among them, a blocked isocyanate compound is preferable from the viewpoint of the strength of the cured film to be obtained and the adhesiveness of the uncured film to be obtained.
  • a blocked isocyanate compound reacts with a hydroxy group and a carboxy group, for example, when at least one of a polymer and a radically polymerizable compound having an ethylenically unsaturated group has at least one of a hydroxy group and a carboxy group, The hydrophilicity of the formed film tends to decrease, and the function as a protective film tends to be strengthened.
  • a blocked isocyanate compound refers to "a compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) with a blocking agent".
  • the dissociation temperature of the blocked isocyanate compound is not particularly limited, it is preferably 100°C to 160°C, more preferably 130°C to 150°C.
  • the dissociation temperature of the blocked isocyanate means "the temperature of the endothermic peak associated with the deprotection reaction of the blocked isocyanate when measured by DSC (Differential Scanning Calorimetry) analysis using a differential scanning calorimeter".
  • DSC Different Scanning Calorimetry
  • a differential scanning calorimeter for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be preferably used. However, the differential scanning calorimeter is not limited to this.
  • Blocking agents having a dissociation temperature of 100° C. to 160° C. include active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)] and oxime compounds.
  • malonic acid diesters dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.
  • the blocking agent having a dissociation temperature of 100° C. to 160° C. is preferably at least one selected from oxime compounds from the viewpoint of storage stability.
  • the blocked isocyanate compound preferably has an isocyanurate structure in terms of, for example, improving the brittleness of the film and improving the adhesion to the transferred material.
  • a blocked isocyanate compound having an isocyanurate structure is obtained, for example, by isocyanurating hexamethylene diisocyanate and protecting it.
  • blocked isocyanate compounds having an isocyanurate structure compounds having an oxime structure using an oxime compound as a blocking agent tend to have a dissociation temperature within a preferred range and produce less development residue than compounds having no oxime structure. It is preferable because it is easy to
  • the blocked isocyanate compound may have a polymerizable group.
  • the polymerizable group is not particularly limited, and any known polymerizable group can be used, and a radically polymerizable group is preferred.
  • Polymerizable groups include groups having ethylenically unsaturated groups such as (meth)acryloxy groups, (meth)acrylamide groups, and styryl groups, and epoxy groups such as glycidyl groups. Among them, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth)acryloxy group, and still more preferably an acryloxy group.
  • a commercially available product can be used as the blocked isocyanate compound.
  • Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (manufactured by Showa Denko K.K.), block type Duranate series (for example, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation).
  • a compound having the following structure can also be used as the blocked isocyanate compound.
  • the thermally crosslinkable compound may be used singly or in combination of two or more.
  • the content of the thermally crosslinkable compound is preferably 1% by mass to 50% by mass, and 5% by mass to 30% by mass, based on the total mass of the photosensitive layer. % is more preferable.
  • the photosensitive layer may contain a surfactant.
  • the surfactant will be described below.
  • surfactants examples include those described in paragraph [0017] of Japanese Patent No. 4502784 and paragraphs [0060] to [0071] of JP-A-2009-237362.
  • a nonionic surfactant a fluorosurfactant or a silicone surfactant is preferred.
  • Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (above , manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW- 100
  • fluorosurfactants include, for example, Megafac (registered trademark) F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143 , F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F -557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, MFS-578, MFS -579, MFS-586, MFS-587, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94 , RS-72-K, DS-21 (manufactured by DIC Corporation), Florard FC430, FC431, FC171 (manufactured by Sum), Flor
  • an acrylic compound that has a molecular structure with a functional group containing a fluorine atom and in which the portion of the functional group containing the fluorine atom is cleaved and the fluorine atom volatilizes when heat is applied can also be preferably used.
  • fluorine-based surfactants include Megafac (registered trademark) DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), For example, Megafac (registered trademark) DS-21 can be mentioned.
  • fluorosurfactant it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.
  • a block polymer can also be used as a fluorosurfactant.
  • the fluorine-based surfactant has a structural unit derived from a (meth)acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups).
  • a fluorine-containing polymer compound containing a structural unit derived from a (meth)acrylate compound can also be preferably used.
  • a fluoropolymer having an ethylenically unsaturated bond-containing group in its side chain can also be used.
  • fluorine-based surfactants from the viewpoint of improving environmental friendliness, compounds having linear perfluoroalkyl groups having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), are used.
  • PFOA perfluorooctanoic acid
  • PFOS perfluorooctane sulfonic acid
  • Surfactants derived from alternative materials are preferred.
  • silicone-based surfactants include straight-chain polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups are introduced into side chains and terminals.
  • silicone surfactants include DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (toray ⁇ Dow Corning Co., Ltd.), X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF- 643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (manufactured by Shin-Etsu Chemical Co., Ltd.), F-4440, TSF-4300, TSF- 4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), BYK307, BYK323,
  • the surfactants may be used singly or in combination of two or more.
  • the content of the surfactant is preferably 0.01% by mass to 3.0% by mass, based on the total mass of the photosensitive layer, and 0.01% by mass. % to 1.0% by mass, more preferably 0.05% to 0.80% by mass.
  • the photosensitive layer may contain a polymerization inhibitor.
  • the polymerization inhibitor will be described below.
  • a polymerization inhibitor means a compound that has the function of delaying or inhibiting a polymerization reaction.
  • the polymerization inhibitor for example, known compounds used as polymerization inhibitors can be used.
  • polymerization inhibitors include phenothiazine, bis-(1-dimethylbenzyl)phenothiazine, and phenothiazine compounds such as 3,7-dioctylphenothiazine; bis[3-(3-tert-butyl-4-hydroxy-5- methylphenyl)propionic acid][ethylenebis(oxyethylene)]2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4- hydroxybenzyl), 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3 ,5-di-t-butylanilino)-1,3,5-triazine and hindered phenol compounds such as pentaerythritol tetrakis 3-(3,5-di-tert
  • the polymerization inhibitor is preferably at least one selected from the group consisting of phenothiazine compounds, nitroso compounds or salts thereof, and hindered phenol compounds, and phenothiazine, bis[3-(3-tert-butyl-4 -hydroxy-5-methylphenyl)propionic acid], [ethylenebis(oxyethylene)]2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di- t-butyl-4-hydroxybenzyl), p-methoxyphenol, and N-nitrosophenylhydroxylamine aluminum salt are more preferred.
  • the polymerization inhibitor may be used singly or in combination of two or more.
  • the content of the polymerization inhibitor is preferably 0.001% by mass to 5.0% by mass, based on the total mass of the photosensitive layer, and 0.01% by mass. % to 3.0 mass %, more preferably 0.02 mass % to 2.0 mass %.
