WO2021132384A1 - 導電性基板の製造方法、導電性基板、タッチセンサー、アンテナ、電磁波シールド材料 - Google Patents

導電性基板の製造方法、導電性基板、タッチセンサー、アンテナ、電磁波シールド材料 Download PDF

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WO2021132384A1
WO2021132384A1 PCT/JP2020/048262 JP2020048262W WO2021132384A1 WO 2021132384 A1 WO2021132384 A1 WO 2021132384A1 JP 2020048262 W JP2020048262 W JP 2020048262W WO 2021132384 A1 WO2021132384 A1 WO 2021132384A1
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Prior art keywords
group
conductive
photosensitive resin
substrate
resin layer
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PCT/JP2020/048262
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English (en)
French (fr)
Japanese (ja)
Inventor
漢那　慎一
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Fujifilm Corp
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Fujifilm Corp
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Priority to KR1020227021229A priority Critical patent/KR20220106784A/ko
Priority to CN202080089449.3A priority patent/CN114868462A/zh
Priority to JP2021567571A priority patent/JPWO2021132384A1/ja
Publication of WO2021132384A1 publication Critical patent/WO2021132384A1/ja
Priority to US17/848,924 priority patent/US20220334492A1/en
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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
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • 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
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0395—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having a backbone with alicyclic moieties
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • 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
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
    • G—PHYSICS
    • G06—COMPUTING OR CALCULATING; COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • 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
    • 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
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • 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
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding

Definitions

  • the present invention relates to a method for manufacturing a conductive substrate, a conductive substrate, a touch sensor, an antenna, and an electromagnetic wave shielding material.
  • Conductive films in which a patterned conductive layer is formed on a substrate are widely used in various fields such as various sensors such as pressure sensors and biosensors, printed circuit boards, solar cells, capacitors, electromagnetic wave shielding materials, touch panels, and antennas. It's being used.
  • a step (S1) of adhering a dry film resist on a substrate and exposure and development of the dry film resist by irradiating an energy beam are performed.
  • a step of forming a pattern mold having a desired patterned recess (S2), a step of filling the patterned recess with an ink containing a functional material (S3), and a step of drying the ink (S4) are performed.
  • a method for forming a high-resolution pattern including the above, wherein the thickness ( ⁇ m) of the dry film resist is 100 ⁇ ⁇ / ⁇ [where ⁇ is the body integration ratio (volume%) of the functional material in the ink. ⁇ is the thickness ( ⁇ m) of the high-resolution pattern], and after the step (S3), the pattern template and unnecessary functional materials on it are removed to form a high-resolution pattern.
  • Patent Document 1 discloses an ink containing a conductive material (conductive ink) as an ink containing the functional material.
  • the present inventor made a prototype of a conductive substrate with reference to the pattern forming method described in Patent Document 1, and as a result, examined the pattern-like conductivity formed on the substrate depending on the type of conductive ink used. It has been clarified that various defects such as disconnection, peeling from the substrate, short circuit at the opening, and adhesion of foreign matter may occur frequently in the layer. That is, it was clarified that improvement is required to further reduce the frequency of the various defects that may occur in the conductive layer.
  • a method for manufacturing a conductive substrate having a substrate and a patterned conductive layer arranged on the substrate The following step X1, the following step X2, the following step X3, the following step X4, the following step X6, the following step X7, and the following step X8 are performed in this order, and the photosensitive resin layer becomes a conductive composition in the following step X4.
  • Step X1 A step of forming a photosensitive resin layer formed from a positive photosensitive resin composition on a substrate
  • Step X2 A step of exposing the photosensitive resin layer in a pattern
  • Step X3 The exposed photosensitive Step of developing the resin layer with an alkaline developing solution to form an opening penetrating the photosensitive resin layer
  • Step X4 A conductive composition is supplied to the opening in the photosensitive resin layer to form a conductive composition.
