WO2022138154A1 - 積層体の製造方法、回路配線の製造方法、転写フィルム - Google Patents

積層体の製造方法、回路配線の製造方法、転写フィルム Download PDF

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Publication number
WO2022138154A1
WO2022138154A1 PCT/JP2021/045044 JP2021045044W WO2022138154A1 WO 2022138154 A1 WO2022138154 A1 WO 2022138154A1 JP 2021045044 W JP2021045044 W JP 2021045044W WO 2022138154 A1 WO2022138154 A1 WO 2022138154A1
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WIPO (PCT)
Prior art keywords
photosensitive composition
composition layer
layer
transfer film
mass
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Ceased
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PCT/JP2021/045044
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English (en)
French (fr)
Japanese (ja)
Inventor
知樹 松田
壮二 石坂
大輔 有岡
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Fujifilm Corp
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Fujifilm Corp
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Priority to JP2022572099A priority Critical patent/JP7759347B2/ja
Priority to CN202180085907.0A priority patent/CN116670593A/zh
Publication of WO2022138154A1 publication Critical patent/WO2022138154A1/ja
Anticipated expiration legal-status Critical
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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
    • G03F7/004—Photosensitive materials
    • 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
    • G03F7/38—Treatment before imagewise removal, e.g. prebaking
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process

Definitions

  • the present invention relates to a method for manufacturing a laminated body, a method for manufacturing a circuit wiring, and a transfer film.
  • a photosensitive composition layer is arranged on an arbitrary substrate using a transfer film, and the photosensitive composition layer is exposed to the photosensitive composition layer through a mask.
  • the developing method is widely used.
  • Patent Document 1 discloses a method for manufacturing a laminate using a photosensitive resin laminate in which a predetermined intermediate layer and a predetermined photosensitive resin layer are sequentially laminated on a support film.
  • the present inventors have studied a method for producing a laminate using a conventional transfer film or the like as described in Patent Document 1, and found that the shape of the obtained pattern tends to be defective.
  • the above problem is likely to occur when the temporary support is peeled off and exposed in order to obtain a higher-definition pattern.
  • a transfer film is attached to a transfer target, the temporary support is peeled off, pattern exposure is performed, and further development is performed to obtain a desired pattern.
  • the pattern shape tends to become a hem-spreading shape in which the width of the pattern widens as it approaches the substrate side from the opposite side of the substrate side.
  • the hem spreading shape means a pattern shape in which the length of the lower base (on the substrate side) is longer than the length of the upper base (on the side opposite to the substrate) in the obtained pattern shape. More specifically, as shown in FIG. 1, in the pattern 2 arranged on the substrate 1, there is a problem that the skirt spreading portion 3 as shown by the broken line portion is generated.
  • the fact that the obtained pattern does not easily become a hem-spreading shape is also referred to as being excellent in pattern shape.
  • the surface of the transfer film having the temporary support, the intermediate layer, and the photosensitive composition layer in this order is brought into contact with the substrate on the side opposite to the intermediate layer side of the photosensitive composition layer.
  • the bonding process of bonding the transfer film and the above substrate, A peeling step of peeling the temporary support between the temporary support and the intermediate layer,
  • the exposure step of pattern-exposing the photosensitive composition layer and It has a developing step of developing the exposed photosensitive composition layer with an alkaline developer to form a pattern.
  • a method for manufacturing a laminated body, wherein the difference between the contact angle X determined by the measurement X described later and the contact angle Y determined by the measurement Y described later is 20 degrees or less.
  • [2] The method for manufacturing a laminate according to [1], wherein the contact angle X is 50 to 80 degrees.
  • the photosensitive composition layer contains a resin and contains a resin.
  • the method for producing a laminate according to any one of [1] to [4], wherein the I / O value of the resin is 0.50 to 0.70.
  • the photosensitive composition layer contains a bifunctional or higher functional compound and a resin, and contains.
  • the intermediate layer contains at least one selected from the group consisting of polyhydric alcohols, oxide adducts of polyhydric alcohols, phenol derivatives, water-soluble cellulose derivatives, polyether resins and polyamide resins.
  • the exposure step is an exposure step in which the exposed intermediate layer and the mask are brought into contact with each other for pattern exposure.
  • the surface of the transfer film having the temporary support, the intermediate layer, and the photosensitive composition layer in this order on the opposite side of the photosensitive composition layer from the intermediate layer side is formed on a substrate having a conductive layer.
  • a method for manufacturing a circuit wiring wherein the difference between the contact angle X obtained by the measurement X described later and the contact angle Y obtained by the measurement Y described later is 20 degrees or less.
  • a temporary support, an intermediate layer, and a photosensitive composition layer are provided in this order.
  • the photosensitive composition layer contains a resin and contains a resin.
  • the transfer film according to any one of [13] to [16], wherein the I / O value of the resin is 0.5 to 0.7.
  • the photosensitive composition layer contains a bifunctional or higher functional compound and a resin, and contains.
  • the intermediate layer contains at least one selected from the group consisting of polyhydric alcohols, oxide adducts of polyhydric alcohols, phenol derivatives, water-soluble cellulose derivatives, polyether resins and polyamide resins. , [13] to [19].
  • the numerical range represented by using “-" means a range including the numerical values before and after "-" as the lower limit and the upper limit.
  • the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of another numerical range described in stages.
  • the upper limit or the lower limit described in a certain numerical range may be replaced with the values shown in the examples.
  • process is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes. ..
  • transparent means that the average transmittance of visible light having a wavelength of 400 to 700 nm is 80% or more, and is preferably 90% or more.
  • the average transmittance of visible light is a value measured by using a spectrophotometer, and can be measured by, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are TSKgel GMHxL, TSKgel G4000HxL, TSKgel G2000HxL (all trade names manufactured by Toso Co., Ltd.) and elution as columns. It is a value converted by using THF (tetrahydrofuran) as a liquid, a differential refractometer as a detector, and polystyrene as a standard material, and polystyrene as a standard material measured by a gel permeation chromatography (GPC) analyzer.
  • THF tetrahydrofuran
  • the molecular weight of a compound having a molecular weight distribution is the weight average molecular weight (Mw).
  • Mw weight average molecular weight
  • the content of the metal element is a value measured by using an inductively coupled plasma (ICP) spectroscopic analyzer.
  • the refractive index is a value measured using an ellipsometer at a wavelength of 550 nm.
  • the hue is a value measured using a color difference meter (CR-221, manufactured by Minolta Co., Ltd.).
  • (meth) acrylic is a concept that includes both acrylic and methacrylic
  • (meth) acryloxy group is a concept that includes both an acryloxy group and a metaacryloxy group.
  • alkali-soluble means that the solubility of sodium carbonate in 100 g of a 1% by mass aqueous solution at 22 ° C. is 0.1 g or more.
  • water-soluble means that the solubility in 100 g of water having a liquid temperature of 22 ° C. and a pH of 7.0 is 0.1 g or more.
  • the water-soluble resin is intended to be a resin that satisfies the above-mentioned solubility conditions.
  • the "solid content" of the composition means a component forming a composition layer (photosensitive composition layer, intermediate layer, thermoplastic resin layer, etc.) formed by using the composition.
  • a solvent organic solvent, water, etc.
  • the liquid component is also regarded as a solid content.
  • a feature of the method for manufacturing a laminated body of the present invention is that the difference between the contact angle X determined by the measurement X described later and the contact angle Y determined by the measurement Y described later is 20 degrees or less.
  • the layer (cured layer) obtained by exposing the photosensitive composition layer has a low affinity for the alkaline developer, and therefore, It is presumed that when the pattern is developed using an alkaline developer, the pattern shape is excellent as a result of suppressing the swelling and dissolution of the pattern, which makes it difficult to form a hem-spreading shape.
  • excellent pattern shape is also referred to as excellent effect of the present invention.
  • the difference between the contact angle X determined by the measurement X and the contact angle Y determined by the measurement Y is 20 degrees or less, preferably 1 to 20 degrees, preferably 10 to 20 degrees. More preferred.
  • the above difference is a numerical value obtained by subtracting the smaller one from the larger one of the contact angle X and the contact angle Y. For example, when the contact angle Y is larger than the contact angle X, the above difference is obtained by "contact angle Y-contact angle X". If the contact angle X and the contact angle Y have the same numerical value, the difference is 0.
  • the contact angle X is preferably 10 to 170 degrees, more preferably 30 to 100 degrees, further preferably 50 to 80 degrees, particularly preferably 50 to 70 degrees, and most preferably 50 to 64 degrees.
  • the contact angle X is a value obtained by the following measurement X.
  • measurement X the surface of the photosensitive composition layer of the transfer film opposite to the intermediate layer side is brought into contact with the substrate, the transfer film and the substrate are bonded together, and the temporary support and the intermediate layer are obtained from the obtained laminate.
  • the temporary support is peeled off from the exposed intermediate layer side to expose the entire surface of the photosensitive composition layer, and then the photosensitive composition layer is brought into contact with the alkaline developer used in the developing step to obtain the exposed cured layer.
  • the exposure conditions (type of light source, exposure amount, etc.) for full-scale exposure are the same as the exposure conditions used in the exposure step described later. That is, the full exposure performed by the measurement X corresponds to the exposure in which the exposure range of the pattern exposure carried out in the exposure step described later is changed to the entire surface of the photosensitive composition layer.
  • a method for measuring the water contact angle for example, at room temperature (25 ° C.), 2 to 10 ⁇ L of ion-exchanged water is dropped onto the surface of the exposed cured layer, and a contact angle meter (DSA25S, manufactured by KRUSS) is used.
  • the measurement X is performed after the protective film is peeled off from the transfer film.
  • the contact angle Y is preferably 10 to 170 degrees, more preferably 50 to 120 degrees, more preferably more than 70 degrees and 120 degrees or less, further preferably more than 70 degrees and 90 degrees or less, and particularly preferably more than 70 degrees and less than 80 degrees. ..
  • the contact angle Y is a value obtained by the following measurement Y. In the measurement Y, the surface of the photosensitive composition layer of the transfer film opposite to the intermediate layer side was brought into contact with the substrate, the transfer film and the substrate were bonded together, and the temporary support and the intermediate layer were obtained from the obtained laminate.
  • the temporary support is peeled off from the surface of the exposed intermediate layer to expose the entire photosensitive composition layer, and then the photosensitive composition layer is brought into contact with water to measure the water contact angle on the surface of the exposed cured layer.
  • the measurement is such that the contact angle is Y.
  • the measurement Y is the same measurement method as the measurement X except that the alkaline developer is changed to water in the measurement X.
  • Examples of the method for measuring the water contact angle include the method for measuring the water contact angle used in the above-mentioned contact angle X.
  • the exposure conditions (type of light source, exposure amount, etc.) at the time of full-scale exposure are the same as the exposure conditions carried out in the exposure step described later.
  • the full-scale exposure performed in the measurement Y corresponds to an exposure in which the exposure range of the pattern exposure performed in the exposure step described later is changed to the entire surface of the photosensitive composition layer.
  • the measurement Y is performed after the protective film is peeled off from the transfer film.
  • Examples of the method for adjusting the contact angle X and the contact angle Y include changing the type and content of the resin contained in the photosensitive composition layer. Specifically, a method of using a resin in which the weight average molecular weight, acid value and Tg (glass transition temperature) are adjusted to each suitable embodiment described later is used, and a resin synthesized by using a trifunctional or higher functional monomer is used. Examples thereof include a method to be used and a method in which these are combined.
  • the bonding step the surface of the transfer film having the temporary support, the intermediate layer, and the photosensitive composition layer in this order is brought into contact with the substrate on the side opposite to the intermediate layer side, and the transfer is performed. This is the process of bonding the film and the substrate.
  • the bonding step may be performed after the protective film is peeled off.
  • the surface of the photosensitive composition layer of the transfer film opposite to the intermediate layer side is brought into contact with the substrate and pressure-bonded.
  • the crimping method include known transfer methods and laminating methods. Among them, as a crimping method, it is preferable to superimpose the surface of the transfer film on the side opposite to the intermediate layer side of the photosensitive composition layer on the substrate, and perform pressurization and heating by a roll or the like.
  • the bonding method include a bonding method using a known laminator such as a vacuum laminator and an auto-cut laminator.
  • the laminating temperature is preferably 70 to 130 ° C.
  • a substrate having a conductive layer is preferable.
  • the substrate having a conductive layer any layer other than the conductive layer may be formed on the substrate, if necessary. That is, the substrate is preferably a conductive substrate having at least a conductive layer arranged on the substrate. Examples of the substrate include a resin substrate, a glass substrate, and a semiconductor substrate.
  • the substrate paragraph [0140] of International Publication No. 2018/155193 is preferable, and these contents are incorporated in the present specification.
  • the material of the resin substrate cycloolefin polymer or polyimide is preferable.
  • the thickness of the resin substrate is preferably 5 to 200 ⁇ m, more preferably 10 to 100 ⁇ m.
  • the conductive layer at least one conductive layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer and a conductive polymer layer is preferable from the viewpoint of conductivity and fine wire forming property. .. Only one conductive layer may be arranged on the substrate, or two or more layers may be arranged. When two or more conductive layers are arranged, it is preferable that the conductive layers arranged in two or more layers are conductive layers made of different materials. As the conductive layer, paragraph [0141] of International Publication No. 2018/155193 is preferable, and these contents are incorporated in the present specification.
  • the peeling step is a step of peeling the temporary support between the temporary support and the intermediate layer.
  • Examples of the method for peeling the temporary support include known peeling methods. Specifically, the cover film peeling mechanism described in paragraphs [0161] to [0162] of JP-A-2010-072589 can be mentioned.
  • the exposure step is a step of pattern-exposing the photosensitive composition layer.
  • the "pattern exposure” is a form of exposure in a pattern, that is, an exposure in a form in which an exposed portion and a non-exposed portion are present.
  • the positional relationship between the exposed area and the unexposed area in the pattern exposure is not particularly limited and can be adjusted as appropriate.
  • the exposure direction is not particularly limited, but the exposure may be performed from the intermediate layer side of the photosensitive composition layer, or may be exposed from the side opposite to the intermediate layer side (substrate side) of the photosensitive composition layer.
  • the exposure step it is preferable that the intermediate layer exposed by the above-mentioned peeling step and the mask are brought into contact with each other for pattern exposure.
  • a high-definition pattern can be obtained by exposing the pattern in contact with the mask.
  • a curing reaction of the components contained in the photosensitive composition layer occurs in the exposed region (position corresponding to the opening of the mask) of the photosensitive composition layer. obtain.