  • the content of the polymerization inhibitor is preferably 0.005% by mass to 5.0% by mass, and 0.01% by mass to 3.0% by mass, relative to the total mass of the polymerizable compound. is more preferable, and 0.01% by mass to 1.0% by mass is even more preferable.
  • the photosensitive layer may contain a hydrogen donating compound.
  • the hydrogen donating compound is described below.
  • the hydrogen-donating compound has effects such as further improving the sensitivity of the photopolymerization initiator to actinic rays and suppressing inhibition of polymerization of the polymerizable compound by oxygen.
  • Hydrogen-donating compounds include, for example, amines and amino acid compounds.
  • amines for example, M.I. R. "Journal of Polymer Society" by Sander et al., Vol. JP-A-60-084305, JP-A-62-018537, JP-A-64-033104, and Research Disclosure 33825. More specifically, 4,4′-bis(diethylamino)benzophenone, tris(4-dimethylaminophenyl)methane (alias: leuco crystal violet), triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyl dimethylaniline and p-methylthiodimethylaniline. Among them, amines are preferably at least one selected from the group consisting of 4,4'-bis(diethylamino)benzophenone and tris(4-dimethylaminophenyl)methane.
  • amino acid compounds examples include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine. Among them, N-phenylglycine is preferable as the amino acid compound.
  • the hydrogen-donating compound for example, an organometallic compound (such as tributyltin acetate) described in JP-B-48-042965, a hydrogen donor described in JP-B-55-034414, and JP-A-6 Also included are sulfur compounds (such as trithiane) described in JP-A-308727.
  • organometallic compound such as tributyltin acetate
  • hydrogen donor such as JP-B-55-034414
  • JP-A-6 also included are sulfur compounds (such as trithiane) described in JP-A-308727.
  • the hydrogen-donating compounds may be used singly or in combination of two or more.
  • the content of the hydrogen-donating compound is 0 with respect to the total mass of the photosensitive layer, from the viewpoint of improving the curing speed due to the balance between the polymerization growth speed and the chain transfer. It is preferably 0.01% by mass to 10.0% by mass, more preferably 0.01% by mass to 8.0% by mass, and further preferably 0.03% by mass to 5.0% by mass. preferable.
  • the photosensitive layer may contain a predetermined amount of impurities. Impurities are described below.
  • impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens and their ions.
  • halide ions, sodium ions, and potassium ions are likely to be mixed as impurities, so the following contents are preferable.
  • the content of impurities in the photosensitive layer is preferably 80 ppm or less, more preferably 10 ppm or less, and even more preferably 2 ppm or less on a mass basis.
  • the content of impurities in the photosensitive layer can be 1 ppb or more or 0.1 ppm or more on a mass basis.
  • the impurities within the above range it is possible to select a raw material for the photosensitive layer with a low impurity content, to prevent the contamination of the impurities during the formation of the photosensitive layer, and to remove the impurities by washing. mentioned. By such a method, the amount of impurities can be made within the above range.
  • Impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.
  • ICP Inductively Coupled Plasma
  • the content of compounds such as benzene, formaldehyde, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive layer should be small. is preferred.
  • the content of these compounds in the photosensitive layer is preferably 100 ppm or less, more preferably 20 ppm or less, and even more preferably 4 ppm or less, based on mass.
  • the lower limit can be 10 ppb or more, and can be 100 ppb or more on a mass basis.
  • the content of these compounds can be suppressed in the same manner as the metal impurities described above. Moreover, it can quantify by a well-known measuring method.
  • the water content in the photosensitive layer is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass, from the viewpoint of improving reliability and lamination properties. preferable.
  • the photosensitive layer may contain residual monomers of each constitutional unit of the alkali-soluble resin described above. The remaining monomers are described below.
  • the content of the residual monomer is preferably 5,000 ppm by mass or less, and preferably 2,000 ppm by mass or less, relative to the total mass of the alkali-soluble resin, from the viewpoints of patterning properties and reliability. More preferably, it is 500 ppm by mass or less. Although the lower limit is not particularly limited, it is preferably 1 mass ppm or more, more preferably 10 mass ppm or more.
  • the residual monomer of each structural unit of the alkali-soluble resin is preferably 3,000 ppm by mass or less, and 600 ppm by mass or less, relative to the total mass of the photosensitive layer from the viewpoint of patterning property and reliability. It is more preferably 100 ppm by mass or less. Although the lower limit is not particularly limited, it is preferably 0.1 mass ppm or more, more preferably 1 mass ppm or more.
  • the amount of residual monomers when synthesizing an alkali-soluble resin in a polymer reaction is also preferably within the above range.
  • the content of glycidyl acrylate is preferably within the above range.
  • the amount of residual monomers can be measured by known methods such as liquid chromatography and gas chromatography.
  • the photosensitive layer may contain components other than the components described above (hereinafter also referred to as "other components"). Other components are described below.
  • Other components include, for example, colorants, antioxidants, and particles (eg, metal oxide particles). Further, as other components, other additives described in paragraphs [0058] to [0071] of JP-A-2000-310706 can also be mentioned.
  • the photosensitive layer may contain a small amount of coloring agent (pigment, dye, etc.), but it is preferred that it contains substantially no coloring agent, for example, from the viewpoint of transparency.
  • the content of the coloring agent is preferably less than 1% by weight, more preferably less than 0.1% by weight, based on the total weight of the photosensitive layer.
  • antioxidants examples include 1-phenyl-3-pyrazolidone (alias: phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl- 3-pyrazolidones such as 3-pyrazolidone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chlorohydroquinone; paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, and paraphenylenediamine be done.
  • the antioxidant is preferably 3-pyrazolidones, more preferably 1-phenyl-3-pyrazolidone.
  • the content of the antioxidant is preferably 0.001% by mass or more, and 0.005% by mass or more, relative to the total mass of the photosensitive layer. is more preferable, and 0.01% by mass or more is even more preferable.
  • the upper limit is not particularly limited, it is preferably 1% by mass or less.
  • the particles are preferably metal oxide particles.
  • Metals in metal oxide particles also include semimetals such as B, Si, Ge, As, Sb, and Te.
  • the average primary particle size of the particles is, for example, preferably 1 to 200 nm, more preferably 3 to 80 nm, from the viewpoint of the transparency of the cured film.
  • the average primary particle diameter of particles is calculated by measuring the particle diameters of 200 arbitrary particles using an electron microscope and arithmetically averaging the measurement results. When the shape of the particles is not spherical, the longest side is taken as the particle diameter.
  • the photosensitive layer contains particles, it may contain only one type of particles having different metal species and different sizes, or may contain two or more types.