  • Step X6 Step of exposing the photosensitive resin layer in which the conductive composition layer is formed in the opening
  • Step X7 The exposed photosensitive resin layer contains water as a main component.
  • Step X8 Step of sintering the conductive composition layer on the substrate by heating [2]
  • the conductive composition contains a solvent, and the main component of the solvent is water.
  • Step X5 Step of drying the conductive composition layer by heating [4]
  • the substrate is transparent.
  • a polymer having a polar group protected by a protecting group that is deprotected by the action of the acid contains a structural unit represented by any of the formulas A1 to A3 described later, [9] or [10]. ]
  • the step X1 is a step of forming the photosensitive resin layer on the substrate by using a photosensitive transfer member having the temporary support and the photosensitive resin layer arranged on the temporary support.
  • Any of [1] to [11] which is a step of bringing the surface of the photosensitive resin layer on the side opposite to the temporary support side into contact with the substrate and adhering the photosensitive transfer member to the substrate.
  • An electromagnetic wave shielding material containing the conductive substrate according to [14].
  • the present invention it is possible to provide a method for manufacturing a conductive substrate having a low defect rate. Further, according to the present invention, it is possible to provide a conductive substrate obtained by the above-mentioned method for manufacturing a conductive substrate. Further, according to the present invention, it is possible to provide a touch sensor including the conductive substrate, an antenna, and an electromagnetic wave shielding material.
  • (meth) acrylic acid is a concept including both acrylic acid and methacrylic acid
  • (meth) acrylate is a concept including both acrylate and methacrylate
  • ( "Meta) acryloyl group” is a concept that includes both an acryloyl group and a methacryloyl group.
  • the term "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. ..
  • the term "exposure” as used herein includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams.
  • the light used for exposure is generally the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV (Extreme ultraviolet lithography) light), and active rays such as X-rays (activity). Energy rays).
  • the method for manufacturing a conductive substrate of the present invention is A method for manufacturing a conductive substrate having a substrate and a patterned conductive layer arranged on the substrate.
  • Step X1 A step of forming a photosensitive resin layer formed from a positive photosensitive resin composition on a substrate
  • Step X2 A step of exposing the photosensitive resin layer in a pattern
  • Step X3 The exposed photosensitive Step of developing the resin layer with an alkaline developing solution to form an opening penetrating the photosensitive resin layer
  • Step X4 A conductive composition is supplied to the opening in the photosensitive resin layer to form a conductive composition.
  • Step X6 Step of exposing the photosensitive resin layer in which the conductive composition layer is formed in the opening
  • Step X7 The exposed photosensitive resin layer contains water as a main component.
  • Step X8 A step of sintering the conductive composition layer on the substrate by heating.
  • the manufacturing method preferably includes a step of drying the conductive composition layer obtained in the step X4 between the steps X4 and the step X6.
  • the step of drying the conductive composition layer obtained in step X4 is preferably the following step X5.
  • Step X5 A step of drying the conductive composition layer by heating.
  • the conductive substrate obtained by the method for manufacturing a conductive substrate having the above configuration has a low defect rate. That is, the patterned conductive layer formed on the substrate suppresses the occurrence of various defects such as disconnection, peeling from the substrate, short circuit at the opening, and adhesion of foreign matter.
  • the mechanism of action between the above configuration and the effect is presumed as follows. According to the present invention, the above-mentioned various defects are caused by excessive adhesion between the photosensitive resin layer functioning as a template for supplying the conductive composition and the conductive composition. It is presumed that it occurs mainly during the peeling process of step X7.
  • the sticking is suppressed by using a conductive composition that does not substantially dissolve the photosensitive resin layer in step X4. As a result, it is considered that the defective rate during the peeling process is reduced.
  • the method for manufacturing the conductive substrate of the present invention will be described in detail for each step with reference to the drawings. Further, the conductive substrate will be described in detail together with the description of the method for manufacturing the conductive substrate of the present invention.
  • the description of the constituent elements described below may be based on a typical embodiment of the present invention, but the present invention is not limited to such an embodiment.