  • an alkaline development treatment after exposure the non-exposed region of the photosensitive composition layer is removed, and a pattern is formed.
  • the method for producing the laminate preferably includes a peeling step of peeling off the mask used in the exposure step between the exposure step and the developing process.
  • the light source for pattern exposure is such that it can irradiate at least light in a wavelength range capable of curing the photosensitive composition layer (for example, 365 nm and 405 nm). , Can be selected and used as appropriate.
  • a wavelength range capable of curing the photosensitive composition layer for example, 365 nm and 405 nm.
  • the main wavelength of the exposure light for pattern exposure is preferably 365 nm.
  • the main wavelength means the wavelength having the highest intensity.
  • Examples of the light source include various lasers, light emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps and metal halide lamps.
  • the exposure amount is preferably 5 to 200 mJ / cm 2 , more preferably 10 to 200 mJ / cm 2 .
  • Examples of the light source, the amount of exposure, and the method of exposure include paragraphs [0146] to [0147] of International Publication No. 2018/155193, the contents of which are incorporated in the present specification.
  • the developing step is a step of developing the exposed photosensitive composition layer with an alkaline developer to form a pattern.
  • the photosensitive composition layer is a negative photosensitive layer
  • the non-exposed area of the photosensitive composition layer is removed by developing with an alkaline developer, and a pattern in which the opening of the mask is a convex portion is formed. It is formed.
  • an alkaline aqueous solution is preferable.
  • the alkaline compound (compound that dissolves in water and shows alkalinity) contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, and tetramethylammonium hydroxide. , Tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and choline (2-hydroxyethyltrimethylammonium hydroxide).
  • Examples of the developing method include known developing methods. Specific examples include paddle development, shower development, spin development and dip development. As the developing method, the developing method described in paragraph [0195] of International Publication No. 2015/093271 is preferable.
  • post-exposure process and post-baking process In the method for producing a laminate of the present invention, a step of further exposing the pattern obtained by the developing step (hereinafter, also referred to as “post-exposure step”) and / or a step of heating (hereinafter, “post-baking step””. Also referred to as).
  • post-exposure step a step of further exposing the pattern obtained by the developing step
  • post-baking step a step of heating
  • the post-baking temperature is preferably 80 to 250 ° C, more preferably 90 to 160 ° C.
  • the post-baking time is preferably 1 to 180 minutes, more preferably 10 to 60 minutes.
  • the position and size of the pattern formed on the substrate obtained by the method for manufacturing the laminate are not particularly limited.
  • the pattern is preferably a fine line.
  • the width of the pattern is preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, further preferably 10 ⁇ m or less, and particularly preferably 5 ⁇ m or less.
  • the lower limit is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more.
  • the laminate produced by the method for producing a laminate of the present invention can be applied to various devices.
  • the device provided with the laminated body include an input device, a touch panel is preferable, and a capacitive touch panel is more preferable.
  • the input device can be applied to a display device such as an organic EL (organic electroluminescence) display device and a liquid crystal display device.
  • the etching step is a step of etching the conductive layer in the region where the pattern is not arranged. Specifically, in the etching step, the pattern obtained from the photosensitive composition layer by the developing step in the above-mentioned method for manufacturing a laminated body is used as an etching resist, and the conductive layer is etched.
  • the substrate has the same meaning as the substrate in the above-mentioned method for manufacturing a laminated body, and the preferred embodiment is also the same.
  • Examples of the etching treatment method include known etching methods. Specifically, the method described in paragraphs [0209] to [0210] of JP-A-2017-120435, the method described in paragraphs [0048]-[0054] of JP-A-2010-152155, and an etching solution. Examples thereof include wet etching and dry etching such as plasma etching.
  • an acidic or alkaline etching solution can be appropriately selected according to the etching target.
  • the acidic etching solution is, for example, an acidic aqueous solution containing one or more acidic compounds, and at least selected from the group consisting of the acidic compounds and ferric chloride, ammonium fluoride and potassium permanganate.
  • An acidic mixed aqueous solution with one kind of salt can be mentioned.
  • the acidic compound contained in the acidic aqueous solution is at least one acidic compound selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid and phosphoric acid. Is preferable.
  • the alkaline etching solution include an alkaline aqueous solution containing one or more alkaline compounds, and an alkaline mixed aqueous solution of an alkaline compound and a salt (for example, potassium permanganate).
  • alkaline compound compound that dissolves in water and exhibits alkalinity
  • examples of the alkaline compound contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, ammonia, an organic amine, and a salt of an organic amine (for example, tetramethylammonium hydroxide). At least one selected from the group consisting of is preferable.
  • the circuit wiring manufacturing method of the present invention may include a removal step of removing the remaining pattern.
  • the removal step is preferably carried out after the etching step described above.
  • Examples of the method for removing the remaining pattern include a method for removing by chemical treatment, and a method for removing with a removing liquid is preferable.
  • the liquid temperature of the removing liquid is preferably 30 to 80 ° C, more preferably 50 to 80 ° C.
  • a method of immersing a substrate having a pattern to be removed in a removing liquid during stirring having a liquid temperature of 50 to 80 ° C. for 1 to 30 minutes can be mentioned.
  • Examples of the method for removing the remaining pattern include a method of removing the remaining pattern by a known method such as a spray method, a shower method and a paddle method using a removing liquid.
  • Examples of the removing solution include a removing solution in which an alkaline inorganic compound or an alkaline organic compound is dissolved in at least one solution selected from the group consisting of water, dimethyl sulfoxide, N-methylpyrrolidone and a mixed solution thereof. Be done.
  • Examples of the alkaline inorganic compound include sodium hydroxide and potassium hydroxide.
  • Examples of the alkaline organic compound include a primary amine compound, a secondary amine compound, a tertiary amine compound and a quaternary ammonium salt compound.
  • the circuit wiring manufacturing method may include other steps in addition to the above-mentioned steps.
  • steps for example, the step of reducing the visible light reflectance described in paragraph [0172] of International Publication No. 2019/022089 and the surface of the insulating film described in paragraph [0172] of International Publication No. 2019/022089.
  • a step of forming a new conductive layer can be mentioned.
  • the method for manufacturing a circuit wiring may include a step of reducing the visible light reflectance of a part or all of the plurality of conductive layers of the substrate.
  • the treatment for reducing the visible light reflectance include an oxidation treatment.
  • the visible light reflectance of the conductive layer can be lowered by oxidizing copper to copper oxide and blackening the conductive layer.
  • Examples of the treatment for reducing the visible light reflectance include paragraphs [0017] to [0025] of JP-A-2014-150118 and paragraphs [0041], [0042], and [0048] of JP-A-2013-206315. And [0058], the contents of which are incorporated herein.
  • the method for manufacturing a circuit wiring may include a step of forming an insulating film on the surface of the circuit wiring and a step of forming a new conductive layer on the surface of the insulating film.
  • the first electrode pattern and the insulated second electrode pattern can be formed.
  • the step of forming the insulating film include a known method of forming a permanent film.
  • an insulating film having a desired pattern may be formed by photolithography using a photosensitive composition having an insulating property.
  • a new conductive layer having a desired pattern may be formed by photolithography using a photosensitive composition having conductivity.
  • a substrate having a plurality of conductive layers on both surfaces of the substrate may be used to form circuit wiring sequentially or simultaneously with respect to the conductive layers formed on both surfaces of the substrate.
  • a circuit wiring for a touch panel in which the first conductive pattern is formed on the surface of one substrate and the second conductive pattern is formed on the surface of the other substrate. It is also preferable to form the touch panel circuit wiring having the above configuration from both sides of the substrate by roll-to-roll.
  • the circuit wiring manufactured by the method of manufacturing the circuit wiring can be applied to various devices.
  • Examples of the device provided with the circuit wiring include an input device, a touch panel is preferable, and a capacitive touch panel is more preferable.
  • the input device can be applied to a display device such as an organic EL display device and a liquid crystal display device.
  • the transfer film of the present invention has a temporary support, an intermediate layer, and a photosensitive composition layer in this order, and is developed with an alkaline developer after the exposure treatment to form a pattern.
  • the difference between the contact angle X obtained by the measurement X and the contact angle Y obtained by the measurement Y is 20 degrees or less.
  • the difference between the contact angle X, the contact angle Y, and the contact angle X and the contact angle Y in the transfer film is the contact angle X, the contact angle Y, the contact angle X, and the contact angle Y, respectively, in the above-described method for manufacturing the laminated body. It is synonymous with the difference between, and the preferable range is also the same.
  • the transfer film may have other layers in addition to the photosensitive composition layer and the intermediate layer.
  • the other layer include a thermoplastic resin layer described later.
  • the transfer film may have a structure in which a protective film described later is provided on the photosensitive composition layer.
  • the embodiment of the transfer film is not particularly limited, and examples thereof include the following configurations. (1) “Temporary support / intermediate layer / photosensitive composition layer / protective film” (2) “Temporary support / thermoplastic resin layer / intermediate layer / photosensitive composition layer / protective film” As the photosensitive composition layer in each of the above configurations, a negative type photosensitive composition layer is preferable. Further, as the photosensitive composition layer, a colored resin layer is also preferable.
  • the maximum width of the waviness of the transfer film is preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less, still more preferably 60 ⁇ m or less.
  • the lower limit is preferably 0 ⁇ m or more, more preferably 0.1 ⁇ m or more, still more preferably 1 ⁇ m or more.
  • the maximum width of the waviness of the transfer film is a value measured by the following procedure. First, the transfer film is cut in a direction perpendicular to the main surface so as to have a size of 20 cm in length ⁇ 20 cm in width to prepare a test sample. When the transfer film has a protective film, the protective film is peeled off from the transfer film.
  • test sample is placed on a stage having a smooth and horizontal surface so that the surface of the temporary support faces the stage.
  • the surface of the sample sample was scanned with a laser microscope (for example, VK-9700SP manufactured by KEYENCE) for a range of 10 cm square in the center of the test sample to obtain a three-dimensional surface image, and the obtained three-dimensional surface image was obtained.
  • a laser microscope for example, VK-9700SP manufactured by KEYENCE
  • the transmittance of light having a wavelength of 365 nm in the photosensitive composition layer is preferably 10% or more, more preferably 30% or more, still more preferably 50% or more.
  • the upper limit is not particularly limited, but is preferably 99.9% or less.
  • the transfer film 10 shown in FIG. 1 has a temporary support 11, a composition layer 17 including an intermediate layer 13 and a photosensitive composition layer 15, and a protective film 19 in this order.
  • the transfer film 10 shown in FIG. 1 has a form in which the protective film 19 is arranged, but the protective film 19 may not be arranged.
  • each layer excluding the protective film 19 that can be arranged on the temporary support 11 is also referred to as a composition layer 17.
  • the transfer film may have a thermoplastic resin layer in addition to the above layer, and it is preferable that the thermoplastic resin layer is arranged between the temporary support 11 and the intermediate layer 13.
  • the transfer film has a temporary support.
  • the temporary support is a member that supports the photosensitive composition layer, and is finally removed by a peeling treatment.
  • the temporary support may have a single-layer structure or a multi-layer structure.
  • a film is preferable, and a resin film is more preferable.
  • a film having flexibility and not causing significant deformation, shrinkage or elongation under pressure, pressure and heating is preferable, and a film without deformation and scratches such as wrinkles is also preferable.
  • the film include polyethylene terephthalate film (for example, biaxially stretched polyethylene terephthalate film), polymethylmethacrylate film, cellulose triacetate film, polystyrene film, polyimide film and polycarbonate film, and polyethylene terephthalate film is preferable.
  • the temporary support is preferably highly transparent because the pattern can be exposed through the temporary support.
  • the transmittance of the temporary support at a wavelength of 365 nm is preferably 60% or more, more preferably 70% or more.
  • the upper limit is preferably less than 100%. From the viewpoint of pattern formation during pattern exposure via the temporary support and transparency of the temporary support, it is preferable that the haze of the temporary support is small. Specifically, the haze of the temporary support is preferably 2% or less, more preferably 0.5% or less, still more preferably 0.1% or less.
  • the lower limit is preferably 0% or more.
  • the number of fine particles, foreign substances and defects in the temporary support is small.
  • the number of fine particles for example, fine particles having a diameter of 1 ⁇ m
  • foreign matter and defects in the temporary support is preferably 50 pieces / 10 mm 2 or less, more preferably 10 pieces / 10 mm 2 or less, and 3 pieces / 10 mm. 2 or less is more preferable, and 0 pieces / 10 mm 2 is particularly preferable.
  • the thickness of the temporary support is preferably 5 to 200 ⁇ m, more preferably 5 to 150 ⁇ m, still more preferably 5 to 50 ⁇ m, and particularly preferably 5 to 25 ⁇ m from the viewpoint of ease of handling and versatility.
  • the thickness of the temporary support is calculated as an average value of any five points measured by cross-sectional observation with an SEM (Scanning Electron Microscope).
  • the temporary support may have a layer (lubricant layer) containing fine particles on one side or both sides of the temporary support.
  • the diameter of the fine 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 surface of the temporary support in contact with the photosensitive composition layer may be surface-modified.
  • the surface modification treatment include treatment using UV irradiation, corona discharge, plasma, and the like.
  • the exposure amount in UV irradiation is preferably 10 to 2000 mJ / cm 2 , more preferably 50 to 1000 mJ / cm 2 .
  • the lamp output and the illuminance are not particularly limited.
  • Light sources for UV irradiation include, for example, low pressure mercury lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps and light emitting diodes that emit light in the wavelength band of 150 to 450 nm. (LED) can be mentioned.
  • Examples of the temporary support include a biaxially stretched polyethylene terephthalate film having a thickness of 16 ⁇ m, a biaxially stretched polyethylene terephthalate film having a thickness of 12 ⁇ m, and a biaxially stretched polyethylene terephthalate film having a thickness of 9 ⁇ m.
  • Examples of the provisional support include paragraphs [0017] to [0018] of JP-A-2014-085643, paragraphs [0019] to [0026] of JP-A-2016-0273363, and International Publication No. 2012/081680. Paragraphs [0041] to [0057] of the issue and paragraphs [0029] to [0040] of International Publication No.
  • Examples of commercially available temporary supports include Lumirror 16KS40, Lumirror 16FB40 (above, manufactured by Toray Industries, Inc.), Cosmoshine A4100, Cosmoshine A4300, and Cosmoshine A8300 (above, manufactured by Toyobo Industries, Ltd.).