  • the photosensitive layer does not contain particles, or when the photosensitive layer contains particles, the content of the particles is more than 0% by mass and 35% by mass or less with respect to the total mass of the photosensitive layer. is preferable, and it is more preferable that it does not contain particles, or the content of particles is more than 0% by mass and 10% by mass or less with respect to the total mass of the photosensitive layer, and it does not contain particles, or particles It is more preferable that the content of is more than 0% by mass and 5% by mass or less with respect to the total mass of the photosensitive layer, and does not contain particles, or the content of particles is based on the total mass of the photosensitive layer More than 0% by weight and up to 1% by weight is particularly preferred, and it is very preferably free of particles.
  • the method of disposing the photosensitive layer on the substrate is not limited.
  • the photosensitive layer may be formed on the substrate, or a pre-prepared photosensitive layer may be disposed on the substrate.
  • the photosensitive layer can be arranged on the substrate by applying the photosensitive composition onto the substrate and drying the photosensitive composition as necessary.
  • a transfer film containing a temporary support and a photosensitive layer is attached to a substrate, whereby the photosensitive layer and the temporary support can be arranged in this order on the substrate.
  • the disposing step uses a transfer film to dispose the photosensitive layer on the substrate.
  • the components of the photosensitive composition are selected from the components of the photosensitive layer described above, depending on the intended composition of the photosensitive layer. Matters related to the components of the photosensitive layer described above, by reading "photosensitive layer” as “photosensitive composition” and “total weight of photosensitive layer” as “photosensitive composition”, It applies to the composition aspect. Preferred components of the photosensitive composition are the same as the preferred components of the photosensitive layer previously described.
  • the photosensitive composition may contain a solvent, if necessary.
  • a solvent an organic solvent is preferred.
  • organic solvents include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (also known as 1-methoxy-2-propyl acetate), diethylene glycol ethyl methyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, and caprolactam. , n-propanol, and 2-propanol.
  • an organic solvent having a boiling point of 180 to 250° C. (high boiling point solvent) can also be used, if necessary.
  • a solvent may be used individually by 1 type, and can also use 2 or more types together.
  • the total solid content of the photosensitive composition is preferably 5% by mass to 80% by mass, more preferably 5% by mass to 40% by mass, relative to the total mass of the photosensitive composition, and 5% by mass. % to 30 mass %. That is, the content of the solvent in the photosensitive composition is preferably 20% by mass to 95% by mass, more preferably 60% by mass to 95% by mass, relative to the total mass of the photosensitive composition. More preferably, it is still more preferably 70% by mass to 95% by mass.
  • the viscosity of the photosensitive composition at 25° C. is, for example, preferably from 1 mPa ⁇ s to 50 mPa ⁇ s, more preferably from 2 mPa ⁇ s to 40 mPa ⁇ s, and even more preferably from 3 mPa ⁇ s to 30 mPa ⁇ s, from the viewpoint of coating properties. .
  • Viscosity is measured using a viscometer.
  • a viscometer for example, a viscometer manufactured by Toki Sangyo Co., Ltd. (trade name: VISCOMETER TV-22) can be preferably used.
  • the viscometer is not limited to the viscometers described above.
  • the surface tension of the photosensitive composition at 25° C. is, for example, preferably from 5 mN/m to 100 mN/m, more preferably from 10 mN/m to 80 mN/m, more preferably from 15 mN/m to 40 mN/m, from the viewpoint of applicability. preferable.
  • Surface tension is measured using a surface tensiometer.
  • a surface tensiometer manufactured by Kyowa Interface Science Co., Ltd. (trade name: Automatic Surface Tensiometer CBVP-Z) can be preferably used.
  • the surface tension meter is not limited to the surface tension meter described above.
  • Examples of methods for applying the photosensitive composition include printing, spraying, roll coating, bar coating, curtain coating, spin coating, and die coating (that is, slit coating).
  • Heat drying and vacuum drying are preferable as the method for drying the photosensitive composition.
  • drying is meant removing at least a portion of the solvent contained in the composition. Drying methods include, for example, natural drying, heat drying, and vacuum drying. The methods described above can be applied singly or in combination.
  • the drying temperature is preferably 80° C. or higher, more preferably 90° C. or higher. Further, the upper limit thereof is preferably 130° C. or lower, more preferably 120° C. or lower. Drying can also be performed by changing the temperature continuously.
  • the drying time is preferably 20 seconds or longer, more preferably 40 seconds or longer, and even more preferably 60 seconds or longer. Although the upper limit is not particularly limited, it is preferably 600 seconds or less, more preferably 300 seconds or less.
  • the transfer film used in the placement step preferably includes a temporary support and a photosensitive layer in this order.
  • the transfer film will be described below. However, in the following description, the mode of the photosensitive layer in the transfer film is omitted because it is the same as the mode of the photosensitive layer described above.
  • the transfer film preferably contains a temporary support.
  • a temporary support is a member that supports the photosensitive layer, and is finally removed by a peeling treatment.
  • the temporary support may have a single layer structure or a multilayer structure.
  • the temporary support is preferably a film, more preferably a resin film.
  • the temporary support is preferably a film that has flexibility and does not undergo significant deformation, shrinkage, or elongation under pressure or under pressure and heat.
  • the film include polyethylene terephthalate film (eg, biaxially stretched polyethylene terephthalate film), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, and polycarbonate film.
  • polyethylene terephthalate film is preferable as the temporary support.
  • the film used as the temporary support does not have deformation such as wrinkles, scratches, or the like.
  • the temporary support preferably has high transparency from the viewpoint that pattern exposure can be performed through the temporary support, and the transmittance at 313 nm, 365 nm, 405 nm and 436 nm is preferably 60% or more, preferably 70% or more. is more preferably 80% or more, and most preferably 90% or more.
  • Preferred transmittance values include, for example, 87%, 92%, 98%, and the like.
  • the haze of the temporary support is small.
  • the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, and even more preferably 0.1% or less.
  • the number of fine particles, foreign matter and defects contained in the temporary support is small.
  • the number of fine particles having a diameter of 1 ⁇ m or more, foreign matter, and defects in the temporary support is preferably 50/10 mm 2 or less, more preferably 10/10 mm 2 or less, and 3/10 mm 2 or less. It is more preferably less than or equal to, and particularly preferably 0/10 mm 2 .
  • the thickness of the temporary support is preferably 5 ⁇ m to 200 ⁇ m.
  • the thickness of the temporary support is more preferably 5 ⁇ m to 150 ⁇ m, still more preferably 5 ⁇ m to 50 ⁇ m, particularly preferably 5 ⁇ m to 25 ⁇ m, from the viewpoints of ease of handling and versatility.
  • the thickness of the temporary support is represented by the arithmetic mean of five thicknesses measured by cross-sectional observation using a scanning electron microscope (SEM).