  • the first embodiment of the method for manufacturing a conductive substrate has the following steps X1A, the following steps X2, the following steps X3, the following steps X4, the following steps X5, the following steps X6, the following steps X7, and the following steps X8 in this order.
  • Step X1A A photosensitive resin layer is placed on a substrate by using a photosensitive transfer member having a temporary support and a photosensitive resin layer formed from a positive photosensitive resin composition arranged on the temporary support.
  • Step X2 Step of exposing the photosensitive resin layer in a pattern
  • Step X3 The exposed photosensitive resin layer is developed with an alkaline developing solution, and an opening penetrating the photosensitive resin layer is formed.
  • Step of forming Step X4 Step of supplying the conductive composition to the opening in the photosensitive resin layer to form the conductive composition layer
  • Step X5 Step of drying the conductive composition layer by heating
  • X6 Step of exposing the photosensitive resin layer in which the conductive composition layer is formed in the opening
  • Step X7 Step of removing the exposed photosensitive resin layer with a stripping solution containing water as a main component.
  • Step X8 A step of sintering the conductive composition layer on the substrate by heating.
  • FIG. 1 is a schematic view of the conductive substrate 10 formed by the first embodiment of the method for manufacturing a conductive substrate.
  • the conductive substrate 10 has a substrate 1 and a patterned conductive layer 2 arranged on the substrate 1.
  • the thickness of the patterned conductive layer 2 is preferably 5.0 ⁇ m or less, more preferably 3.0 ⁇ m or less, in that the defective rate of the formed conductive substrate is lower.
  • the lower limit is, for example, 0.1 ⁇ m or more, preferably 0.2 ⁇ m or more.
  • step X1A a photosensitive resin layer is formed on a substrate by using a photosensitive transfer member having a temporary support and a photosensitive resin layer formed from a positive photosensitive resin composition arranged on the temporary support. This is the process of forming on top.
  • a photosensitive transfer member having a temporary support and a photosensitive resin layer formed from a positive photosensitive resin composition arranged on the temporary support.
  • the positive photosensitive resin composition may be a chemically amplified positive photosensitive resin composition or a non-chemically amplified positive photosensitive resin composition, but the sensitivity in exposure is more excellent. In that respect, a chemically amplified photosensitive resin composition is preferable.
  • the chemically amplified positive photosensitive resin composition is not particularly limited, and known ones can be applied.
  • the chemically amplified positive photosensitive resin composition is more excellent in sensitivity, resolution, and removability, and is a polar group protected by a protecting group that is deprotected by the action of an acid (hereinafter referred to as "acid-degradable group").
  • the composition contains a polymer having (also referred to as) (hereinafter, also referred to as “acid-degradable resin”) and a photoacid generator.
  • the acid-degradable resin is not limited as long as it is a resin capable of partially decomposing a part of its molecular structure by action with an acid, and examples thereof include a polymer containing a structural unit having an acid-degradable group, which will be described later.
  • the acid generated in response to active radiation (hereinafter, also referred to as “active light”) is contained in the acid-degradable resin. It acts as a catalyst in the deprotection reaction of acid-degradable groups. Since the acid produced by the action of one photon contributes to many deprotection reactions, the quantum yield exceeds 1, which is a large value such as the power of 10, which is high as a result of so-called chemical amplification. Sensitivity is obtained.
  • the positive photosensitive resin composition contains a polymer (acid-degradable resin) having a polar group (acid-degradable group) protected by a protecting group that is deprotected by the action of an acid.
  • the acid-degradable resin is preferably a polymer containing a structural unit having an acid-degradable group (hereinafter, also referred to as “constituent unit A”) (hereinafter, also referred to as “polymer A”).
  • consisttituent unit A hereinafter, also referred to as “polymer A”.
  • the polymer A contains a structural unit having an acid-degradable group (constituent unit A).
  • the acid-degradable group is deprotected by the action of an acid generated by exposure and converted into a polar group. Therefore, the photosensitive resin layer formed of the positive photosensitive resin composition has increased solubility in an alkaline developer upon exposure.