  • the transfer film of the present invention has a photosensitive composition layer.
  • a display device equipped with a touch panel such as a capacitance type input device (for example, an organic EL display device, a liquid crystal display device, etc.), the electrode pattern corresponding to the sensor of the visual recognition unit, the wiring of the peripheral wiring portion and the wiring of the extraction wiring portion, etc.
  • a conductive layer pattern is provided inside the touch panel.
  • a negative photosensitive composition layer (photosensitive layer) is provided on a substrate using a transfer film or the like, and a mask having a desired pattern for the photosensitive layer is used. A method of developing after exposure is widely adopted. Therefore, as the photosensitive composition layer, a negative type photosensitive composition layer is preferable.
  • the photosensitive composition layer is a negative photosensitive composition layer, the formed pattern corresponds to a cured layer.
  • the photosensitive composition layer preferably contains a resin, a polymerizable compound and a polymerization initiator, which will be described later. Further, as described later, the photosensitive composition layer preferably contains an alkali-soluble resin (such as a resin which is an alkali-soluble resin). That is, the photosensitive composition layer preferably contains a resin containing an alkali-soluble resin, a polymerizable compound, and a polymerization initiator.
  • the photosensitive composition layer contains 10 to 90% by mass of the resin, 5 to 70% by mass of the polymerizable compound, and 0.01 to 20% by mass of the polymerization initiator with respect to the total mass of the photosensitive composition layer. It is preferable to include it.
  • the photosensitive composition layer may contain a resin.
  • a resin an alkali-soluble resin is preferable.
  • an alkali-soluble resin in the thermoplastic resin layer described later may be used.
  • the resin preferably contains a structural unit derived from a monomer having an aromatic hydrocarbon group, from the viewpoint of suppressing line width thickening and deterioration of resolution when the focal position is deviated during exposure.
  • the aromatic hydrocarbon group include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group.
  • the content of the structural unit derived from the monomer having an aromatic hydrocarbon group in the resin is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the resin.
  • the upper limit is preferably 80% by mass or less, more preferably 60% by mass or less, still more preferably 38% by mass or less, based on the total mass of the resin.
  • the photosensitive composition layer contains a plurality of resins, it is preferable that the average value of the content of the structural units derived from the monomer having an aromatic hydrocarbon group is within the above range. As the average value, the mass average value is used.
  • the monomer having an aromatic hydrocarbon group examples include a monomer having an aralkyl group, styrene and a polymerizable styrene derivative (for example, methyl styrene, vinyl toluene, tert-butoxy styrene, acetoxy styrene, 4-vinyl).
  • a monomer having an aralkyl group or styrene is preferable, and styrene is more preferable.
  • the content of the structural unit derived from styrene is preferably 10 to 80% by mass, preferably 10 to 60% by mass, based on the total mass of the resin. Is more preferable, 20 to 60% by mass is further preferable, 20 to 50% by mass is particularly preferable, and 20 to 38% by mass is most preferable.
  • the photosensitive composition layer contains a plurality of resins, it is preferable that the average value of the content of the structural unit having an aromatic hydrocarbon group is within the above range. As the average value, the mass average value is used.
  • aralkyl group examples include a substituted or unsubstituted phenylalkyl group (excluding the benzyl group) and a substituted or unsubstituted benzyl group, and a substituted or unsubstituted benzyl group is preferable.
  • Examples of the monomer having a phenylalkyl group include phenylethyl (meth) acrylate.
  • Examples of the monomer 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 vinylbenzyl alcohol. Can be mentioned. Of these, benzyl (meth) acrylate is preferable.
  • the monomer component having an aromatic hydrocarbon group in the resin is benzyl (meth) acrylate
  • the content of the structural unit derived from benzyl (meth) acrylate is 50 to 95% by mass with respect to the total mass of the resin. % Is preferable, 60 to 90% by mass is more preferable, 70 to 90% by mass is further preferable, and 75 to 90% by mass is particularly preferable.
  • the resin containing a structural unit derived from the monomer having an aromatic hydrocarbon group includes a monomer having an aromatic hydrocarbon group, at least one of the first monomer described later, and / or the first item described later. It is preferably obtained by polymerizing with at least one of the monomers of 2.
  • the resin containing no structural unit derived from the monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one of the first monomers described later, and the first monomer is preferable. It is more preferable to obtain it by copolymerizing at least one of the above and at least one of the second monomer described later.
  • the first monomer is a monomer having a carboxy group in the molecule.
  • the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic acid anhydride and maleic acid semi-ester. Meta) Acrylic acid is preferred.
  • the content of the structural unit derived from the first monomer in the resin is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and the effect of the present invention is more excellent with respect to the total mass of the resin. From the point of view, 15 to 30% by mass is more preferable, and 15 to 20% by mass is particularly preferable.
  • the content When the content is 5% by mass or more, excellent developability and edge fuseability control can be realized. When the content is 50% by mass or less, high resolution of the resist pattern, control of the shape of the resist, and high chemical resistance of the resist pattern can be realized. Further, when the content is within the above range, the above-mentioned contact angle X and the above-mentioned contact angle Y can be adjusted.
  • the second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule.
  • Examples of the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate.
  • (Meta) acrylates such as tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate and 2-ethylhexyl (meth) acrylate; vinyl acetate Esters of vinyl alcohols such as; (meth) acrylonitrile.
  • methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate or n-butyl (meth) acrylate is preferable, and methyl (meth) acrylate or ethyl (meth) acrylate is more preferable.
  • the content of the structural unit derived from the second monomer in the resin is preferably 5 to 80% by mass, more preferably 15 to 60% by mass, and further preferably 30 to 60% by mass with respect to the total mass of the resin. preferable.
  • the resin contains a structural unit derived from a monomer having an aralkyl group and / or a structural unit derived from styrene, it is possible to suppress line width thickening and deterioration of resolution when the focal position is deviated during exposure.
  • the resin includes a copolymer containing a structural unit derived from methacrylic acid, a structural unit derived from benzyl methacrylate, and a structural unit derived from styrene, a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and benzyl.
  • a copolymer containing a constituent unit derived from methacrylate and a constituent unit derived from styrene or a copolymer containing a constituent unit derived from methacrylic acid, a constituent unit derived from methyl methacrylate, and a constituent unit derived from styrene.
  • the structural unit derived from the monomer having an aromatic hydrocarbon group is 20 to 60% by mass
  • the structural unit derived from the first monomer is 10 to 40% by mass, and the like.
  • the constituent unit derived from the second monomer is contained in an amount of 15 to 60% by mass.
  • the structural unit derived from the monomer having an aromatic hydrocarbon group is 70 to 90% by mass
  • the structural unit derived from the first monomer is 10 to 25% by mass.
  • the resin may have any of a linear structure, a branched structure and an alicyclic structure in the side chain.
  • a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain can be introduced into the side chain of the resin.
  • the group having an alicyclic structure may be either a monocyclic ring or a polycyclic ring.
  • Examples of the monomer containing a group having a branched structure in the side chain include isopropyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and (meth). ) Isoamyl acrylate, tert-amyl (meth) acrylate, sec-amyl (meth) acrylate, 2-octyl (meth) acrylate, 3-octyl (meth) acrylate and tert-octyl (meth) acrylate Can be mentioned.
  • isopropyl (meth) acrylate, isobutyl (meth) acrylate or tert-butyl methacrylate are preferable, and isopropyl methacrylate or tert-butyl methacrylate is more preferable.
  • the monomer containing a group having an alicyclic structure in the side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group.
  • a (meth) acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms can be mentioned.
  • (meth) acrylic acid (bicyclo [2.2.1] heptyl-2), (meth) acrylic acid-1-adamantyl, (meth) acrylic acid-2-adamantyl, (meth) acrylic acid- 3-Methyl-1-adamantyl, (meth) acrylate-3,5-dimethyl-1-adamantyl, (meth) acrylate-3-ethyladamantyl, (meth) acrylate-3-methyl-5-ethyl-1 -Adamanthyl, (meth) acrylic acid-3,5,8-triethyl-1-adamantyl, (meth) acrylic acid-3,5-dimethyl-8-ethyl-1-adamantyl, (meth) acrylic acid 2-methyl- 2-adamantyl, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, octahydro-4,7-ment
  • Fentyl acrylate, 1-mentyl (meth) acrylate or tricyclodecane (meth) acrylate are preferred, cyclohexyl (meth) acrylate, (nor) bornyl (nor) acrylate, isobornyl (meth) acrylate, (meth). ) -2-adamantyl acrylate or tricyclodecane (meth) acrylate is more preferred.
  • the glass transition temperature (Tg) of the resin is preferably 30 to 150 ° C, more preferably 100 to 150 ° C, and even more preferably more than 110 ° C and 130 ° C or lower.
  • the I / O value of the resin is preferably 0.30 to 0.90, more preferably 0.45 to 0.70, and even more preferably 0.50 to 0.70.
  • the I / O value is a parameter representing a measure of hydrophilicity / lipophilicity of the resin.
  • the I / O value refer to "Organic Conceptual Diagram" (Yoshio Koda, Sankyo Publishing, 1984). The closer the I / O value of the resin is to 0 (zero), the smaller the polarity of the resin (the higher the lipophilicity of the resin), and the larger the I / O value of the resin, the greater the polarity of the resin. It means (the resin has high hydrophilicity).
  • I (hydrophilicity) and O (lipophilicity) were calculated respectively based on the chemical structure of the resin, and the I / O value was calculated.
  • the acid value of the resin 10 to 200 mgKOH / g is preferable, 30 to 150 mgKOH / g is more preferable, 50 to 150 mgKOH / g is further preferable, and 90 to 150 mgKOH / g is preferable because the effect of the present invention is more excellent. 130 mgKOH / g is particularly preferable.
  • the acid value (mgKOH / g) is the mass (mg) of potassium hydroxide required to neutralize 1 g of the sample.
  • the acid value can be determined, for example, according to the method described in JIS K0070: 1992.
  • the acid value of the resin can be adjusted by the type of the constituent unit of the resin and / or the content of the constituent unit containing the acid group.
  • the weight average molecular weight of the resin is preferably 5,000 to 500,000, more preferably 10,000 to 100,000, still more preferably 20,000 to 50,000, and particularly preferably 20,000 to 40,000.
  • the weight average molecular weight is 500,000 or less, the resolution and developability can be improved.
  • the weight average molecular weight is 5,000 or more, the properties of the developed aggregate and the properties of the unexposed film such as the edge fuse property and the cut chip property of the transfer film can be controlled.
  • the edge fuse property refers to the degree of ease with which the photosensitive composition layer protrudes from the end face of the roll when the transfer film is wound into a roll.
  • the cut chip property refers to the degree of ease of chip flying when the unexposed film is cut with a cutter.
  • the dispersity of the resin is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, still more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.
  • the photosensitive composition layer may contain other resins in addition to the above-mentioned resins.
  • other resins include acrylic resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyamide resin, epoxy resin, polyacetal resin, polyhydroxystyrene resin, and polyimide resin.
  • examples thereof include polybenzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine and polyalkylene glycol.
  • the resin may be used alone or in combination of two or more.
  • two kinds of resins containing a structural unit derived from a monomer having an aromatic hydrocarbon group may be mixed and used, or derived from a monomer having an aromatic hydrocarbon group. It is preferable to mix and use a resin containing a structural unit to be used and a resin not containing a structural unit derived from a monomer having an aromatic hydrocarbon group.
  • the content of the resin containing a structural unit derived from a monomer having an aromatic hydrocarbon group is preferably 50% by mass or more, more preferably 70% by mass or more, based on the total mass of the resin. , 80% by mass or more is more preferable, and 90% by mass or more is particularly preferable.
  • the upper limit is preferably 100% by mass or less.
  • the content of the resin is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, further preferably 30 to 70% by mass, and 40 to 60% by mass with respect to the total mass of the photosensitive composition layer. Especially preferable.
  • the content of the resin is 90% by mass or less with respect to the total mass of the photosensitive composition layer, the development time can be controlled. Further, when the content of the resin is 10% by mass or more with respect to the total mass of the photosensitive composition layer, the edge fuse resistance can be improved.
  • a radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile is added to a solution obtained by diluting the above-mentioned single or plurality of monomers with a solvent such as acetone, methyl ethyl ketone and isopropanol. Is added in an appropriate amount and heated and stirred. A part of the mixture may be added dropwise to the reaction solution for synthesis. Further, after the reaction is completed, a solvent may be further added to adjust the concentration to a desired value.
  • examples of the resin synthesis method include bulk polymerization, suspension polymerization and emulsion polymerization.
  • the photosensitive composition layer preferably contains a polymerizable compound having a polymerizable group.
  • the "polymerizable compound” means a compound that polymerizes under the action of a polymerization initiator described later, and is different from the above-mentioned resin.
  • the polymerizable group of the polymerizable compound is not particularly limited as long as it is a group involved in the polymerization reaction, but has, for example, an ethylenically unsaturated group such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group and a maleimide group.
  • Group examples thereof include a group having a cationically polymerizable group such as an epoxy group and an oxetane group.
  • a group having an ethylenically unsaturated group is preferable, and an acryloyl group or a metaacryloyl group is more preferable.
  • a compound having one or more ethylenically unsaturated groups is preferable because the photosensitive composition layer is more excellent in photosensitivity, and two or more in one molecule.
  • a compound having an ethylenically unsaturated group (polyfunctional ethylenically unsaturated compound) is more preferable.
  • the number of ethylenically unsaturated groups contained in one molecule of the ethylenically unsaturated compound is preferably 1 to 6, more preferably 1 to 3, and 2 to 3 in terms of more excellent resolution and peelability. Is more preferable, and 3 is particularly preferable.
  • the content of the bifunctional ethylenically unsaturated compound is preferably 20% by mass or more, more preferably more than 40% by mass, and further more preferably 55% by mass or more, based on the excellent peelability with respect to the total mass of the polymerizable compound. It is preferable, and 90% by mass or more is particularly preferable.
  • the upper limit is not particularly limited, but is preferably 100% by mass or less. That is, all the polymerizable compounds contained in the photosensitive composition layer may be bifunctional ethylenically unsaturated compounds.
  • the content of the trifunctional ethylenically unsaturated compound is preferably 10% by mass or more, more preferably 20% by mass or more, from the viewpoint that the contact angle X and the contact angle Y can be adjusted with respect to the total mass of the polymerizable compound.