  • the surface of the temporary support facing the photosensitive layer may be surface-modified by ultraviolet irradiation, corona discharge, plasma, or the like.
  • the exposure dose is preferably 10 mJ/cm 2 to 2000 mJ/cm 2 , more preferably 50 mJ/cm 2 to 1000 mJ/cm 2 .
  • Light sources for ultraviolet irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and luminescence that emit light in the wavelength band of 150 nm to 450 nm. A diode (LED) etc. are mentioned. As long as the amount of light irradiation is within the range described above, the lamp output and illuminance are not limited.
  • Examples of the temporary support include a biaxially stretched polyethylene terephthalate film with a thickness of 16 ⁇ m, a biaxially stretched polyethylene terephthalate film with a thickness of 12 ⁇ m, and a biaxially stretched polyethylene terephthalate film with a thickness of 9 ⁇ m.
  • the temporary support may be a recycled product. Recycled products include those obtained by washing used films, cutting them into chips, and making films using these as materials. A specific example of the recycled product is Toray's Ecouse series.
  • Preferred forms of the temporary support include, for example, paragraphs [0017] to [0018] of JP-A-2014-085643, paragraphs [0019] to [0026] of JP-A-2016-027363, International Publication No. 2012/ Paragraphs [0041] to [0057] of No. 081680 and paragraphs [0029] to [0040] of WO 2018/179370 are mentioned, and the contents of these publications are incorporated herein.
  • a layer containing fine particles may be provided on the surface of the temporary support in terms of imparting handleability.
  • the lubricant layer may be provided on one side or both sides of the temporary support.
  • the diameter of the particles contained in the lubricant layer is preferably 0.05 to 0.8 ⁇ m.
  • the thickness of the lubricant layer is preferably 0.05 to 1.0 ⁇ m.
  • the transfer film preferably further includes a refractive index adjusting layer.
  • the transfer film preferably includes a temporary support, a photosensitive layer, and a refractive index adjusting layer in this order.
  • a known refractive index adjustment layer can be applied as the refractive index adjustment layer.
  • Materials contained in the refractive index adjusting layer include, for example, polymers, polymerizable compounds, metal salts and particles.
  • the method for controlling the refractive index of the refractive index adjusting layer is not particularly limited, and examples include a method using a resin having a predetermined refractive index alone, a method using a polymer and particles, and a composite of a polymer and a resin. A method using the body is mentioned.
  • Polymers include, for example, the polymers already described as components of the photosensitive layer.
  • Examples of the polymerizable compound include the polymerizable compounds already described as components of the photosensitive layer.
  • Particles include, for example, metal oxide particles and metal particles. The type of metal oxide particles is not particularly limited, and known metal oxide particles can be used. Metals in metal oxide particles also include semimetals such as B, Si, Ge, As, Sb, and Te.
  • metal oxide particles include zirconium oxide particles ( ZrO2 particles), Nb2O5 particles, titanium oxide particles ( TiO2 particles), silicon dioxide particles ( SiO2 particles), and composites thereof. At least one selected from the group consisting of particles is preferred. Among these, at least one selected from the group consisting of zirconium oxide particles and titanium oxide particles is more preferable as the metal oxide particles, for example, from the viewpoint that the refractive index can be easily adjusted.
  • metal oxide particles include calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F04), calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F74), Baked zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F75), calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F76), zirconium oxide particles (Nanouse OZ-S30M, Nissan Kagaku Kogyo Co., Ltd.), and zirconium oxide particles (Nanouse OZ-S30K, Nissan Chemical Industries, Ltd.).
  • the average primary particle size of the particles is, for example, preferably 1 nm to 200 nm, more preferably 3 nm to 80 nm, from the viewpoint of the transparency of the cured film.
  • the average primary particle diameter of particles is calculated by measuring the particle diameters of 200 arbitrary particles using an electron microscope and arithmetically averaging the measurement results. When the shape of the particles is not spherical, the longest side is taken as the particle diameter.
  • the particles may be used singly or in combination of two or more.
  • the content of the particles in the refractive index adjusting layer is preferably 1% by mass to 95% by mass, more preferably 20% by mass to 90% by mass, and 40% by mass with respect to the total mass of the refractive index adjusting layer. % to 85 mass %.
  • the content of the titanium oxide particles is preferably 1% by mass to 95% by mass, more preferably 20% by mass to 90% by mass, based on the total mass of the refractive index adjusting layer. and more preferably 40% by mass to 85% by mass.
  • the refractive index of the refractive index adjusting layer is preferably higher than that of the photosensitive layer.
  • the refractive index of the refractive index adjusting layer is preferably 1.50 or more, more preferably 1.55 or more, even more preferably 1.60 or more, and particularly preferably 1.65 or more. preferable.
  • the refractive index of the refractive index adjusting layer is preferably 2.10 or less, more preferably 1.85 or less, and even more preferably 1.78 or less.
  • the thickness of the refractive index adjusting layer is preferably 50 nm to 500 nm, more preferably 55 nm to 110 nm, and even more preferably 60 nm to 100 nm.
  • the thickness of the refractive index adjusting layer is represented by an arithmetic mean of five thicknesses measured by cross-sectional observation using a scanning electron microscope (SEM).
  • the refractive index adjusting layer is manufactured using, for example, a composition for forming a refractive index adjusting layer.
  • the composition for forming the refractive index adjusting layer preferably contains the above-described various components for forming the refractive index adjusting layer and a solvent.
  • the preferred range of the content of each component with respect to the total solid content of the composition is the same as the preferred range of the content of each component with respect to the total mass of the refractive index adjustment layer. be.
  • the solvent is not particularly limited as long as it can dissolve or disperse the components contained in the refractive index adjustment layer, and is preferably at least one selected from the group consisting of water and water-miscible organic solvents. Mixed solvents with water-miscible organic solvents are more preferred. Examples of water-miscible organic solvents include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, with alcohols having 1 to 3 carbon atoms being preferred, and methanol or ethanol being more preferred.
  • a solvent may be used individually by 1 type, and may be used 2 or more types.
  • the content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, even more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition.
  • the refractive index adjusting layer may be produced by applying a composition for forming a refractive index adjusting layer.
  • coating methods include slit coating, spin coating, curtain coating, and inkjet coating.
  • the transfer film preferably further contains a protective film.
  • the transfer film preferably includes a temporary support, a photosensitive layer, and a protective film in this order.
  • the transfer film preferably includes a temporary support, a photosensitive layer, a refractive index adjusting layer, and a protective film in this order.
  • a resin film having heat resistance and solvent resistance can be used.
  • examples thereof include polyolefin films such as polypropylene films and polyethylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, and polystyrene films. be done.