  • the polymer A is preferably an addition polymerization type resin, and more preferably a polymer containing a structural unit derived from (meth) acrylic acid or (meth) acrylic acid ester.
  • the polymer A contains a structural unit other than the structural unit derived from (meth) acrylic acid or (meth) acrylic acid ester (for example, a structural unit derived from styrene, a structural unit derived from a vinyl compound, etc.). You may be.
  • the structural units that the polymer A may contain will be described.
  • Polymer A contains a structural unit having an acid-degradable group.
  • the acid-degradable group can be converted to a polar group by the action of an acid, as described above.
  • the “polar group” refers to a proton dissociative group having a pKa of 12 or less.
  • Examples of the polar group include known acid groups such as a carboxy group and a phenolic hydroxy group.
  • the polar group is preferably a carboxy group or a phenolic hydroxy group.
  • the protecting group is not particularly limited, and examples thereof include known protecting groups.
  • the protecting groups include, for example, a protecting group capable of protecting a polar group in the form of acetal (for example, a tetrahydropyranyl group, a tetrahydrofuranyl group, and an ethoxyethyl group), and a protecting group capable of protecting a polar group in the form of an ester (for example, a protecting group capable of protecting a polar group in the form of an ester (eg, a tetrahydropyranyl group, a tetrahydrofuranyl group, and an ethoxyethyl group).
  • a protecting group capable of protecting a polar group in the form of acetal for example, a tetrahydropyranyl group, a tetrahydrofuranyl group, and an ethoxyethyl group
  • an ester for example, a protecting group capable of protecting a polar group in
  • Examples of the acid-degradable group include acetal-based functional groups such as an ester group, a tetrahydropyranyl ester group, and a tetrahydrofuranyl ester group contained in a structural unit represented by the formula A3 described later, which are relatively easily decomposed by an acid. ), And a group that is relatively difficult to decompose with an acid (for example, a tertiary alkyl ester group such as a tert-butyl ester group and a tertiary alkyl carbonate group such as a tert-butyl carbonate group) can be used.
  • a tertiary alkyl ester group such as a tert-butyl ester group
  • a tertiary alkyl carbonate group such as a tert-butyl carbonate group
  • the acid-degradable group is preferably a group in which a carboxy group or a phenolic hydroxy group is protected in the form of acetal.
  • the structural unit A is selected from the group consisting of the structural unit represented by the formula A1, the structural unit represented by the formula A2, and the structural unit represented by the formula A3 in that the sensitivity and the resolution are more excellent. It is preferably a structural unit of more than one kind, and more preferably one or more kinds of structural units selected from the group consisting of the structural unit represented by the formula A1 and the structural unit represented by the formula A3. It is more preferable that the structural unit is one or more selected from the group consisting of the structural unit represented by the formula A1-2 and the structural unit represented by the formula A3-3 described later.
  • the structural unit represented by the formula A1 and the structural unit represented by the formula A2 are structural units having an acid-degradable group protected by a protecting group in which the phenolic hydroxy group is deprotected by the action of an acid.
  • the structural unit represented by the formula A3 is a structural unit having an acid-degradable group protected by a protecting group in which the carboxy group is deprotected by the action of an acid.
  • R 11 and R 12 independently represent a hydrogen atom, an alkyl group, or an aryl group, respectively. However, at least one of R 11 and R 12 represents an alkyl group or an aryl group.
  • R 13 represents an alkyl group or an aryl group.
  • R 14 represents a hydrogen atom or a methyl group.
  • X 1 represents a single bond or a divalent linking group.
  • R 15 represents a substituent.
  • n represents an integer from 0 to 4.
  • one of the linked may form a cyclic ether (R 11 and R 12 form a cyclic ether linked together with R 13 together, R 11 And the other of R 12 may be a hydrogen atom, i.e. the other of R 11 and R 12 may not be an alkyl or aryl group).