  • the upper limit is not particularly limited, but is preferably 100% by mass or less, more preferably 80% by mass or less, still more preferably 50% by mass or less. That is, all the polymerizable compounds contained in the photosensitive composition layer may be trifunctional ethylenically unsaturated compounds.
  • a (meth) acrylate compound having a (meth) acryloyl group as a polymerizable group is preferable.
  • the photosensitive composition layer preferably contains a polymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups.
  • the polymerizable compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule among the above-mentioned polymerizable compounds B.
  • aromatic ring contained in the polymerizable compound B1 examples include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring and an anthracene ring; aromatic rings such as a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a triazole ring and a pyridine ring. Heterocycles; include these fused rings, preferably aromatic hydrocarbon rings, more preferably benzene rings.
  • the aromatic ring may have a substituent.
  • the polymerizable compound B1 may have only one aromatic ring or may have two or more aromatic rings.
  • the polymerizable compound B1 preferably has a bisphenol structure from the viewpoint of improving the resolution by suppressing the swelling of the photosensitive composition layer due to the developing solution.
  • the bisphenol structure include 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).
  • examples thereof include an F structure and a bisphenol B structure derived from bisphenol B (2,2-bis (4-hydroxyphenyl) butane), and a bisphenol A structure is preferable.
  • Examples of the polymerizable compound B1 having a bisphenol structure include a compound 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 may be bonded via one or more alkyleneoxy groups. As the alkyleneoxy group added to both ends of the bisphenol structure, an ethyleneoxy group or a propyleneoxy group is preferable, and an ethyleneoxy group is more preferable.
  • the number of alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16 per molecule, more preferably 6 to 14.
  • paragraphs [0072] to [0080] of JP-A-2016-224162 are mentioned, and the contents thereof are incorporated in the present specification.
  • the polymerizable compound B1 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, Hitachi Chemical Co., Ltd.).
  • a compound represented by the formula (B1) is also preferable.
  • R 1 and R 2 each independently represent a hydrogen atom or a methyl group.
  • A represents C 2 H 4 .
  • B represents C 3 H 6 .
  • n1 and n3 each independently represent an integer of 1 to 39.
  • n1 + n3 is an integer of 2 to 40.
  • n2 and n4 each independently represent an integer from 0 to 29.
  • n2 + n4 is an integer of 0 to 30.
  • the sequence of constituent units of-(AO)-and-(BO)- may be random or block. In the case of a block, any of-(AO)-and-(BO)-may be on the bisphenyl group side.
  • n1 + n2 + n3 + n4 2 to 20 is preferable, 2 to 16 is more preferable, and 4 to 12 is further preferable. Further, n2 + n4 is preferably 0 to 10, more preferably 0 to 4, further preferably 0 to 2, and particularly preferably 0.
  • the polymerizable compound B1 may be used alone or in combination of two or more.
  • the content of the polymerizable compound B1 is preferably 10% by mass or more, more preferably 20% by mass or more, and more preferably 25% by mass or more, based on the total mass of the photosensitive composition layer, from the viewpoint of better resolution. More preferred.
  • the upper limit is not particularly limited, but is preferably 70% by mass or less, more preferably 60% by mass or less, from the viewpoint of transferability and edge fusion (a phenomenon in which the photosensitive composition exudes from the end portion of the transfer member).
  • the content of the polymerizable compound B1 is preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 55% by mass or more, from the viewpoint of better resolution with respect to the total mass of the polymerizable compound. , 60% by mass or more is particularly preferable.
  • the upper limit is not particularly limited, but from the viewpoint of peelability, 100% by mass or less is preferable, 99% by mass or less is more preferable, 95% by mass or less is further preferable, 90% by mass or less is particularly preferable, and 85% by mass or less is the most preferable. preferable.
  • the photosensitive composition layer may contain other polymerizable compounds in addition to the above-mentioned polymerizable compound B1.
  • the other polymerizable compound is not particularly limited, but can be appropriately selected from known polymerizable compounds.
  • a compound having one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compound), a bifunctional ethylenically unsaturated compound having no aromatic ring, and a trifunctional or higher functional ethylenically unsaturated compound.
  • a compound having one ethylenically unsaturated group in one molecule monofunctional ethylenically unsaturated compound
  • a bifunctional ethylenically unsaturated compound having no aromatic ring and a trifunctional or higher functional ethylenically unsaturated compound.
  • Examples of the monofunctional ethylenically unsaturated compound include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, polyethylene glycol mono (meth) acrylate, and polypropylene glycol mono (meth) acrylate. And phenoxyethyl (meth) acrylates.
  • Examples of the bifunctional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, urethane di (meth) acrylate and trimethylolpropane diacrylate.
  • Examples of the alkylene glycol di (meth) acrylate include tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), tricyclodecanedimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and the like.
  • 1,9-Nonandiol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), ethylene glycol dimethacrylate , 1,10-decanediol diacrylate and neopentyl glycol di (meth) acrylate.
  • the polyalkylene glycol di (meth) acrylate include polyethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate and polypropylene glycol di (meth) acrylate.
  • Examples of the urethane di (meth) acrylate include propylene oxide-modified urethane di (meth) acrylate and ethylene oxide and propylene oxide-modified urethane di (meth) acrylate.
  • Examples of commercially available products include 8UX-015A (manufactured by Taisei Fine Chemical Industry Co., Ltd.), UA-32P (manufactured by Shin Nakamura Chemical Industry Co., Ltd.) and UA-1100H (manufactured by Shin Nakamura Chemical Industry Co., Ltd.).
  • Examples of the trifunctional or higher functional ethylenically unsaturated compound include dipentaerythritol (tri / tetra / penta / hexa) (meth) acrylate, pentaerythritol (tri / tetra) (meth) acrylate, and trimethylolpropane tri (meth).
  • Examples thereof include acrylates, trimethylolpropane tetra (meth) acrylates, trimethylolethanetri (meth) acrylates, isocyanuric acid tri (meth) acrylates, glycerintri (meth) acrylates and alkylene oxide modified products thereof.
  • (tri / tetra / penta / hexa) (meth) acrylate) is a concept including 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.
  • alkylene oxide-modified product of the trifunctional or higher ethylenically unsaturated compound examples include caprolactone-modified (meth) acrylate compound (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd. and A-9300 manufactured by Shin-Nakamura Chemical Industry Co., Ltd.). -1CL, etc.), alkylene oxide-modified (meth) acrylate compound (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Industry Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel Ornex Co., Ltd., etc.
  • Ethanolylated glycerin triacrylate (A-GLY-9E manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), Aronix (registered trademark) TO-2349 (manufactured by Toa Synthetic Co., Ltd.), Aronix M-520 (manufactured by Toa Synthetic Co., Ltd.) and Aronix M. -510 (manufactured by Toa Synthetic Co., Ltd.) can be mentioned.
  • the polymerizable compound may be a polymerizable compound having an acid group (carboxy group or the like).
  • the acid group may form an acid anhydride group.
  • examples of the polymerizable compound having an acid group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei), Aronix (registered trademark) M-520 (manufactured by Toagosei) and Aronix (registered trademark) M-510. (Manufactured by Toagosei Co., Ltd.) can be mentioned.
  • Examples of the polymerizable compound having an acid group include the polymerizable compounds having an acid group described in paragraphs [0025] to [0030] of JP-A-2004-239942.
  • the molecular weight (weight average molecular weight when having a molecular weight distribution) of the polymerizable compound (including the polymerizable compound B1) is preferably 200 to 3,000, more preferably 280 to 2,200, and preferably 300 to 2,200. More preferred.
  • the polymerizable compound may be used alone or in combination of two or more.
  • the content of the polymerizable compound is preferably 10 to 70% by mass, more preferably 15 to 70% by mass, still more preferably 20 to 70% by mass, based on the total mass of the photosensitive composition layer.
  • the mass ratio of the content of the bifunctional or higher polymerizable compound to the resin content is 0.10 because the effect of the present invention is more excellent. It is preferably ⁇ 1.00, more preferably 0.50 to 1.00, further preferably 0.60 to 1.00, and particularly preferably 0.60 to 0.80.
  • the photosensitive composition layer preferably contains the above-mentioned polymerizable compound B1 and a trifunctional or higher ethylenically unsaturated compound, and the above-mentioned polymerizable compound B1 and two or more trifunctional or higher functional ethylenically unsaturated compounds. It is more preferable to include it.
  • the mass ratio of the mass of the polymerizable compound B1 to the mass of the trifunctional or higher functional ethylenically unsaturated compound is preferably 1.0 to 5.0, more preferably 1.2 to 4.0, and 1.5 to 3. 0 is more preferred.
  • the photosensitive composition layer preferably contains the above-mentioned polymerizable compound B1 and a trifunctional ethylenically unsaturated compound.
  • the photosensitive composition layer also preferably contains a polymerization initiator.
  • the polymerization initiator is selected according to the type of the polymerization reaction, and examples thereof include a thermal polymerization initiator and a photopolymerization initiator.
  • the polymerization initiator may be a radical polymerization initiator or a cationic polymerization initiator.
  • the photosensitive composition layer preferably contains a photopolymerization initiator.
  • the photopolymerization initiator is a compound that initiates the polymerization of a polymerizable compound by receiving active rays such as ultraviolet rays, visible rays and X-rays.
  • the photopolymerization initiator is not particularly limited, but a known photopolymerization initiator can be used. Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator, and a photoradical polymerization initiator is preferable.
  • Examples of the photoradical polymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an ⁇ -aminoalkylphenone structure, a photopolymerization initiator having an ⁇ -hydroxyalkylphenone structure, and an acylphosphine oxide. Examples thereof include a photopolymerization initiator having a structure and a photopolymerization initiator having an N-phenylglycine structure.
  • the photosensitive composition layer contains a 2,4,5-triarylimidazole dimer as a photoradical polymerization initiator and a dimer thereof from the viewpoint of photosensitive, visibility and resolution of exposed and unexposed areas. It preferably contains at least one selected from the group consisting of derivatives.
  • the two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and its derivatives may be the same or different.
  • Derivatives of the 2,4,5-triarylimidazole dimer include, for example, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di.
  • photoradical polymerization initiator examples include the polymerization initiators described in paragraphs [0031] to [0042] of JP-A-2011-095716 and paragraphs [0064] to [0081] of JP-A-2015-014783. Can be mentioned.
  • photoradical polymerization initiator examples include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p, p'-dimethoxybenzyl), and TAZ-110 (trade name:).
  • Oxime ester-based photopolymerization initiator (trade name: Lunar 6, manufactured by DKSH Japan), 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbisimidazole (2- (2-Chlorophenyl) -4,5-diphenylimidazole dimer) (trade name: B-CIM, manufactured by Hampton), 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer (trade name: B-CIM, manufactured by Hampton) Product Name: BCTB, manufactured by Tokyo Kasei Kogyo Co., Ltd.), 1- [4- (Phenylthio) Phenyl] -3-cyclopentylpropane-1,2-dione-2- (O-benzoyloxime) (Product name: TR-PBG- 305, manufactured by Changzhou Strong Electronics New Materials Co., Ltd.), 1,2-Prodanion, 3-cyclohexyl-1- [9-
  • the photocationic polymerization initiator is a compound that generates an acid by receiving active light rays.
  • a compound that is sensitive to active light having a wavelength of 300 nm or more preferably a wavelength of 300 to 450 nm
  • a photocationic polymerization initiator that is not directly sensitive to active light with a wavelength of 300 nm or more is also a sensitizer if it is a compound that is sensitive to active light with a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. Can be preferably used in combination with.
  • a photocationic polymerization initiator that generates an acid having a pKa of 4 or less is preferable, a photocationic polymerization initiator that generates an acid having a pKa of 3 or less is more preferable, and an acid having a pKa of 2 or less is used.
  • the generated photocationic polymerization initiator is particularly preferred.
  • the lower limit of pKa is not particularly specified, but -10.0 or more is preferable.
  • Examples of the photocationic polymerization initiator include an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator.
  • Examples of the ionic photocationic polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.
  • Examples of the ionic photocationic polymerization initiator include the ionic photocationic polymerization initiator described in paragraphs [0114] to [0133] of JP-A-2014-085643.
  • nonionic photocationic polymerization initiator examples include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds and oxime sulfonate compounds.
  • examples of the trichloromethyl-s-triazines, diazomethane compounds and imide sulfonate compounds include the compounds described in paragraphs [0083] to [0088] of JP2011-22149A.
  • examples of the oxime sulfonate compound examples include the compounds described in paragraphs [0084] to [0088] of International Publication No. 2018/179640.
  • the polymerization initiator may be used alone or in combination of two or more.
  • the content of the polymerization initiator (preferably photopolymerization initiator) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total mass of the photosensitive composition layer.
  • the upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, based on the total mass of the photosensitive composition layer.
  • the photosensitive composition layer has a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 to 780 nm at the time of color development from the viewpoint of visibility of exposed and unexposed areas, and pattern visibility and resolution after development.
  • a dye also referred to as "dye N"
  • the detailed mechanism is unknown, but the adhesion to the adjacent layer (for example, a water-soluble resin layer) is improved and the resolution is excellent.
  • the term "the maximum absorption wavelength is changed by an acid, a base or a radical” means that the dye in a color-developing state is decolorized by an acid, a base or a radical, and the dye in a decolorized state is an acid. It may mean any aspect of a mode in which a color is developed by a base or a radical and a mode in which a dye in a color-developing state changes to a color-developing state of another hue.
  • the dye N may be a compound that changes its color from the decolorized state by exposure and may be a compound that changes its color from the decolorized state by exposure.
  • the dye may be a dye whose color development or decolorization state is changed by the acid, base or radical generated and acted on in the photosensitive composition layer by exposure, and the photosensitive composition may be changed by the acid, base or radical. It may be a dye whose color development or decolorization state changes by changing the state in the layer (for example, pH). Further, it may be a dye whose color development or decolorization state changes by directly receiving an acid, a base or a radical as a stimulus without going through exposure.
  • the dye N is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by a radical, from the viewpoint of visibility and resolution of the exposed part and the non-exposed part. ..
  • the photosensitive composition layer is a photosensitive composition layer
  • the maximum absorption wavelength of the photosensitive composition layer is changed by radicals as the dye N from the viewpoint of visibility and resolution of the exposed portion and the non-exposed portion. It preferably contains both a dye and a photoradical polymerization initiator.
  • the dye N is preferably a dye that develops color by an acid, a base or a radical.
  • a coloring mechanism of the dye N for example, a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator) or a photobase generator is added to the photosensitive composition layer, and a photoradical polymerization initiator is added after exposure.