  • a resin film made of the same material as the temporary support may be used.
  • the protective film is preferably a polyolefin film, more preferably a polypropylene film or a polyethylene film, and still more preferably a polyethylene film.
  • the thickness of the protective film is preferably 1 ⁇ m to 100 ⁇ m, more preferably 5 ⁇ m to 50 ⁇ m, even more preferably 5 ⁇ m to 40 ⁇ m, and particularly preferably 15 ⁇ m to 30 ⁇ m.
  • the thickness of the protective film is preferably 1 ⁇ m or more in terms of excellent mechanical strength, and preferably 100 ⁇ m or less in terms of relatively low cost.
  • the thickness of the protective film is represented by the arithmetic mean of five thicknesses measured by cross-sectional observation using a scanning electron microscope (SEM).
  • the number of fisheyes with a diameter of 80 ⁇ m or more contained in the protective film is preferably 5/m 2 or less.
  • “Fish eye” refers to the fact that when a film is produced by methods such as heat melting, kneading, extrusion, biaxial stretching and casting, foreign matter, undissolved matter, and oxidative deterioration of the material are removed from the film. It is taken inside.
  • the number of particles with a diameter of 3 ⁇ m or more contained in the protective film is preferably 30 particles/mm 2 or less, more preferably 10 particles/mm 2 or less, and further preferably 5 particles/mm 2 or less. preferable.
  • a reduction in the number of fisheyes can suppress defects caused by the unevenness caused by particles contained in the protective film being transferred to a layer such as a photosensitive layer that contacts the protective film.
  • the surface of the protective film opposite to the surface in contact with the photosensitive layer preferably has an arithmetic mean roughness Ra of 0.01 ⁇ m or more, more preferably 0.02 ⁇ m or more. More preferably, it is still more preferably 0.03 ⁇ m or more.
  • the above roughness Ra is preferably less than 0.50 ⁇ m, more preferably 0.40 ⁇ m or less, even more preferably 0.30 ⁇ m or less.
  • the surface roughness Ra of the surface of the protective film in contact with the photosensitive layer is preferably 0.01 ⁇ m or more, more preferably 0.02 ⁇ m or more, and more preferably 0.03 ⁇ m or more. is more preferable.
  • the above roughness Ra is preferably less than 0.50 ⁇ m, more preferably 0.40 ⁇ m or less, even more preferably 0.30 ⁇ m or less.
  • the protective film is introduced into the transfer film, for example, by laminating the protective film and the photosensitive layer or refractive index adjusting layer. Bonding of the protective film and the photosensitive layer or the refractive index adjusting layer is performed using, for example, a known laminator.
  • Laminators include, for example, vacuum laminators and autocut laminators.
  • the laminator includes heatable rollers.
  • the laminator preferably has a function of applying pressure and heating in bonding.
  • the method of laminating the transfer film and the base material is not limited. Bonding of the transfer film and the substrate is performed using, for example, a known laminator. Laminators include, for example, vacuum laminators and autocut laminators. The bonding of the transfer film and the substrate is preferably carried out under pressure and heating conditions. The temperature is preferably between 70°C and 130°C. When the transfer film includes a protective film, the protective film is peeled off before lamination of the transfer film and the substrate.
  • the photosensitive layer is pattern-exposed. According to the exposure step, an exposed portion and a non-exposed portion are formed in the photosensitive layer.
  • the positional relationship between the exposed area and the non-exposed area is not limited. The positional relationship between the exposed portion and the non-exposed portion is determined, for example, according to the desired shape of the resin pattern.
  • the light for pattern-exposing the photosensitive layer may be irradiated along a direction from the photosensitive layer toward the substrate or a direction from the substrate toward the photosensitive layer.
  • the light source in the exposure step is selected, for example, from a light source that emits light having a wavelength (eg, 365 nm or 405 nm) capable of causing a chemical change in the photosensitive layer.
  • the dominant wavelength of light is preferably 365 nm.
  • “dominant wavelength” is meant the wavelength with the highest intensity.
  • Examples of light sources include various lasers, light-emitting diodes (LEDs), ultrahigh-pressure mercury lamps, high-pressure mercury lamps, and metal halide lamps.
  • the exposure amount in the exposure step is preferably 5 mJ/cm 2 to 200 mJ/cm 2 , more preferably 10 mJ/cm 2 to 200 mJ/cm 2 .
  • a developer containing at least one component selected from the group consisting of sodium ions and potassium ions is used to remove the exposed or non-exposed areas of the photosensitive layer to form a resin pattern.
  • the photosensitive layer is of a negative type
  • the non-exposed areas of the photosensitive layer are usually removed by a developer, and the exposed areas of the photosensitive layer form a resin pattern.
  • the photosensitive layer is of a positive type
  • the exposed areas of the photosensitive layer are usually removed by a developer, and the non-exposed areas of the photosensitive layer form the resin pattern.
  • a developer containing at least one component selected from the group consisting of sodium ions and potassium ions is produced, for example, by mixing a solvent with at least one component selected from the group consisting of sodium compounds and potassium compounds. be done.
  • solvents include water.
  • Sodium compounds include, for example, compounds that generate sodium ions in a solvent (eg, sodium salts).
  • Sodium salts include, for example, sodium hydroxide, sodium carbonate and sodium bicarbonate.
  • Potassium compounds include, for example, compounds that yield potassium ions in a solvent (eg, potassium salts).
  • Potassium salts include, for example, potassium hydroxide, potassium carbonate and potassium hydrogen carbonate.
  • the temperature of the developer is preferably 22°C to 33°C, more preferably 24°C to 30°C, and even more preferably 26°C.
  • the temperature of the developer is 22° C. or higher, development defects are reduced.
  • the temperature of the developer is 33° C. or less, the depth of presence of the specific component in the resin pattern is easily adjusted to 3.0 ⁇ m or less.
  • the processing time in the developing step is preferably 22 seconds to 50 seconds, more preferably 22 seconds to 40 seconds, even more preferably 22 seconds to 30 seconds, and particularly preferably 25 seconds. .
  • the processing time is 22 seconds or longer, poor development is reduced.
  • the treatment time is 50 seconds or less, the presence depth of the specific component in the resin pattern is easily adjusted to 3.0 ⁇ m or less.
  • a preferable developing method includes, for example, the developing method described in paragraph [0195] of International Publication No. 2015/093271.
  • washing process In the cleaning step, water is used to clean the resin pattern.
  • the washing process can not only remove the residue after development and the developer adhering to the base material and the resin pattern, but also can adjust the existence depth of the specific component in the resin pattern according to, for example, the temperature of the water and the treatment time.
  • the resin pattern may be cleaned by immersion in water.
  • the resin pattern may be cleaned with jetted water.