  • R 21 and R 22 independently represent a hydrogen atom, an alkyl group, or an aryl group, respectively. However, at least one of R 21 and R 22 represents an alkyl group or an aryl group.
  • R 23 represents an alkyl group or an aryl group.
  • R 24 is independently a hydroxy group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an aralkyl group, an alkoxycarbonyl group, a hydroxyalkyl group, an arylcarbonyl group, an aryloxycarbonyl group, or a cyclo.
  • m represents an integer of 0 to 3.
  • R 21 or R 22 and R 23 may be linked to each other to form a cyclic ether (when one of R 21 and R 22 is linked to R 23 to form a cyclic ether, R 21 and R
  • the other of 22 may be a hydrogen atom, i.e. the other of R 21 and R 22 may not be an alkyl or aryl group).
  • R 31 and R 32 each independently represent a hydrogen atom, an alkyl group, or an aryl group. However, at least one of R 31 and R 32 represents an alkyl group or an aryl group.
  • R 33 represents an alkyl group or an aryl group.
  • R 34 represents a hydrogen atom or a methyl group.
  • X 0 represents a single bond or a divalent linking group.
  • R 31 or R 32 and R 33 may be connected to each other to form a cyclic ether (when one of R 31 and R 32 is connected to R 33 to form a cyclic ether, R 31 may be formed.
  • the other of R 32 may be a hydrogen atom, that is, the other of R 31 and R 32 may not be an alkyl or aryl group).
  • the number of carbon atoms of the alkyl group represented by R 11 and R 12 is preferably 1 to 10.
  • the aryl group represented by R 11 and R 12 a phenyl group is preferable.
  • R 11 and R 12 are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • examples of the alkyl group or aryl group represented by R 13 include those similar to the alkyl group and aryl group represented by R 11 and R 12.
  • alkyl and aryl groups in R 11 , R 12 , and R 13 may further have substituents.
  • R 11 or R 12 and R 13 are connected to each other to form a cyclic ether.
  • the number of ring members of the cyclic ether is preferably 5 or 6, and more preferably 5.
  • the alkylene group may be linear, branched, or cyclic, and may further have a substituent.
  • the alkylene group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.
  • the RN represents an alkyl group or a hydrogen atom, and an alkyl group or a hydrogen atom having 1 to 4 carbon atoms is preferable, and a hydrogen atom is more preferable.
  • the group represented by -OC (R 11 ) (R 12 ) -OR 13 specified in the formula and X 1 are specified in the formula in terms of steric hindrance of the acid-degradable group. It is preferable that they are bonded to each other at the para position on the benzene ring. That is, the structural unit represented by the formula A1 is preferably the structural unit represented by the following formula A1-1. Incidentally, R 11 in the formula A1-1, R 12, R 13, R 14, R 15, X 1, and n, respectively, R 11 in the formula A1, R 12, R 13, R 14, R 15, X It is synonymous with 1 and n.
  • R 15 is preferably an alkyl group or a halogen atom.
  • the alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.
  • n is preferably 0 or 1, more preferably 0.
  • the R 14 in that the glass transition temperature of the polymer A (Tg) may be lower and a hydrogen atom is preferable. More specifically, the content of the structural unit in which R 14 is a hydrogen atom in the formula A1 is preferably 20% by mass or more with respect to the total content of the structural unit A contained in the polymer A. The content of the structural unit in which R 14 in the formula A1 is a hydrogen atom in the structural unit A is confirmed by the intensity ratio of the peak intensity calculated by a conventional method from 13 C-nuclear magnetic resonance spectrum (NMR) measurement. it can.
  • NMR 13 C-nuclear magnetic resonance spectrum
  • the structural unit represented by the following formula A1-2 is more preferable in that the deformation suppression of the pattern shape is more excellent.
  • R B4 represents a hydrogen atom or a methyl group.
  • R B5 to R B11 independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • RB12 represents a substituent.
  • n represents an integer from 0 to 4.
  • R B4 is preferably a hydrogen atom.