  • a radical-reactive dye, an acid-reactive dye or a base-reactive dye for example, a leuco dye
  • a radical-reactive dye, an acid-reactive dye or a base-reactive dye for example, a leuco dye
  • the maximum absorption wavelength in the wavelength range of 400 to 780 nm at the time of color development of the dye N is preferably 550 nm or more, more preferably 550 to 700 nm, and further preferably 550 to 650 nm.
  • the dye N may have only one maximum absorption wavelength in the wavelength range of 400 to 780 nm at the time of color development, or may have two or more.
  • the maximum absorption wavelength having the highest absorbance among the two or more maximum absorption wavelengths may be 450 nm or more.
  • the transmission spectrum of the solution containing the dye N (liquid temperature 25 ° C.) is measured in the range of 400 to 780 nm using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) in an atmospheric atmosphere. However, it can be measured by detecting the wavelength at which the light intensity becomes the minimum (maximum absorption wavelength).
  • Examples of the dye that develops or decolorizes by exposure include leuco compounds.
  • Examples of the dye to be decolorized by exposure include leuco compounds, diarylmethane dyes, oxadin dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes and anthraquinone dyes.
  • As the dye N a leuco compound is preferable from the viewpoint of visibility of the exposed portion and the non-exposed portion.
  • the leuco compound examples include a leuco compound having a triarylmethane skeleton (triarylmethane dye), a leuco compound having a spiropyran skeleton (spiropylan dye), a leuco compound having a fluorane skeleton (fluorane dye), and a diarylmethane skeleton.
  • Leuco compound having a leuco compound diarylmethane dye
  • leuco compound having a rhodamine lactam skeleton leuco compound having an indrill phthalide skeleton (indrill phthalide dye)
  • leuco having a leuco auramine skeleton examples include a leuco compound having a triarylmethane skeleton (triarylmethane dye), a leuco compound having a spiropyran skeleton (spiropylan dye), a leuco compound having a fluorane skeleton (fluorane dye), and
  • Examples thereof include compounds (leukooramine-based dyes). Of these, triarylmethane-based dyes or fluorane-based dyes are preferable, and leuco compounds (triphenylmethane-based dyes) or fluorane-based dyes having a triphenylmethane skeleton are more preferable.
  • the leuco compound preferably has a lactone ring, a surujin ring, or a sultone ring from the viewpoint of visibility of the exposed portion and the non-exposed portion.
  • the lactone ring, sultin ring, or sulton ring of the leuco compound is reacted with the radical generated from the photoradical polymerization initiator or the acid generated from the photocationic polymerization initiator to change the leuco compound into a closed ring state.
  • the color can be decolorized or the leuco compound can be changed to a ring-opened state to develop a color.
  • the leuco compound has a lactone ring, a sultone ring or a sultone ring, and a compound in which the lactone ring, the sultone ring or the sultone ring is opened by a radical or an acid to develop a color is preferable, and the lactone ring has a radical or an acid.
  • a compound in which the lactone ring is opened and the color is developed is more preferable.
  • Examples of the dye N include dyes and leuco compounds.
  • Dyes include, for example, Brilliant Green, Ethyl Violet, Methyl Green, Crystal Violet, Basic Fuxin, Methyl Violet 2B, Kinaldine Red, Rose Bengal, Metanil Yellow, Timor Sulfophthalene, Xylenol Blue, Methyl Orange, Paramethyl Red.
  • leuco compounds examples include p, p', p''-hexamethyltriaminotriphenylmethane (leucocrystal violet), Pergascript Blue SRB (manufactured by Ciba Geigy), crystal violet lactone, malakite green lactone, and benzoyl leucomethylene blue.
  • Dye N is preferably a dye whose maximum absorption wavelength is changed by radicals, and is a dye that develops color by radicals, because it is excellent in visibility of exposed and unexposed areas, pattern visibility after development, and resolution. It is more preferable to have.
  • As the dye N leuco crystal violet, crystal violet lactone, brilliant green or Victoria pure blue-naphthalene sulfonate are preferable.
  • the dye N may be used alone or in combination of two or more.
  • the content of the dye N is 0.1% by mass or more with respect to the total mass of the photosensitive composition layer from the viewpoint of excellent visibility of the exposed portion and the non-exposed portion, pattern visibility after development, and resolution. Is preferable, 0.1 to 10% by mass is more preferable, 0.1 to 5% by mass is further preferable, and 0.1 to 1% by mass is particularly preferable.
  • the content of the dye N means the content of the dye when all of the dye N contained in the total mass of the photosensitive composition layer is in a colored state.
  • a method for quantifying the content of dye N will be described by taking a dye that develops color by radicals as an example.
  • a solution in which 0.001 g of the dye N is dissolved and a solution in which 0.01 g of the dye are dissolved are prepared in 100 mL of methyl ethyl ketone.
  • a photoradical polymerization initiator (Irgacure OXE01, manufactured by BASF Japan, Inc.) is added to each of the obtained solutions, and radicals are generated by irradiating with light having a wavelength of 365 nm to bring all the dyes N into a colored state. Then, in an atmospheric atmosphere, the absorbance of each solution having a liquid temperature of 25 ° C. is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), and a calibration curve is prepared. Next, the absorbance of the solution in which all the dyes are colored is measured by the same method as above except that 3 g of the photosensitive composition layer is dissolved in methyl ethyl ketone instead of the dye N.
  • the photosensitive composition layer of 3 g is the same as the total solid content of 3 g in the photosensitive resin composition.
  • the photosensitive composition layer may contain a heat-crosslinkable compound in terms of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.
  • the heat-crosslinkable compound having an ethylenically unsaturated group which will be described later, is not treated as a polymerizable compound, but is treated as a heat-crosslinkable compound.
  • the heat-crosslinkable compound include a methylol compound and a blocked isocyanate compound. Of these, a blocked isocyanate compound is preferable from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.
  • the blocked isocyanate compound reacts with a hydroxy group and a carboxy group, for example, when a resin and / or a polymerizable compound has at least one of a hydroxy group and a carboxy group, the hydrophilicity of the formed film is lowered and the film is photosensitive. When a film obtained by curing the sex composition layer is used as a protective film, the function tends to be enhanced.
  • the blocked isocyanate compound means "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 preferably 100 to 160 ° C, more preferably 130 to 150 ° C.
  • the dissociation temperature of the blocked isocyanate means "the temperature of the heat absorption 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 Co., Ltd. can be preferably used.
  • the differential scanning calorimeter is not limited to this.
  • the blocking agent having a dissociation temperature of 100 to 160 ° C. examples include an active methylene compound (malonic acid diester (for example, dimethyl malonate, diethyl malonate, din-butyl malonate, di2-ethylhexyl malonic acid, etc.)).
  • malonic acid diester for example, dimethyl malonate, diethyl malonate, din-butyl malonate, di2-ethylhexyl malonic acid, etc.
  • the blocking agent having a dissociation temperature of 100 to 160 ° C. for example, at least one selected from oxime compounds is preferable from the viewpoint of storage stability.
  • the blocked isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoint of improving the brittleness of the membrane and improving the adhesion to the transferred material.
  • the blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by subjecting hexamethylene diisocyanate to isocyanurate to protect it.
  • the oxime compound was used as the blocking agent as the blocked isocyanate compound having an isocyanurate structure from the viewpoint that the dissociation temperature can be easily set in a preferable range and the development residue can be easily reduced as compared with the compound having no oxime structure.
  • Compounds having an oxime structure are preferred.
  • the blocked isocyanate compound may have a polymerizable group.
  • the polymerizable group is not particularly limited, and a known polymerizable group can be used, and a radically polymerizable group is preferable.
  • the polymerizable group include an ethylenically unsaturated group such as a (meth) acryloxy group, a (meth) acrylamide group and a styryl group, and a group having an epoxy group such as a glycidyl group.
  • an ethylenically unsaturated group is preferable, a (meth) acryloxy group is more preferable, and an acryloxy group is further preferable.
  • Examples of the blocked isocyanate compound include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP (all manufactured by Showa Denko KK), and a block type duranate series. (For example, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc. and Asahi Kasei Chemicals Co., Ltd.) can be mentioned. Examples of the blocked isocyanate compound include compounds having the following structures.
  • the heat-crosslinkable compound may be used alone or in combination of two or more.
  • the content of the heat-crosslinkable compound is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, based on the total mass of the photosensitive composition layer. preferable.
  • the photosensitive composition layer may be a colored resin layer containing a pigment.
  • liquid crystal display windows of electronic devices may be provided with a cover glass having a black frame-shaped light-shielding layer formed on the peripheral edge of the back surface of a transparent glass substrate or the like in order to protect the liquid crystal display window.
  • a colored resin layer can be used to form such a light-shielding layer.
  • the pigment may be appropriately selected according to the desired hue, and can be selected from black pigments, white pigments, and chromatic pigments other than black and white. Among them, when forming a black pattern, a black pigment is preferably selected as the pigment.
  • Black pigment As the black pigment, known black pigments (organic pigments, inorganic pigments, etc.) can be appropriately selected as long as the effects of the present invention are not impaired. Among them, carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide or graphite are preferable, and carbon black is more preferable as the black pigment from the viewpoint of optical density. As the carbon black, carbon black having at least a part of the surface coated with a resin is preferable from the viewpoint of surface resistance.
  • the particle size (number average particle size) of the black pigment is preferably 0.001 to 0.1 ⁇ m, more preferably 0.01 to 0.08 ⁇ m from the viewpoint of dispersion stability.
  • the particle size refers to the diameter of the circle when the area of the pigment particles is obtained from the photographic image of the pigment particles taken with an electronic microscope and the circle having the same area as the area of the pigment particles is considered, and the number average particle size is ,
  • the above particle size is obtained for any 100 particles, and is an average value obtained by averaging the obtained 100 particle sizes.
  • the white pigment examples include inorganic pigments and white pigments described in paragraphs [0015] and [0114] of JP-A-2005-007765.
  • the inorganic pigment titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide or barium sulfate are preferable, titanium oxide or zinc oxide is more preferable, titanium oxide is further preferable, and rutyl type or Anatase-type titanium oxide is particularly preferable, and rutile-type titanium oxide is most preferable.
  • the surface of titanium oxide may be subjected to silica treatment, alumina treatment, titania treatment, zirconia treatment or organic substance treatment, or may be subjected to two or more treatments.
  • the catalytic activity of titanium oxide is suppressed, and heat resistance and fading are improved.
  • the photosensitive composition layer When the photosensitive composition layer is a colored resin layer, the photosensitive composition layer preferably contains a chromatic pigment other than the black pigment and the white pigment from the viewpoint of transferability.
  • a chromatic pigment When a chromatic pigment is contained, the particle size of the chromatic pigment is preferably 0.1 ⁇ m or less, more preferably 0.08 ⁇ m or less, in that the dispersibility is more excellent. The lower limit is preferably 10 nm or more.
  • chromatic pigments include Victoria Pure Blue BO (Color Index (hereinafter CI) 42595), Auramine (CI41000), Fat Black HB (CI26150), and Monolite.
  • the pigment may be used alone or in combination of two or more.
  • the content of the pigment is preferably more than 3% by mass and 40% by mass or less, preferably more than 3% by mass and 35% by mass or less, based on the total mass of the photosensitive composition layer. More preferably, it is more preferably more than 5% by mass and 35% by mass or less, and particularly preferably 10 to 35% by mass.
  • the content of the pigment other than the black pigment is preferably 30% by mass or less with respect to the total mass of the black pigment. 1 to 20% by mass is more preferable, and 3 to 15% by mass is further preferable.
  • the black pigment (preferably carbon black) is preferably introduced into the photosensitive composition in the form of a pigment dispersion.
  • the dispersion liquid may be prepared by adding a mixture obtained by premixing a black pigment and a pigment dispersant to an organic solvent (or vehicle) and dispersing it with a disperser.
  • the pigment dispersant may be selected depending on the pigment and the solvent, and for example, a commercially available dispersant can be used.
  • the vehicle refers to the portion of the medium in which the pigment is dispersed when the pigment is dispersed, and is a liquid, a binder component that holds the black pigment in a dispersed state, and a solvent component that dissolves and dilutes the binder component. (Organic solvent) and included.
  • disperser examples include known dispersers such as a kneader, a roll mill, an attritor, a super mill, a dissolver, a homomixer, and a sand mill. Further, it may be finely pulverized by mechanical grinding using frictional force. Examples of the disperser and fine pulverization include the description of "Encyclopedia of Pigments" (Kunizo Asakura, First Edition, Asakura Shoten, 2000, 438, 310).
  • the photosensitive composition layer may contain known additives (other additives), if necessary.
  • additives include radical polymerization inhibitors, benzotriazoles, carboxybenzotriazoles, sensitizers, surfactants, plasticizers, heterocyclic compounds (triazole, etc.), pyridines (isonicotinamide, etc.) and Examples include purine bases (adenin and the like).
  • Other additives include metal oxide particles, antioxidants, dispersants, acid growth agents, development accelerators, conductive fibers, UV absorbers, thickeners, cross-linking agents and organic or inorganic precipitation inhibitors. , Japanese Patent Laid-Open No. 2014-085643 [0165] to [0184], and the contents thereof are incorporated in the present specification. Other additives may be used alone or in combination of two or more.
  • radical polymerization inhibitor examples include the thermal polymerization inhibitor described in paragraph [0018] of Japanese Patent No. 4502784, and phenothiazine, phenoxazine or 4-methoxyphenol are preferable.
  • examples of the radical polymerization inhibitor include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt and diphenylnitrosamine. Of these, the nitrosophenylhydroxylamine aluminum salt is preferable because it does not impair the sensitivity of the photosensitive composition layer.
  • the radical polymerization inhibitor may be used alone or in combination of two or more.
  • the content of the radical polymerization inhibitor is preferably 0.001 to 5.0% by mass, preferably 0.01, based on the total mass of the photosensitive composition layer. -3.0% by mass is more preferable, and 0.02 to 2.0% by mass is further preferable.
  • the content of the radical polymerization inhibitor is preferably 0.005 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, and 0.01 to 1. 0% by mass is more preferable.
  • benzotriazoles examples include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, and the like. Examples thereof include bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole and bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole.
  • carboxybenzotriazoles examples include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and N- (N, N-di-2-ethylhexyl) aminomethylene. Examples thereof include carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole and N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole. Specific examples of the carboxybenzotriazoles include CBT-1 (Johoku Chemical Industry Co., Ltd., trade name).