  • components other than the resin pattern may be cleaned together with the resin pattern.
  • the temperature of water in the washing step is preferably 21°C to 35°C, more preferably 21°C to 30°C, even more preferably 21°C to 25°C, most preferably 21°C. preferable.
  • the water temperature is 21° C. or higher, the presence depth of the specific component in the resin pattern is easily adjusted to 0.3 ⁇ m or more.
  • the temperature of the water is 35° C. or less, the existence depth of the specific component in the resin pattern is easily adjusted to 3.0 ⁇ m or less.
  • the treatment time in the washing step is preferably 21 seconds to 50 seconds, more preferably 22 seconds to 40 seconds, even more preferably 23 seconds to 30 seconds, and particularly preferably 25 seconds. .
  • the treatment time is 21 seconds or more, the existence depth of the specific component in the resin pattern is easily adjusted to 0.3 ⁇ m or more.
  • the treatment time is 50 seconds or less, the presence depth of the specific component in the resin pattern is easily adjusted to 3.0 ⁇ m or less.
  • the water used in the cleaning process includes, for example, pure water and ultrapure water.
  • a mixed solvent of water and a solvent other than water may be used.
  • water temperature is read as “mixed solvent temperature”.
  • the stationary step can greatly contribute to the adjustment of the presence depth of the specific component in the resin pattern.
  • the presence depth of the specific component in the resin pattern can be adjusted, for example, according to the standing time.
  • Standing means letting time elapse without performing a post-process. Therefore, if the substrate and the resin pattern are not subjected to post-processing, they are included in the stationary step even if they are transported or the ambient temperature and humidity change along with transport.
  • Post-processes include post-exposure and post-baking, which will be described later, and OCA bonding processing for device fabrication.
  • the standing time in the standing step is preferably 1 hour to 72 hours, more preferably 15 hours to 48 hours, and even more preferably 24 hours to 48 hours.
  • the standing time is 1 hour or longer, the depth of presence of the specific component in the resin pattern is easily adjusted to 0.3 ⁇ m or longer.
  • the stationary time is 72 hours or less, the depth of presence of the specific component in the resin pattern is easily adjusted to 3.0 ⁇ m or less.
  • the temperature (eg, ambient temperature) in the standing step is preferably 15°C to 35°C, more preferably 20°C to 30°C.
  • the relative humidity in the standing step is preferably 40% RH to 70% RH, more preferably 50% RH to 60% RH.
  • a method for manufacturing a laminate according to an embodiment of the present disclosure may include other steps as necessary.
  • Other steps include, for example, a stripping step, a post-exposure step, and a post-baking step.
  • other steps are not limited to the above specific examples.
  • Other steps may be selected from known steps depending on the application of the laminate.
  • the temporary support is peeled off.
  • the peeling step is preferably performed between the placement step and the exposure step or between the exposure step and the development step.
  • a mechanism similar to the cover film peeling mechanism described in paragraphs [0161] to [0162] of JP-A-2010-072589 is used.
  • the resin pattern is exposed.
  • the post-exposure step is preferably performed after the resting step.
  • the exposure dose in the post-exposure step is preferably 100 J/cm 2 to 5,000 mJ/cm 2 and more preferably 200 J/cm 2 to 3,000 mJ/cm 2 .
  • the resin pattern is heated.
  • the post-bake step is preferably performed after the post-exposure step.
  • the temperature in the post-baking step is preferably 80°C to 250°C, more preferably 90°C to 160°C.
  • the processing time in the post-baking step is preferably 1 minute to 180 minutes, more preferably 10 minutes to 60 minutes.
  • the present disclosure will be described in detail below with reference to examples. However, the present disclosure is not limited to the following examples. Materials, usage amounts, ratios, processing details, and processing procedures in the following examples may be changed as appropriate without departing from the gist of the present disclosure. "Parts” and “%” are based on mass unless otherwise specified.
  • the weight average molecular weight is the weight average molecular weight determined by gel permeation chromatography (GPC) in terms of polystyrene.
  • the acid number is a theoretical acid number.
  • P-1 solution a solution containing polymer P-1 represented by the following chemical formula (hereinafter sometimes referred to as “P-1 solution”).
  • the solid content concentration of the obtained solution is 36.2% by mass.
  • the amount of residual monomer measured using gas chromatography was less than 0.1% by mass based on the polymer solid content for any monomer.
  • polymer P-1 The properties of polymer P-1 are as follows. Weight-average molecular weight (Mw) and number-average molecular weight (Mn) are molecular weights in terms of standard polystyrene measured by gel permeation chromatography (GPC). ⁇ Weight average molecular weight (Mw): 18,000 ⁇ Number average molecular weight (Mn): 7,800 ⁇ Dispersion degree: 2.3 ⁇ Acid value: 124mgKOH/g
  • the blocked isocyanate compound Q-1 is represented by the following chemical formula.
  • a polyethylene terephthalate film (Lumirror 16KS40, manufactured by Toray Industries, Inc.) having a thickness of 16 ⁇ m was prepared as a temporary support.
  • a photosensitive composition A-1 was applied onto the temporary support using a slit nozzle, and the solvent was volatilized in a drying zone at 100° C. to form a photosensitive layer having a thickness of 5.5 ⁇ m.
  • a protective film (Lumirror 16KS40, manufactured by Toray Industries, Inc.) was pressure-bonded to the photosensitive layer to prepare a transfer film.
  • a substrate including a substrate (cycloolefin polymer film), a transparent film, and a transparent electrode pattern (ITO) in this order was obtained by the following procedure.
  • a cycloolefin polymer film (thickness: 38 ⁇ m, refractive index: 1.53) was prepared as a substrate. Using a high-frequency oscillator, the substrate was subjected to corona discharge treatment under the following conditions. Output voltage: 100% Output: 250W Electrode: Wire electrode with a diameter of 1.2 mm Electrode length: 240 mm Distance between work electrodes: 1.5 mm Processing time: 3 seconds
  • ITO Indium Tin Oxide
  • An ITO (Indium Tin Oxide) film having a thickness of 40 nm and a refractive index of 1.82 is formed on the transparent film by DC magnetron sputtering, and the formed ITO film is patterned by photoetching to obtain a transparent film. A transparent electrode pattern was formed on the film. Formation of the ITO film and patterning of the ITO film were performed by the method described in paragraphs [0119] to [0122] of JP-A-2014-10814.
  • the transfer film was laminated on the substrate so that the photosensitive layer covered the transparent film and the transparent electrode pattern. Lamination was performed using a vacuum laminator manufactured by MCK Co., Ltd.
  • the temperature of the substrate that is, the cycloolefin polymer film
  • the temperature of the rubber roller was 100 ° C.