  • R B5 ⁇ R B11 is preferably a hydrogen atom.
  • R B12 is preferably an alkyl group or a halogen atom.
  • the alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.
  • 0 or 1 is preferable, and 0 is more preferable as n.
  • R B4 in the structural unit of the following represents a hydrogen atom or a methyl group.
  • the number of carbon atoms of the alkyl group represented by R 21 and R 22 is preferably 1 to 10.
  • a phenyl group is preferable.
  • examples of the alkyl group or aryl group represented by R 23 include those similar to the alkyl group and aryl group represented by R 21 and R 22.
  • R 23 an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable.
  • the alkyl and aryl groups in R 21 , R 22 , and R 23 may further have substituents.
  • R 24 is preferably an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms independently, and more preferably an alkyl group having 1 to 4 carbon atoms. preferable.
  • R 24 may further have a substituent. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms.
  • the number of carbon atoms of the alkyl group represented by R 31 and R 32 is preferably 1 to 10.
  • the aryl group represented by R 31 and R 32 a phenyl group is preferable.
  • R 31 and R 32 are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 33 an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable.
  • the alkyl group and aryl group in R 31 to R 33 may further have a substituent.
  • R 31 or R 32 and R 33 are connected to each other to form a cyclic ether.
  • the number of ring members of the cyclic ether is preferably 5 or 6, and more preferably 5.
  • a single bond or an arylene group is preferable, and a single bond is more preferable.
  • the arylene group may further have a substituent.
  • the glass transition temperature of the polymer A (Tg) may be lower and a hydrogen atom is preferable. More specifically, the content of the structural unit in which R 34 is a hydrogen atom in the formula A3 is 20% by mass or more with respect to the total content of the structural unit represented by the formula A3 contained in the polymer A. Is preferable.
  • the content of the structural unit in which R 34 is a hydrogen atom in the structural unit represented by the formula A3 is the peak intensity calculated by a conventional method from the 13 C-nuclear magnetic resonance spectrum (NMR) measurement. It can be confirmed by the strength ratio of.
  • the structural unit represented by the following formula A3-3 is more preferable in that the sensitivity at the time of pattern formation is further increased.
  • R 34 represents a hydrogen atom or a methyl group.
  • R 35 to R 41 independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 34 is preferably a hydrogen atom.
  • R 35 to R 41 are preferably hydrogen atoms.
  • R 34 in the following constitutional unit represents a hydrogen atom or a methyl group.
  • the structural unit A contained in the polymer A only one type may be used alone, or two or more types may be used in combination.
  • the content of the structural unit A in the polymer A is preferably 20% by mass or more, more preferably 20 to 90% by mass, and 20 to 70% by mass with respect to the total mass of the polymer A. Is more preferable.
  • the content of the structural unit A in the polymer A can be confirmed by the intensity ratio of the peak intensity calculated by a conventional method from 13 C-NMR measurement.
  • the polymer A preferably contains a structural unit having a polar group (hereinafter, also referred to as “constituent unit B”).
  • the polymer A contains the structural unit B, the sensitivity at the time of pattern formation is improved, and the solubility in an alkaline developer is improved in the developing step after pattern exposure.
  • the polar group in the structural unit B is a proton dissociative group having a pKa of 12 or less.
  • the upper limit of the pKa of the polar group is preferably 10 or less, more preferably 6 or less, in terms of further improving the sensitivity.
  • the lower limit is preferably ⁇ 5 or higher.
  • Examples of the polar group in the structural unit B include a carboxy group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxy group, a sulfonylimide group and the like.
  • a carboxy group or a phenolic hydroxy group is preferable.
  • Examples of the method for introducing the structural unit B into the polymer A include a method of copolymerizing a monomer having a polar group and a method of copolymerizing a monomer having an acid anhydride structure to hydrolyze the acid anhydride.
  • Examples of the monomer having a carboxy group as a polar group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxystyrene and the like.