  • the total content of the radical polymerization inhibitor, benzotriazols and carboxybenzotriazols is preferably 0.01 to 3% by mass, preferably 0.05 to 1% by mass, based on the total mass of the photosensitive composition layer. More preferably by mass.
  • the content is 0.01% by mass or more, the storage stability of the photosensitive composition layer is more excellent.
  • the content is 3% by mass or less, the maintenance of sensitivity and the suppression of dye decolorization are more excellent.
  • sensitizer examples include known sensitizers, dyes and pigments. Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, and triazole compounds (for example). 1,2,4-triazole), stylben compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds and aminoacridin compounds.
  • the content of the sensitizer is the entire photosensitive composition layer from the viewpoint of improving the sensitivity to a light source and improving the curing rate due to the balance between the polymerization rate and the chain transfer.
  • the mass 0.01 to 5% by mass is preferable, and 0.05 to 1% by mass is more preferable.
  • surfactant examples include the surfactants described in paragraph [0017] of Japanese Patent No. 4502784 and paragraphs [0060] to [0071] of JP-A-2009-237362.
  • a nonionic surfactant a fluorine-based surfactant or a silicone-based surfactant is preferable.
  • the fluorine-based surfactant include Megafuck F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, and 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, EXP.
  • MFS-578 EXP. MFS-578-2, EXP. MFS-579, EXP. MFS-586, EXP. MFS-587, EXP. MFS-628, EXP. MFS-631, EXP.
  • the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and when heat is applied, a portion of the functional group containing a fluorine atom is cut off and the fluorine atom volatilizes. Is also preferable.
  • fluorine-based surfactant include Megafuck DS series manufactured by DIC (The Chemical Daily (February 22, 2016) and Nikkei Sangyo Shimbun (February 23, 2016)).
  • the fluorine-based surfactant 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 the fluorine-based surfactant.
  • 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 is also preferable.
  • fluorine-based surfactant for example, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used, and Megafuck RS-101, RS-102, RS-718K and RS-72- K (above, manufactured by DIC Corporation) can be mentioned.
  • PFOA perfluorooctanoic acid
  • PFOS perfluorooctanesulfonic acid
  • nonionic surfactant examples include glycerol, trimethylolpropane, trimethylolethane, their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, and 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 and 25R2 (above, BASF); Tetronic 304, 701, 704, 901, 904 and 150R1, HYDROPALAT WE 3323 (above, BASF); Solspers 20000 (above, Nippon Lubrizol); NCW -101, NCW-1001 and NCW-1002 (above, manufactured by Fujifilm Wako Junyaku Co., Ltd.); Pionin D-1105, D-6112, D-6112-W and D-6315 (above, manufactured by Takemoto Oil & Fat Co., Ltd.); Orfin Examples thereof include E1010, Surfinol 104, 400 and 440 (all manufactured by
  • silicone-based surfactant examples include a linear polymer composed of a siloxane bond and a modified siloxane polymer having an organic group introduced at the side chain and / or the terminal.
  • silicone-based surfactant examples include EXP. S-309-2, EXP. S-315, EXP. S-503-2, EXP. S-505-2 (all manufactured by DIC Co., Ltd.), DOWSIL 8032 ADDITIVE, Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA and Torre Silicone SH8400 ( (Manufactured by Toray Dow Corning); 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 and KF-6002, KP-101, KP-103, KP-104, KP-105, KP-
  • the content of the surfactant is preferably 0.01 to 3.0% by mass, preferably 0.01 to 1% by mass, based on the total mass of the photosensitive composition layer. 0.0% by mass is more preferable, and 0.05 to 0.8% by mass is further preferable.
  • plasticizer and the heterocyclic compound examples include the compounds described in paragraphs [097] to [0103] and paragraphs [0111] to [0118] of International Publication No. 2018/179640.
  • the photosensitive composition layer may contain impurities.
  • impurities include metal impurities or ions thereof, halide ions, residual organic solvents, residual monomers and water.
  • Metal impurities and halide ions examples include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin and their ions, and halide ions. Among them, sodium ion, potassium ion, and halide ion are easily mixed, and therefore, the content is preferably as follows.
  • the metal impurity is a compound different from the above particles (for example, metal oxide).
  • the content of metal impurities is preferably 80% by mass or less, more preferably 10% by mass or less, still more preferably 2% by mass or less, based on the total mass of the photosensitive composition layer.
  • the lower limit is not particularly limited, but 1 mass ppb or more is preferable, and 0.1 mass ppm or more is more preferable with respect to the total mass of the photosensitive composition layer.
  • a method for adjusting the content of impurities for example, a method of selecting a raw material having a low impurity content as a raw material of the photosensitive composition layer, a method of preventing impurities from being mixed during the formation of the photosensitive composition layer, and cleaning. There is a method of removing it.
  • the content of impurities can be quantified by known methods such as ICP emission spectroscopy, atomic absorption spectroscopy and ion chromatography.
  • residual organic solvent examples include benzene, formaldehyde, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N, N-dimethylformamide, N, N-dimethylacetamide and hexane.
  • the content of the residual organic solvent is preferably 100 mass ppm or less, more preferably 20 mass ppm or less, still more preferably 4 mass ppm or less, based on the total mass of the photosensitive composition layer.
  • the lower limit is not particularly limited, but 10 mass ppb or more is preferable, and 100 mass ppb or more is more preferable.
  • the content of the residual organic solvent can be adjusted by the same method as the above-mentioned metal impurities. Further, the content of the residual organic solvent can be quantified by a known method such as gas chromatography analysis.
  • the photosensitive composition layer may contain residual monomers of each structural unit of the resin described above.
  • the content of the residual monomer is preferably 5000 mass ppm or less, more preferably 2000 mass ppm or less, still more preferably 500 mass ppm or less, based on the total mass of the resin.
  • the lower limit is not particularly limited, but 1 mass ppm or more is preferable, and 10 mass ppm or more is more preferable with respect to the total mass of the resin.
  • the residual monomer of each structural unit of the alkali-soluble resin is preferably 3000 mass ppm or less, more preferably 600 mass ppm or less, and more preferably 100 mass by mass, based on the total mass of the photosensitive composition layer from the viewpoint of patterning property and reliability. It is more preferably ppm or less.
  • the lower limit is not particularly limited, but is preferably 0.1 mass ppm or more, and more preferably 1 mass ppm or more, with respect to the total mass of the photosensitive composition layer.
  • the amount of residual monomer of the monomer when synthesizing the alkali-soluble resin by the polymer reaction is also preferably in the above range.
  • the content of glycidyl acrylate is preferably in the above range.
  • the amount of the residual monomer can be measured by a known method such as liquid chromatography and gas chromatography.
  • the water content in the photosensitive composition 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 laminating property.
  • the thickness (thickness) of the photosensitive composition layer is often 0.1 to 300 ⁇ m, preferably 0.2 to 100 ⁇ m, more preferably 0.5 to 50 ⁇ m, and even more preferably 0.5 to 30 ⁇ m. 1 to 20 ⁇ m is particularly preferable. As a result, the developability of the photosensitive composition layer can be improved, and the resolution can be improved.
  • the content of the double bond in the photosensitive composition layer is preferably 0.8 to 3.0 mmol / g, more preferably 1.0 to 3.0 mmol / g, and more preferably 1.2 to 2.0 mmol / g. More preferred.
  • the acid value of the photosensitive composition layer is preferably 10 to 150 mgKOH / g, more preferably 40 to 100 mgKOH / g, further preferably 50 to 100 mgKOH / g, particularly preferably 50 to 90 mgKOH / g, and more preferably to suppress the development residue. From the viewpoint of superiority, 60 to 90 mgKOH / g is most preferable.
  • the method for measuring the acid value include a method for measuring the acid value in the above-mentioned resin and a method for calculating the acid value from the content of the resin whose acid value is known.
  • the transfer film of the present invention has an intermediate layer.
  • the intermediate layer include a water-soluble resin layer and an oxygen blocking layer having an oxygen blocking function described as a “separation layer” in JP-A-5-07724.
  • an oxygen blocking layer is preferable because the sensitivity at the time of exposure is improved, the time load of the exposure machine is reduced, and the productivity is improved.
  • the oxygen blocking layer can be appropriately selected from known layers described in the publications and the like. Of these, an oxygen blocking layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (1% by mass aqueous solution of sodium carbonate at 22 ° C.) is preferable.
  • an oxygen blocking layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (1% by mass aqueous solution of sodium carbonate at 22 ° C.) is preferable.
  • each component that can be contained in the water-soluble resin layer (intermediate layer) will be
  • the intermediate layer preferably contains a water-soluble resin.
  • the water-soluble resin include polyvinyl alcohol-based resin, polyvinylpyrrolidone-based resin, cellulose-based resin, polyether-based resin, gelatin and polyamide resin.
  • Examples of the cellulosic resin include water-soluble cellulose derivatives.
  • Examples of the water-soluble cellulose derivative include hydroxyethyl cellulose, hydroxypropylmethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, methyl cellulose and ethyl cellulose.
  • polyether resin examples include polyethylene glycol, polypropylene glycol and alkylene oxyside adducts thereof, and vinyl ether resin.
  • polyamide-based resin examples include acrylamide-based resins, vinylamide-based resins, and allylamide-based resins. Among them, as the water-soluble resin, a water-soluble cellulose derivative or a polyamide-based resin is preferable.
  • examples of the water-soluble resin include a (meth) acrylic acid / vinyl compound copolymer.
  • a copolymer of (meth) acrylic acid / vinyl compound a copolymer of (meth) acrylic acid / allyl (meth) acrylic acid is preferable, and a copolymer of methacrylic acid / allyl methacrylate is more preferable.
  • the composition ratio (mol%) is preferably 90/10 to 20/80, more preferably 80/20 to 30/70. ..
  • the weight average molecular weight (Mw) of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, still more preferably 10,000 or more.
  • the upper limit is preferably 200,000 or less, more preferably 100,000 or less, still more preferably 50,000 or less.
  • the dispersity (Mw / Mn) of the water-soluble resin is preferably 1 to 10, more preferably 1 to 5.
  • the water-soluble resin may be used alone or in combination of two or more.
  • the content of the water-soluble resin is preferably 50% by mass or more, more preferably 70% by mass or more, based on the total mass of the intermediate layer, because the effect of the present invention is more excellent and / or the oxygen blocking ability is more excellent.
  • the upper limit is preferably 100% by mass or less, more preferably 99.9% by mass or less, further preferably 99.8% by mass or less, and particularly preferably 99% by mass or less.
  • the intermediate layer may contain other components in addition to the above resin.
  • the molecular weight of the other components is preferably less than 5,000, more preferably 4,000 or less, further preferably 3,000 or less, particularly preferably 2,000 or less, and most preferably 1,500 or less.
  • the lower limit is preferably 60 or more.
  • polyhydric alcohols As other components, polyhydric alcohols, alkylene oxide adducts of polyhydric alcohols, phenol derivatives or amide compounds are preferable, and polyhydric alcohols or phenol derivatives are more preferable.
  • polyhydric alcohols examples include glycerin, diglycerin and diethylene glycol.
  • the number of hydroxyl groups contained in the polyhydric alcohols is preferably 2 to 10.
  • alkylene oxide adduct of the polyhydric alcohol examples include the above-mentioned compounds in which ethylene oxide, propylene oxide and the like are added to the polyhydric alcohols.
  • the average number of additions is preferably 1 to 100, preferably 2 to 50, and more preferably 2 to 20.
  • the phenol derivative examples include bisphenol A and bisphenol S.
  • the amide compound include N-methylpyrrolidone.
  • the intermediate layer preferably contains at least one selected from the group consisting of polyhydric alcohols, oxide adducts of polyhydric alcohols, phenol derivatives, water-soluble cellulose derivatives, polyether resins and polyamide resins.
  • the thickness of the intermediate layer is preferably 3.0 ⁇ m or less, more preferably 2.0 ⁇ m or less.
  • the lower limit is preferably 1.0 ⁇ m or more.
  • the other components may be used alone or in combination of two or more.
  • the content of the other components is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, based on the total mass of the intermediate layer.
  • the upper limit is preferably less than 30% by mass, more preferably 10% by mass or less, still more preferably 5% by mass or less.
  • the transfer film of the present invention may have a thermoplastic resin layer.
  • the thermoplastic resin layer is usually arranged between the temporary support and the photosensitive composition layer.
  • the followability to the substrate in the bonding process between the transfer film and the substrate is improved, and the mixing of air bubbles between the substrate and the transfer film can be suppressed.
  • the adhesion to the layer adjacent to the thermoplastic resin layer for example, a temporary support
  • examples of the thermoplastic resin layer include paragraphs [0189] to [0193] of JP-A-2014-085643, the contents of which are incorporated in the present specification.
  • the thickness (layer thickness) of the thermoplastic resin layer is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, from the viewpoint of adhesion to the adjacent layer.
  • the upper limit is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, still more preferably 8 ⁇ m or less, from the viewpoint of developability and resolvability.
  • the thermoplastic resin layer preferably contains a thermoplastic resin.
  • a thermoplastic resin an alkali-soluble resin is preferable.
  • the alkali-soluble resin include acrylic resin, polystyrene resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyamide resin, epoxy resin, polyacetal resin, and polyhydroxystyrene resin.
  • Polychloride resin polybenzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine and polyalkylene glycol.
  • an acrylic resin is preferable from the viewpoint of developability and adhesion to an adjacent layer.
  • the acrylic resin is selected from the group consisting of a structural unit derived from (meth) acrylic acid, a structural unit derived from (meth) acrylic acid ester, and a structural unit derived from (meth) acrylic acid amide.
  • the total content of the structural unit derived from (meth) acrylic acid, the structural unit derived from (meth) acrylic acid ester, and the structural unit derived from (meth) acrylic acid amide is the total mass of the acrylic resin. On the other hand, 50% by mass or more is preferable.
  • the upper limit is preferably 100% by mass or less with respect to the total mass of the acrylic resin.
  • the total content of the structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic acid ester is preferably 30 to 100% by mass, preferably 50 to 100% by mass, based on the total mass of the acrylic resin. 100% by mass is more preferable.
  • the alkali-soluble resin a polymer having an acid group is preferable.
  • the acid group include a carboxy group, a sulfo group, a phosphoric acid group and a phosphonic acid group, and a carboxy group is preferable.
  • the acid value of the alkali-soluble resin is preferably 60 mgKOH / g or more from the viewpoint of developability.