  • the linear pressure was 3 N / cm
  • the transport speed was was 4 m/min.
  • the exposure mask (quartz exposure mask having a pattern for forming an overcoat) is brought into close contact with the temporary support, and the temporary support is
  • the photosensitive layer was pattern-exposed through the support with an exposure amount of 150 mJ/cm 2 (measured with i-line).
  • the temporary support was peeled off and a 1.0% by mass sodium carbonate aqueous solution (liquid temperature: 25° C. ) for 25 seconds.
  • the sample was rinsed with pure water at 21° C. for 25 seconds from an ultrahigh-pressure cleaning nozzle. After removing the water adhering to the sample by blowing air, the sample was allowed to stand in an environment of 23° C. and 55% RH (relative humidity) for 24 hours.
  • a post-exposure machine manufactured by Ushio Inc.
  • the resin pattern was exposed (post-exposure) with an exposure amount of 400 mJ/cm 2 (measured with i-line).
  • a post-baking treatment was performed at 145° C. for 30 minutes to obtain a laminate including a substrate, a transparent film, a transparent electrode pattern, and a resin pattern in this order.
  • the resin pattern is a cured product of the photosensitive composition A-1.
  • Example 2 A laminate was obtained by the same procedure as in Example 1, except that the temperature of pure water in the water washing treatment was changed to 25°C.
  • Example 3 A laminate was obtained by the same procedure as in Example 1, except that the temperature of the pure water in the water washing treatment was changed to 25° C. and the time of the water washing treatment was changed to 45 seconds.
  • Example 4 A laminate was obtained by the same procedure as in Example 1, except that the standing time after the water washing treatment was changed to 3 hours.
  • Example 5 Same as Example 1 except that the temperature of the pure water in the water washing process was changed to 25° C., the water washing time was changed to 45 seconds, and the standing time after the water washing process was changed to 72 hours. A laminate was obtained by the procedure.
  • Example 6 A laminate was obtained by the same procedure as in Example 1, except that the standing time after the water washing treatment was changed to 48 hours.
  • Example 7 A laminate was obtained in the same manner as in Example 6, except that polymer P-1 was changed to polymer P-2 represented by the following chemical formula. In the following chemical formulas, the numerical value attached to each structural unit represents mol%.
  • polymer P-2 The properties of polymer P-2 are as follows. Weight-average molecular weight (Mw) and number-average molecular weight (Mn) are molecular weights in terms of standard polystyrene measured by gel permeation chromatography (GPC). ⁇ Acid value: 95mgKOH/g ⁇ Weight average molecular weight (Mw): 27,000 ⁇ Number average molecular weight (Mn) is 15,000
  • Example 8 A laminate was obtained by the same procedure as in Example 6, except that the components of the photosensitive composition were changed according to Table 2.
  • Example 9 A laminate was obtained by the same procedure as in Example 6, except that polymer P-1 was changed to polymer P-3.
  • Polymer P-3 is a random copolymer of benzyl methacrylate and methacrylic acid.
  • the "benzyl methacrylate/methacrylic acid” molar ratio in polymer P-3 is 72/28.
  • the weight average molecular weight (Mw) of polymer P-3 is 37,000.
  • Example 10 A laminate was obtained by the same procedure as in Example 6, except that the polymerizable compound in the photosensitive composition A-1 was changed to the following polymerizable compound.
  • ⁇ NK Ester BPE-500 polymerizable compound, 2,2-bis (4-(methacryloxypentaethoxy) phenyl) propane, manufactured by Shin-Nakamura Chemical Co., Ltd.
  • 22.5 parts by mass ⁇ NK Ester BPE-200 ( Polymerizable compound, 2,2-bis (4-(methacryloxydiethoxy) phenyl) propane, manufactured by Shin Nakamura Chemical Co., Ltd.): 10.0 parts by mass
  • NK Ester A-TMPT polymerizable compound, trimethylolpropane Triacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.
  • Example 11 A laminate was obtained by the same procedure as in Example 6, except that the components of the photosensitive composition were changed according to Table 2.
  • Example 12 A laminate was obtained by the same procedure as in Example 6, except that the components of the photosensitive composition were changed according to Table 2.
  • Example 13> A laminate was obtained by the same procedure as in Example 6, except that the thickness of the photosensitive layer was changed to 3.3 ⁇ m.
  • Example 14> A laminate was obtained by the same procedure as in Example 6, except that the thickness of the photosensitive layer was changed to 10.9 ⁇ m.
  • Example 15 A laminate was obtained by the same procedure as in Example 1, except that the developer in the development process was changed to a 1% by mass potassium carbonate aqueous solution.
  • Example 16> A laminate was obtained by the same procedure as in Example 4, except that the developer in the development process was changed to a 1% by mass potassium carbonate aqueous solution.
  • Example 17 A laminate was obtained by the same procedure as in Example 5, except that the developer in the development process was changed to a 1% by mass potassium carbonate aqueous solution.
  • Examples 18 to 20> A laminate was obtained by the same procedure as in Example 6, except that a photosensitive composition containing the components listed in Table 3 was used to form a photosensitive layer.
  • a photosensitive composition containing the components listed in Table 3 was used to form a photosensitive layer.
  • methyl ethyl ketone and 1-methoxy-2-propyl acetate are appropriately added as solvents, and the ratio of methyl ethyl ketone to all solvents in the photosensitive composition is 50% by mass. The amount of solvent was adjusted so that the concentration was 20% by mass.
  • Examples 21-22> A laminate was obtained by the same procedure as in Example 6, except that a photosensitive composition containing the components listed in Table 4 was used to form a photosensitive layer.
  • Examples 23-25> A laminate was obtained by the same procedure as in Example 6, except that a photosensitive composition containing the components listed in Table 5 was used to form a photosensitive layer.
  • Example 1 A laminate was obtained by the same procedure as in Example 6, except that the conditions for the development treatment and the conditions for the washing treatment were changed to the following conditions. ⁇ Temperature of developer: 20°C ⁇ Time for development processing: 20 seconds ⁇ Temperature of pure water in water washing processing: 20°C ⁇ Time of water washing treatment: 20 seconds ⁇ Standing time after water washing treatment: 0 hours
  • Example 2 A laminate was obtained by the same procedure as in Example 6, except that the conditions for the development treatment and the conditions for the washing treatment were changed to the following conditions. ⁇ Temperature of developer: 35°C ⁇ Time for development processing: 60 seconds ⁇ Temperature of pure water in water washing processing: 40°C ⁇ Time of water washing treatment: 60 seconds ⁇ Standing time after water washing treatment: 80 hours
  • the sputtering time when the intensity of the target component first reaches 90% is the sputtering rate. was converted to the depth (that is, the distance from the surface of the resin pattern to the point where the intensity of the target component first reached 90%).