  • Examples of the monomer having a phenolic hydroxy group as a polar group include p-hydroxystyrene and 4-hydroxyphenylmethacrylate.
  • Examples of the monomer having an acid anhydride structure include maleic anhydride and the like.
  • the structural unit B is preferably a structural unit derived from a styrene compound having a polar group, or a structural unit derived from a vinyl compound having a polar group, and a structural unit derived from a styrene compound having a phenolic hydroxy group.
  • it is more preferably a structural unit derived from a vinyl compound having a carboxy group, further preferably a structural unit derived from a vinyl compound having a carboxy group, and a structural unit derived from (meth) acrylic acid. Is particularly preferable.
  • structural unit B only one type may be used alone, or two or more types may be used in combination.
  • the content of the structural unit B in the polymer A is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, based on the total mass of the polymer A. It is more preferably 1 to 10% by mass.
  • the content of the structural unit B in the polymer A can be confirmed by the intensity ratio of the peak intensity calculated by a conventional method from 13 C-NMR measurement.
  • the polymer A may further contain other structural units (hereinafter, also referred to as “constituent unit C”) in addition to the above-mentioned structural unit A and structural unit B.
  • Constituent unit C also referred to as “constituent unit C”
  • Various characteristics of the polymer A can be adjusted by adjusting at least one of the type and the content of the structural unit C contained in the polymer A.
  • the glass transition temperature (Tg) of the polymer A can be easily adjusted by appropriately using the structural unit C.
  • Examples of the monomer forming the structural unit C include styrenes, (meth) acrylic acid alkyl esters, (meth) acrylic acid cyclic alkyl esters, (meth) acrylic acid aryl esters, unsaturated dicarboxylic acid diesters, and bicyclounsaturated compounds. , Maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, unsaturated compounds with an aliphatic cyclic skeleton, and other known unsaturated substances. Saturated compounds and the like can be mentioned.
  • constituent unit C examples include styrene, tert-butoxystyrene, methylstyrene, ⁇ -methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, and (meth) acrylic acid.
  • Examples thereof include structural units derived from benzyl, isobornyl (meth) acrylate, acrylonitrile, mono (meth) acrylate of ethylene glycol monoacetate, and the like.
  • structural unit C a structural unit derived from the compound described in paragraphs 0021 to 0024 of JP2004-246623A can be mentioned.
  • the structural unit C is preferably a structural unit having an aromatic ring or a structural unit having an aliphatic cyclic skeleton from the viewpoint of further improving the electrical characteristics.
  • the monomer forming the above-mentioned structural unit include styrene, tert-butoxystyrene, methylstyrene, ⁇ -methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and Benzyl (meth) acrylate and the like can be mentioned.
  • the structural unit C is preferably a structural unit derived from cyclohexyl (meth) acrylate.
  • the structural unit C is preferably a (meth) acrylic acid alkyl ester in that it has better adhesion, and has an alkyl group having 4 to 12 carbon atoms. More preferably, it is a (meth) acrylic acid alkyl ester. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
  • the polymer A includes, as the structural unit C, a structural unit having an ester of the polar group in the structural unit B, in terms of further improving the solubility in a developing solution and / or optimizing the physical properties. Is also preferable.
  • the polymer A preferably contains a structural unit having a carboxy group as the structural unit B, and further preferably contains a structural unit C containing a carboxylic acid ester group.
  • a structural unit derived from (meth) acrylic acid for example, a structural unit derived from (meth) acrylic acid.
  • ⁇ contains B and a monomer-derived structural unit C selected from the group consisting of cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and n-butyl (meth) acrylate.
  • structural unit C only one type may be used alone, or two or more types may be used in combination.
  • the upper limit of the content of the structural unit C in the polymer A is preferably 80% by mass or less, more preferably 75% by mass or less, and 60% by mass, based on the total mass of the polymer A. It is more preferably% or less, and particularly preferably 50% by mass or less.