  • the upper limit is preferably 300 mgKOH / g or less, more preferably 250 mgKOH / g or less, further preferably 200 mgKOH / g or less, and particularly preferably 150 mgKOH / g or less.
  • an alkali-soluble resin having an acid value of 60 mgKOH / g or more is preferable, and a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more is more preferable.
  • the carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited, but can be appropriately selected from known resins and used.
  • an alkali-soluble resin which is a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more
  • paragraph [0033] of JP-A-2010-237589 Acrylic resin containing a carboxy group having an acid value of 60 mgKOH / g or more among the polymers described in [0052] and 60 mgKOH among the resins described in paragraphs [0053] to [0068] of JP-A-2016-224162.
  • Examples thereof include acrylic resins containing a carboxy group of / g or more.
  • the copolymerization ratio of the structural unit having a carboxy group in the carboxy group-containing acrylic resin is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and 12 to 30% by mass with respect to the total mass of the acrylic resin. Is more preferable.
  • an acrylic resin having a structural unit derived from (meth) acrylic acid is particularly preferable from the viewpoint of developability and adhesion to an adjacent layer.
  • the alkali-soluble resin may have a reactive group.
  • the reactive group may be any addition-polymerizable group, and an ethylenically unsaturated group; a polycondensable group such as a hydroxy group and a carboxy group; a polyaddition reactive group such as an epoxy group and a (block) isocyanate group may be used. Can be mentioned.
  • the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and even more preferably 20,000 to 50,000.
  • the alkali-soluble resin may be used alone or in combination of two or more.
  • the content of the alkali-soluble resin is preferably 10 to 99% by mass, more preferably 20 to 90% by mass, based on the total mass of the thermoplastic resin layer from the viewpoint of developability and adhesion to the adjacent layer. 40 to 80% by mass is more preferable, and 50 to 75% by mass is particularly preferable.
  • the thermoplastic resin layer is a dye having a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 to 780 nm at the time of color development, and the maximum absorption wavelength is changed by an acid, a base or a radical (hereinafter, also simply referred to as “dye B”). It is preferable to include it.
  • the preferred embodiment of the dye B is the same as the preferred embodiment of the dye N described above, except for the points described later.
  • the dye B a dye whose maximum absorption wavelength is changed by an acid or a radical is preferable, and a dye whose maximum absorption wavelength is changed by an acid is more preferable from the viewpoint of visibility and resolution of an exposed portion and a non-exposed portion.
  • the thermoplastic resin layer contains both a dye whose maximum absorption wavelength changes depending on the acid as the dye B and a compound that generates an acid by light, which will be described later, from the viewpoint of visibility and resolution of the exposed part and the non-exposed part. Is preferable.
  • the dye B may be used alone or in combination of two or more.
  • the content of the dye B is preferably 0.2% by mass or more, preferably 0.2 to 6.0% by mass, based on the total mass of the thermoplastic resin layer from the viewpoint of visibility of the exposed portion and the non-exposed portion. More preferably, 0.2 to 5.0% by mass is further preferable, and 0.25 to 3.0% by mass is particularly preferable.
  • the content of the dye B means the content of the dye when all of the dye B contained in the thermoplastic resin layer is in a colored state.
  • a method for quantifying the content of dye B will be described by taking a dye that develops color by radicals as an example.
  • a solution in which 0.001 g of dye B is dissolved and a solution in which 0.01 g of dye is dissolved are prepared in 100 mL of methyl ethyl ketone.
  • a photoradical polymerization initiator (Irgacure OXE01, manufactured by BASF Japan Ltd.) is added to each of the obtained solutions, and radicals are generated by irradiating with light having a wavelength of 365 nm to bring all the dyes B into a colored state.
  • thermoplastic resin layer (3 g) is the same as the solid content of the composition (3 g).
  • the thermoplastic resin layer may contain a compound that generates an acid, a base or a radical by light (hereinafter, also simply referred to as “compound C”).
  • compound C a compound that receives an active ray such as ultraviolet rays and visible rays to generate an acid, a base or a radical is preferable.
  • Examples of the compound C include known photoacid generators, photobase generators and photoradical polymerization initiators (photoradical generators).
  • thermoplastic resin layer may contain a photoacid generator from the viewpoint of resolution.
  • the photoacid generator include a photocationic polymerization initiator that can be contained in the above-mentioned photosensitive composition layer, and the preferred embodiments are the same except for the points described below.
  • the photoacid generator preferably contains at least one compound selected from the group consisting of onium salt compounds and oxime sulfonate compounds from the viewpoint of sensitivity and resolution, and has sensitivity, resolution and adhesion. From the point of view, it is more preferable to contain an oxime sulfonate compound. Further, as the photoacid generator, a photoacid generator having the following structure is also preferable.
  • the thermoplastic resin layer may contain a photoradical polymerization initiator.
  • the photoradical polymerization initiator include a photoradical polymerization initiator that can be contained in the above-mentioned photosensitive composition layer, and the preferred embodiments are the same.
  • the thermoplastic resin composition may contain a photobase generator.
  • the photobase generator include known photobase generators. Specifically, 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, bis [[(2-2-) Nitrobenzyl) Oxy] carbonyl] hexane 1,6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoetan, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, N- ( 2-Nitrobenzyloxycarbonyl) pyrrolidine, hexaammine cobalt (III) tris (triphenylmethylborate), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)
  • Compound C may be used alone or in combination of two or more.
  • the content of the compound C is preferably 0.1 to 10% by mass, preferably 0.5 to 5% by mass, based on the total mass of the thermoplastic resin layer from the viewpoint of visibility and resolution of the exposed and non-exposed areas. More preferably by mass.
  • the thermoplastic resin layer preferably contains a plasticizer from the viewpoints of resolution, adhesion to adjacent layers, and developability.
  • the plasticizer preferably has a smaller molecular weight (weight average molecular weight when it is an oligomer or a polymer and has a molecular weight distribution) than that of an alkali-soluble resin.
  • the molecular weight (weight average molecular weight) of the plasticizer is preferably 200 to 2,000.
  • the plasticizer is not particularly limited as long as it is a compound that is compatible with an alkali-soluble resin and exhibits plasticity, but from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule, and is a polyalkylene glycol. Compounds are more preferred. It is more preferable that the alkyleneoxy group contained in the plasticizer has a polyethyleneoxy structure or a polypropyleneoxy structure.
  • the plasticizer preferably contains a (meth) acrylate compound from the viewpoint of resolution and storage stability.
  • the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth) acrylate compound.
  • the (meth) acrylate compound used as a plasticizer include the (meth) acrylate compound described as a polymerizable compound that can be contained in the above-mentioned photosensitive composition layer.
  • both the thermoplastic resin layer and the photosensitive composition layer contain the same (meth) acrylate compound. This is because the thermoplastic resin layer and the photosensitive composition layer each contain the same (meth) acrylate compound, so that the diffusion of components between the layers is suppressed and the storage stability is improved.
  • the (meth) acrylate compound may not polymerize even in the exposed portion after exposure due to the adhesion between the thermoplastic resin layer and the adjacent layer.
  • the (meth) acrylate compound used as a plasticizer two or more (meth) acryloyl in one molecule from the viewpoint of the resolution of the thermoplastic resin layer, the adhesion to the adjacent layer, and the developability.
  • Polyfunctional (meth) acrylate compounds having a group are preferred.
  • a (meth) acrylate compound having an acid group or a urethane (meth) acrylate compound is also preferable.
  • the plasticizer may be used alone or in combination of two or more.
  • the content of the plasticizer is preferably 1 to 70% by mass with respect to the total mass of the thermoplastic resin layer from the viewpoint of the resolution of the thermoplastic resin layer, the adhesion to the adjacent layer, and the developability. -60% by mass is more preferable, and 20 to 50% by mass is further preferable.
  • the thermoplastic resin layer may contain a sensitizer.
  • the sensitizer is not particularly limited, and examples thereof include the sensitizer that can be contained in the above-mentioned photosensitive composition layer.
  • the sensitizer may be used alone or in combination of two or more.
  • the content of the sensitizer is preferably 0.01 to 5% by mass with respect to the total mass of the thermoplastic resin layer from the viewpoint of improving the sensitivity to the light source and the visibility of the exposed portion and the non-exposed portion. 05 to 1% by mass is more preferable.
  • thermoplastic resin layer may contain other additives in addition to the above components, if necessary.
  • other additives include other additives that can be contained in the above-mentioned photosensitive composition layer.
  • the thermoplastic resin layer may contain impurities.
  • the impurities include impurities that can be contained in the above-mentioned photosensitive composition layer.
  • the transfer film of the present invention may have other members in addition to the above-mentioned members.
  • Examples of other members include a protective film.
  • a resin film having heat resistance and solvent resistance can be used, and examples thereof include a polyolefin film such as a polypropylene film and a polyethylene film, a polyester film such as a polyethylene terephthalate film, a polycarbonate film, and a polystyrene film. Be done. Further, as the protective film, a resin film made of the same material as the above-mentioned temporary support may be used. Among them, as the protective film, a polyolefin film is preferable, a polypropylene film or a polyethylene film is more preferable, and a polyethylene film is further preferable.
  • the thickness of the protective film is preferably 1 to 100 ⁇ m, more preferably 5 to 50 ⁇ m, further preferably 5 to 40 ⁇ m, and particularly preferably 15 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 that it is relatively inexpensive.
  • the protective film preferably has a number of fish eyes having a diameter of 80 ⁇ m or more and 5 pieces / m 2 or less contained in the protective film.
  • Fish eye means that when a film is manufactured by heat-melting the material, kneading, extruding, biaxial stretching, casting method, etc., foreign substances, undissolved substances, oxidative deterioration substances, etc. of the material are contained in the film. Means what was captured.
  • the number of particles having 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.
  • the lower limit is preferably 0 pieces / mm 2 or more. Within these ranges, it is possible to suppress defects caused by the unevenness caused by the particles contained in the protective film being transferred to the photosensitive composition layer or the conductive layer.
  • the arithmetic mean roughness Ra of the surface of the protective film opposite to the surface in contact with the photosensitive composition layer is preferably 0.01 ⁇ m or more, more preferably 0.02 ⁇ m or more, and 0. It is more preferably 3.03 ⁇ m or more.
  • the upper limit is preferably less than 0.50 ⁇ m, more preferably 0.40 ⁇ m or less, still more preferably 0.30 ⁇ m or less.
  • the surface roughness Ra of the surface of the protective film in contact with the photosensitive composition layer is preferably 0.01 ⁇ m or more, more preferably 0.02 ⁇ m or more, still more preferably 0.03 ⁇ m or more from the viewpoint of suppressing defects during transfer.
  • the upper limit is preferably less than 0.50 ⁇ m, more preferably 0.40 ⁇ m or less, still more preferably 0.30 ⁇ m or less.
  • the method for producing the transfer film is not particularly limited, but a known method can be used.
  • a method for producing the transfer film 10 for example, a step of applying a water-soluble resin composition to the surface of the temporary support 11 to form a coating film, and further drying the coating film to form an intermediate layer 13.
  • a method including a step of applying a photosensitive composition to the surface of the intermediate layer 13 to form a coating film, and further drying the coating film to form a photosensitive composition layer 15 can be mentioned.
  • the thermoplastic resin composition is applied to the surface of the temporary support 11 to form a coating film, and the coating film is further dried to form the thermoplastic resin layer. It may include a step of performing.
  • the transfer film 10 is manufactured by crimping the protective film 19 onto the photosensitive composition layer 15 of the laminate manufactured by the above-mentioned manufacturing method.
  • the temporary support 11 and the intermediate layer are provided by including a step of providing the protective film 19 so as to be in contact with the surface of the photosensitive composition layer 15 opposite to the side having the temporary support 11. 13. It is preferable to manufacture the transfer film 10 including the photosensitive composition layer 15 and the protective film 19. Further, the method for producing the transfer film includes a step of providing the protective film 19 so as to be in contact with the surface of the photosensitive composition layer 15 opposite to the side having the temporary support 11, so that the temporary support 11 can be manufactured.
  • It may be a transfer film including a thermoplastic resin layer, an intermediate layer 13, a photosensitive composition layer 15, and a protective film 19.
  • the transfer film 10 may be wound up to prepare and store the transfer film in the form of a roll.
  • the roll-type transfer film can be provided as it is in the bonding process with the substrate in the roll-to-roll method described later.
  • the photosensitive composition layer 15 and the intermediate layer 13 may be formed on the protective film 19, and then the thermoplastic resin layer may be formed on the surface of the intermediate layer 13.
  • Method for forming photosensitive composition and photosensitive composition layer It is preferably formed by a coating method using a photosensitive composition containing the above-mentioned components constituting the photosensitive composition layer (for example, a resin, a polymerizable compound, a polymerization initiator, etc.) and a solvent.
  • a photosensitive composition containing the above-mentioned components constituting the photosensitive composition layer (for example, a resin, a polymerizable compound, a polymerization initiator, etc.) and a solvent.
  • a photosensitive composition is applied onto an intermediate layer to form a coating film, and the coating film is dried at a predetermined temperature to form a photosensitive composition layer.
  • the method of forming is preferred.
  • the amount of residual solvent is adjusted by the drying treatment of the coating film.
  • the photosensitive composition preferably contains various components forming the above-mentioned photosensitive composition layer and a solvent.
  • the preferable range of the content of each component with respect to the total solid content of the photosensitive composition is the same as the preferable range of the content of each component with respect to the total mass of the photosensitive composition layer described above. ..
  • the solvent is not particularly limited as long as each component other than the solvent can be dissolved or dispersed, but a known solvent can be used.
  • alkylene glycol ether solvent for example, alkylene glycol ether solvent, alkylene glycol ether acetate solvent, alcohol solvent (methanol, ethanol, etc.), ketone solvent (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbon solvent (toluene, etc.), aprotonic polarity.
  • examples thereof include a solvent (N, N-dimethylformamide, etc.), a cyclic ether solvent (tetratetra, etc.), an ester solvent (npropyl acetate, etc.), an amide solvent, a lactone solvent, and a mixed solvent containing two or more of these.
  • the solvent preferably contains at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent.
  • a mixed solvent containing at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent and at least one selected from the group consisting of a ketone solvent and a cyclic ether solvent is more preferable.
  • a mixed solvent containing at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, and at least three kinds of a ketone solvent and a cyclic ether solvent is more preferable.
  • alkylene glycol ether solvent examples include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether (for example, propylene glycol monomethyl ether acetate, etc.), propylene glycol dialkyl ether, diethylene glycol dialkyl ether, and dipropylene glycol monoalkyl.