  • the arithmetic average value of the three measured values was taken as the "existing depth”. Tables 2 to 5 show the measurement results.
  • a spherical diamond scratching needle with a tip diameter of 75 ⁇ m was used to scratch the resin pattern with a load of 10 g and a length of 5 cm. The degree of scratching on the resin pattern was confirmed, and the scratch resistance was evaluated according to the following criteria A to D.
  • a or B is a practically acceptable level, and A is preferred.
  • C Scratches are observed in observation with an optical microscope, but no scratches are observed in visual observation.
  • D Scratches are conspicuously observed by visual observation.
  • a cross section near the edge of the resin pattern in the laminate was observed using a scanning electron microscope.
  • the width of the lifted edge of the resin pattern (specifically, the length of the portion where the edge of the resin pattern is lifted) was measured, and the lifted edge was evaluated according to the following criteria A to D.
  • a or B is a practically acceptable level, and A is preferred.
  • A No edge lifting is observed.
  • B The width of edge floating is 0.1 ⁇ m or more and less than 5.0 ⁇ m.
  • C The width of edge floating is 5.0 ⁇ m or more and less than 10.0 ⁇ m.
  • D The width of edge floating is 10.0 ⁇ m or more.
  • the units for the contents of the components described in the "Photosensitive composition” column are parts by mass in terms of solid content.
  • “the depth at which sodium ions or potassium ions exist” specifically means the depth at which sodium ions exist.
  • “the depth of presence of sodium ions or potassium ions” specifically means the depth of presence of potassium ions.
  • Tables 2 to 5 show that Examples 1 to 25 are superior in scratch resistance and that Examples 1 to 25 have less edge floating than Comparative Examples 1 to 2.
  • Examples 1A to 25A> Each transfer film was produced in the same manner as in Examples 1 to 25, except that the temporary support and protective film used in producing the transfer film were changed to the following materials, and evaluated in the same manner. The results were the same as in Examples 1 to 25, respectively.
  • Temporary support product name “Cosmoshine (registered trademark) A4160” manufactured by Toyobo Co., Ltd., thickness 50 ⁇ m
  • PET film Protective film product name “Alphan (registered trademark) E-210F” manufactured by Oji F-Tex Co., Ltd.
  • Examples 1B to 25B> Each transfer film was produced in the same manner as in Examples 1 to 25, except that the temporary support and protective film used in producing the transfer film were changed to the following materials, and evaluated in the same manner. The results were the same as in Examples 1 to 25, respectively.
  • Temporary support product name “Cosmo Shine (registered trademark) A4360” manufactured by Toyobo Co., Ltd., thickness 38 ⁇ m
  • PET film Protective film product name “Alphan (registered trademark) FG-201” manufactured by Oji F-Tex Co., Ltd.
  • Examples 1C to 25C> Each transfer film was produced in the same manner as in Examples 1 to 25, except that the temporary support and protective film used in producing the transfer film were changed to the following materials, and evaluated in the same manner. The results were the same as in Examples 1 to 25, respectively.
  • Temporary support product name “Lumirror (registered trademark) 16FB40” manufactured by Toray Industries, Inc., thickness 16 ⁇ m
  • PET film Protective film product name “Alphan (registered trademark) E-210F” manufactured by Oji F-Tex Co., Ltd. 50 ⁇ m thick
  • polypropylene film
  • composition Y-1 for Forming Transparent Resin Layer A composition Y-1 for forming a transparent resin layer having the composition shown in Table 6 was prepared.
  • a photosensitive layer was formed on the temporary support according to the method described in Example 1, "Preparation of Transfer Film”.
  • the transparent resin layer-forming composition Y-1 was applied onto the photosensitive layer and dried to form a transparent resin layer. The coating amount was adjusted so that the thickness after curing was 73 nm.
  • a protective film (Lumirror 16KS40, manufactured by Toray Industries, Inc.) was pressure-bonded to the transparent resin layer to prepare a transfer film.
  • Laminates of Examples 101 to 125 were obtained by the same procedure as in Examples 1 to 25, except that the laminate was produced using the transfer film containing the transparent resin layer described above. That is, except for the transparent resin layer, the manufacturing conditions of the laminates of Examples 101 to 125 correspond to the manufacturing conditions of the laminates of Examples 1 to 25, respectively. Using the laminate thus obtained, the aforementioned "scratch resistance" and "edge lifting" were evaluated. The evaluation results of Examples 101-125 were the same as the evaluation results of Examples 1-25, respectively.
  • Example 201 Using the transfer films of Examples 1 to 17 and 101 to 117, a liquid crystal display device having a touch panel was manufactured by the following method.
  • a substrate was prepared by forming an ITO transparent electrode pattern and copper routing wiring on a cycloolefin polymer film. Using the transfer film from which the protective film was peeled off, the transfer film was laminated on the substrate at the position where the transfer film covered the ITO transparent electrode pattern and the copper lead-out wiring. Lamination is performed using a vacuum laminator manufactured by MCK Co., Ltd. The temperature of the cycloolefin polymer film is 40 ° C., the temperature of the rubber roller is 100 ° C., the linear pressure is 3 N / cm, and the transport speed is 2 m / min. done on condition.
  • the exposure mask quartz exposure mask having a pattern for forming an overcoat
  • the temporary support After standing for 24 hours in an environment of 23° C. and 55% RH (relative humidity), the photosensitive layer was pattern-exposed through a temporary support with an exposure dose of 150 mJ/cm 2 (i-line). After peeling off the temporary support, development processing was performed for 30 seconds using a 1.0 mass % aqueous solution of sodium carbonate at 23°C. After the development process, the sample was rinsed with pure water at 22° C. for 30 seconds from an ultrahigh-pressure cleaning nozzle.
  • a liquid crystal display device having a touch panel was manufactured by bonding the manufactured touch panel to a liquid crystal display element manufactured by the method described in paragraphs [0097] to [0119] of JP-A-2009-47936. It was confirmed that a liquid crystal display device equipped with a touch panel has excellent display characteristics and operates without problems.

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WO2020196802A1 (ja) * 2019-03-26 2020-10-01 富士フイルム株式会社 銀導電性材料保護膜用転写フィルム、パターン付き銀導電性材料の製造方法、積層体、及び、タッチパネル
WO2021010058A1 (ja) * 2019-07-12 2021-01-21 富士フイルム株式会社 転写フィルム、積層体の製造方法およびタッチパネルの製造方法
WO2021014914A1 (ja) * 2019-07-24 2021-01-28 富士フイルム株式会社 感光性樹脂組成物、転写フィルム、硬化膜、積層体、及び、タッチパネルの製造方法

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