  • examples include ethers and dipropylene glycol dialkyl ethers.
  • alkylene glycol ether acetate solvent examples include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate and dipropylene glycol monoalkyl ether acetate.
  • the solvent examples include the solvent described in paragraphs [0092] to [0094] of International Publication No. 2018/179640 and the solvent described in paragraph [0014] of JP-A-2018-1778889, and these are examples.
  • the contents are incorporated herein.
  • the solvent may be used alone or in combination of two or more.
  • the content of the solvent is preferably 50 to 1900 parts by mass, more preferably 100 to 1200 parts by mass, still more preferably 100 to 900 parts by mass with respect to 100 parts by mass of the total solid content of the composition.
  • Examples of the method for applying the photosensitive composition include a printing method, a spray method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method and a die coating method (slit coating method).
  • the drying temperature is preferably 90 ° C. or higher, more preferably 100 ° C. or higher, and even more preferably 110 ° C. or higher.
  • the upper limit is preferably 130 ° C. or lower, more preferably 120 ° C. or lower. It is also possible to continuously change the temperature for drying.
  • the drying time is preferably 20 seconds or longer, more preferably 40 seconds or longer, and even more preferably 60 seconds or longer.
  • the upper limit is preferably 600 seconds or less, more preferably 450 seconds or less, still more preferably 300 seconds or less.
  • the transfer film may be produced by adhering the protective film to the photosensitive composition layer.
  • a method of adhering the protective film to the photosensitive composition layer for example, a known method can be mentioned.
  • the device for adhering the protective film to the photosensitive composition layer include known laminators such as a vacuum laminator and an auto-cut laminator. It is preferable that the laminator is provided with an arbitrary heatable roller such as a rubber roller and can be pressurized and heated.
  • the water-soluble resin composition preferably contains various components forming the above-mentioned intermediate layer (water-soluble resin layer) and a solvent.
  • the preferable range of the content of each component with respect to the total solid content of the composition is the same as the preferable range of the content of each component with respect to the total mass of the water-soluble resin layer described above.
  • the solvent is not particularly limited as long as it can dissolve or disperse the water-soluble resin, but at least one selected from the group consisting of water and a water-mixable organic solvent is preferable, and water or a water-mixable organic solvent is preferable. A mixed solvent with a solvent is more preferable.
  • water-miscible organic solvent examples include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol and glycerin, and alcohols having 1 to 3 carbon atoms are preferable, and methanol or ethanol is more preferable.
  • the solvent may be used alone or in combination of two or more.
  • the content of the solvent is preferably 50 to 2500 parts by mass, more preferably 50 to 1900 parts by mass, still more preferably 100 to 900 parts by mass with respect to 100 parts by mass of the total solid content of the composition.
  • the method for forming the water-soluble resin layer is not particularly limited as long as it can form a layer containing the above components, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, and inkjet coating).
  • the method for forming the thermoplastic resin layer on the temporary support is not particularly limited, but a known method can be used. For example, it can be formed by applying a composition for forming a thermoplastic resin layer on a temporary support and drying it if necessary.
  • the composition for forming the thermoplastic resin layer preferably contains the above-mentioned various components for forming the thermoplastic resin layer and a solvent.
  • the preferable range of the content of each component with respect to the total solid content of the composition is the same as the preferable range of the content of each component with respect to the total mass of the thermoplastic resin layer described above. be.
  • the solvent is not particularly limited as long as each component other than the solvent can be dissolved or dispersed, but a known solvent can be used.
  • the solvent include the same solvents as those contained in the photosensitive composition described later, and the preferred embodiments are also the same.
  • the content of the solvent is preferably 50 to 1900 parts by mass, more preferably 100 to 900 parts by mass with respect to 100 parts by mass of the total solid content of the composition.
  • thermoplastic resin layer is not particularly limited as long as it can form a layer containing the above components, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.). ..
  • the present invention will be described in more detail based on examples.
  • the materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limiting by the examples shown below.
  • “part” and “%” are based on mass unless otherwise specified.
  • the weight average molecular weight of the resin is the weight average molecular weight (Mw) obtained in terms of polystyrene by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the theoretical acid value was used as the acid value.
  • the I / O value was measured by the method described above.
  • a solution containing V-601 (1.0 part by mass) and PGMEA (33.0 parts by mass) was added dropwise to the flask solution maintained at 90 ° C. ⁇ 2 ° C. over 30 minutes. After completion of the dropping, the solution in the flask is stirred at 90 ° C. ⁇ 2 ° C. for 1 hour, and PGMEA (100.0 parts by mass) is added to dilute the resin A1 (solid content concentration 30.0% by mass). Obtained.
  • a solution containing V-601 (1.0 part by mass) and PGMEA (33.0 parts by mass) was added dropwise to the flask solution maintained at 90 ° C. ⁇ 2 ° C. over 30 minutes. After completion of the dropping, the solution in the flask is stirred at 90 ° C. ⁇ 2 ° C. for 1 hour, and PGMEA (100.0 parts by mass) is added to dilute the resin A2 (solid content concentration 30.0% by mass). Obtained.
  • a solution containing V-601 (1.0 part by mass) and PGMEA (33.0 parts by mass) was added dropwise to the flask solution maintained at 90 ° C. ⁇ 2 ° C. over 30 minutes. After completion of the dropping, the solution in the flask is stirred at 90 ° C. ⁇ 2 ° C. for 1 hour, and PGMEA (100.0 parts by mass) is added to dilute the resin A3 (solid content concentration 30.0% by mass). Obtained.
  • a solution containing V-601 (1.0 part by mass) and PGMEA (33.0 parts by mass) was added dropwise to the flask solution maintained at 90 ° C. ⁇ 2 ° C. over 30 minutes. After completion of the dropping, the solution in the flask is stirred at 90 ° C. ⁇ 2 ° C. for 1 hour, and PGMEA (100.0 parts by mass) is added to dilute the resin A4 (solid content concentration 30.0% by mass). Obtained.
  • a solution containing V-601 (1.0 part by mass) and PGMEA (33.0 parts by mass) was added dropwise to the flask solution maintained at 90 ° C. ⁇ 2 ° C. over 30 minutes. After completion of the dropping, the solution in the flask is stirred at 90 ° C. ⁇ 2 ° C. for 1 hour, and PGMEA (100.0 parts by mass) is added to dilute the resin A5 (solid content concentration 30.0% by mass). Obtained.
  • a solution containing V-601 (1.0 part by mass) and PGMEA (33.0 parts by mass) was added dropwise to the flask solution maintained at 90 ° C. ⁇ 2 ° C. over 30 minutes. After completion of the dropping, the solution in the flask is stirred at 90 ° C. ⁇ 2 ° C. for 1 hour, and PGMEA (100.0 parts by mass) is added to dilute the resin A6 (solid content concentration 30.0% by mass). Obtained.
  • a solution containing V-601 (1.0 part by mass) and PGMEA (33.0 parts by mass) was added dropwise to the flask solution maintained at 90 ° C. ⁇ 2 ° C. over 30 minutes. After completion of the dropping, the solution in the flask is stirred at 90 ° C. ⁇ 2 ° C. for 1 hour, and PGMEA (100.0 parts by mass) is added to dilute the resin A7 (solid content concentration 30.0% by mass). Obtained.
  • the resins A1 to A7 are shown.
  • the abbreviations of the monomers for forming each structural unit are shown.
  • the resins A1 to A7 correspond to alkali-soluble resins.
  • composition for forming an intermediate layer The composition 1 for forming an intermediate layer was prepared using each of the following components.
  • 4-88 LA (67.86% by mass): Kuraray, polyvinyl alcohol PVP K30 (31.06% by mass): Fujifilm, Polyvinylpyrrolidone Metros 60SH03 (1.00% by mass): Shin-Etsu Chemical Water-soluble cellulose derivative manufactured by Kogyo Co., Ltd.
  • ⁇ F444 (0.08% by mass): Surfactant manufactured by DIC Co., Ltd.
  • Each transfer film composed of a temporary support, an intermediate layer, and a photosensitive composition layer was prepared so as to have the configuration shown in Table 3. Specifically, it is as follows. First, the composition 1 for forming an intermediate layer for forming the above-mentioned intermediate layer is dried on a temporary support (polyethylene terephthalate film having a thickness of 16 ⁇ m (Lumilar 16KS40, manufactured by Toray Industries, Inc.)) using a bar coater. The latter was applied so as to have a thickness of 1.0 ⁇ m, and dried at 90 ° C. using an oven to form an intermediate layer.
  • a temporary support polyethylene terephthalate film having a thickness of 16 ⁇ m (Lumilar 16KS40, manufactured by Toray Industries, Inc.)
  • the latter was applied so as to have a thickness of 1.0 ⁇ m, and dried at 90 ° C. using an oven to form an intermediate layer.
  • the photosensitive composition for forming the photosensitive composition layer shown in Table 3 is applied onto the intermediate layer using a bar coater so as to have the thickness after drying shown in Table 3, and the oven is heated. It was dried at 80 ° C. to form a negative photosensitive composition layer.
  • a polyethylene terephthalate (16KS40, manufactured by Toray Industries, Inc.) having a thickness of 16 ⁇ m was pressure-bonded onto the obtained negative photosensitive composition layer to prepare transfer films of Examples and Comparative Examples.
  • ⁇ Pattern shape (wide hem shape)> The protective film of the transfer film produced above is peeled off, and the surface of the exposed photosensitive composition layer is laminated on a substrate having a conductive layer with Ni plating (thickness 100 nm) on glass (lamination condition: base).
  • the material temperature was 80 ° C.
  • the rubber roller temperature was 110 ° C.
  • the linear pressure was 3 N / cm
  • the transport speed was 2 m / min) to obtain a laminated body.
  • the temporary support was peeled off from the obtained laminate, and a photomask having a pattern of 1/1 line ( ⁇ m) / space ( ⁇ m) was adhered to the surface of the obtained laminate on the intermediate layer side. I let you.
  • the photosensitive composition layer was exposed at 100 mJ / cm 2 by irradiating with light using a high-pressure mercury lamp exposure machine (MAP-1200L, manufactured by Dainippon Kaken Co., Ltd., main wavelength: 365 nm). Then, a pattern was formed by shower developing for 30 seconds using an aqueous sodium carbonate solution having a liquid temperature of 25 ° C. By observing the cross-sectional shape of the obtained pattern with a scanning electron microscope, the length of the portion (the hem spreading portion in FIG. 1) protruding from the upper surface portion (the surface opposite to the substrate side) of the pattern on the side surface of each pattern. The pattern shape was evaluated according to the following evaluation criteria using the longest hem length.
  • MAP-1200L manufactured by Dainippon Kaken Co., Ltd., main wavelength: 365 nm
  • Hem length is 0.3 ⁇ m or less
  • B Hem length is more than 0.3 ⁇ m and 0.5 ⁇ m or less
  • C Hem length is more than 0.5 ⁇ m and 0.7 ⁇ m or less
  • D Hem length is 0. Over 7 ⁇ m
  • the protective film of the transfer film produced above was peeled off, and the surface of the exposed photosensitive composition layer was laminated on a conductive substrate with Ni plating (thickness 100 nm) on glass (lamination condition: substrate temperature).
  • the laminated body was obtained by subjecting the mixture to 80 ° C., a rubber roller temperature of 110 ° C., a linear pressure of 3 N / cm, and a transport speed of 2 m / min). Next, the temporary support was peeled off from the obtained laminate, and a photomask having a pattern of 1/1 line ( ⁇ m) / space ( ⁇ m) was adhered to the surface of the obtained laminate on the intermediate layer side. I let you.
  • the photosensitive composition layer was exposed at 100 mJ / cm 2 by irradiating with light using a high-pressure mercury lamp exposure machine (MAP-1200L, manufactured by Dainippon Kaken Co., Ltd., main wavelength: 365 nm). Then, a pattern was formed by shower developing for 30 seconds using an aqueous sodium carbonate solution having a liquid temperature of 25 ° C. The minimum line width of the obtained pattern was defined as the resolution ( ⁇ m).
  • ⁇ Development residue inhibitory property> A pattern was formed in the same manner as in the above ⁇ resolution>, and the obtained line / space pattern was measured by measuring the thickness of the residue in the space portion by observing with a scanning electron microscope and visually observing, and based on the following criteria. The development residue inhibitory property was evaluated.
  • C Residue thickness of space part is more than 50 nm
  • Table 3 shows the evaluation results.
  • the “M / B” column indicates the mass ratio of the content of the bifunctional or higher polymerizable compound to the resin content (content of the bifunctional or higher polymerizable compound / resin content).
  • the column of “YX” indicates a value (YX) obtained by subtracting the contact angle X from the contact angle Y.
  • "I / O value” and “Tg” indicate each value of the resin contained in the photosensitive composition layer.
  • “M / B”, “double bond content” and “acid value” indicate each value of the photosensitive composition layer.

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009069589A (ja) * 2007-09-14 2009-04-02 Fujifilm Corp 画像形成方法
WO2010116868A1 (ja) * 2009-03-30 2010-10-14 旭化成イーマテリアルズ株式会社 感光性樹脂組成物及びその積層体
JP2019032474A (ja) * 2017-08-09 2019-02-28 太陽インキ製造株式会社 感光性樹脂組成物、ドライフィルム、硬化物、およびプリント配線板
JP2019105761A (ja) * 2017-12-13 2019-06-27 日立化成株式会社 半導体用感光性樹脂組成物及び半導体装置の製造方法
WO2019244898A1 (ja) * 2018-06-22 2019-12-26 旭化成株式会社 感光性樹脂組成物およびレジストパターンの形成方法

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JP4979391B2 (ja) * 2007-01-17 2012-07-18 旭化成イーマテリアルズ株式会社 感光性樹脂積層体

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009069589A (ja) * 2007-09-14 2009-04-02 Fujifilm Corp 画像形成方法
WO2010116868A1 (ja) * 2009-03-30 2010-10-14 旭化成イーマテリアルズ株式会社 感光性樹脂組成物及びその積層体
JP2019032474A (ja) * 2017-08-09 2019-02-28 太陽インキ製造株式会社 感光性樹脂組成物、ドライフィルム、硬化物、およびプリント配線板
JP2019105761A (ja) * 2017-12-13 2019-06-27 日立化成株式会社 半導体用感光性樹脂組成物及び半導体装置の製造方法
WO2019244898A1 (ja) * 2018-06-22 2019-12-26 旭化成株式会社 感光性樹脂組成物およびレジストパターンの形成方法

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