  • the lower limit of the content of the structural unit C in the polymer A may be 0% by mass, preferably 1% by mass or more, and 5% by mass or more, based on all the structural units constituting the polymer A. Is more preferable.
  • the polymer A may be used alone or in combination of two or more.
  • the content of the polymer A in the positive photosensitive resin composition is preferably 50 to 99.9% by mass, more preferably 70 to 98% by mass, based on the total solid content of the composition.
  • the glass transition temperature (Tg) of the polymer A is preferably 90 ° C. or lower, more preferably 20 to 60 ° C. from the viewpoint of transferability. , 30 to 50 ° C. is particularly preferable.
  • the glass transition temperature (Tg) of the polymer A As a method of adjusting the glass transition temperature (Tg) of the polymer A within the above numerical range, for example, a method of adjusting the type and mass fraction of each structural unit contained in the polymer A by using the FOX equation as a guideline. Can be mentioned.
  • the glass transition temperature (Tg) of the polymer A is adjusted from the glass transition temperature (Tg) of the homopolymer of each structural unit contained in the polymer A and the mass fraction of each structural unit. it can. Further, the glass transition temperature (Tg) of the polymer A can be adjusted by adjusting the weight average molecular weight of the polymer A.
  • the glass transition temperature of the homopolymer of the first structural unit is Tg1
  • the mass fraction of the first structural unit contained in the copolymer is W1
  • the glass transition temperature of the homopolymer of the second structural unit Is Tg2, and when the mass fraction of the second constituent unit contained in the copolymer in the copolymer is W2, Tg0 of the copolymer containing the first constituent unit and the second constituent unit is taken as Tg0.
  • K can be estimated according to the following formula.
  • the acid value of polymer A is preferably 0 to 200 mgKOH / g, more preferably 0 to 100 mgKOH / g.
  • the acid value of the polymer represents the mass of potassium hydroxide required to neutralize the acidic component per 1 g of the polymer.
  • the obtained solution is neutralized and titrated with a 0.1 M aqueous sodium hydroxide solution at 25 ° C.
  • the acid value is calculated by the following formula with the inflection point of the titration pH curve as the titration end point.
  • the weight average molecular weight of the polymer A is preferably 2,000 to 60,000, more preferably 3,000 to 50,000.
  • the weight average molecular weight of the polymer A can be measured by GPC (gel permeation chromatography), and various commercially available devices can be used as the measuring device.
  • GPC gel permeation chromatography
  • HLC registered trademark
  • -8220 GPC manufactured by Tosoh Corporation
  • TSKgel registered trademark
  • Super HZM-M 4.
  • the calibration curve is "Standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-40", “F-20”, “F-4", “F-1", "A-5000", “A”. It can be prepared using any of 7 samples of "-2500” and "A-1000".
  • the ratio (dispersity) of the number average molecular weight of the polymer A to the weight average molecular weight is preferably 1.0 to 5.0, and more preferably 1.05 to 3.5.
  • the method for producing polymer A is not particularly limited, but to give an example, a polymerizable monomer for forming the structural unit A and a polymerizable monomer for forming the structural unit B.
  • a monomer and, if necessary, a polymerizable monomer for forming the structural unit C can be synthesized by polymerizing in an organic solvent with a polymerization initiator. Further, the polymer A can also be synthesized by a so-called polymer reaction.
  • the positive photosensitive resin composition may further contain a polymer containing no structural unit having an acid-degradable group (hereinafter, also referred to as “other polymer”).
  • Examples of other polymers include polyhydroxystyrene and the like.
  • Examples of polyhydroxystyrene include SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, and SMA 3840F (all manufactured by Sartmer), ARUFON UC-3000, ARUFON UC-3510, and ARUFON UC-. 3900, ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (above, manufactured by Toa Synthetic Co., Ltd.), and Joncryl 690, Joncryl 678, Joncryl 67, and Joncryl 586 (above, BASF) Goods can be used.
  • the content of the other polymers in the positive photosensitive resin composition is based on the total content of the polymer A and the other polymers. It is preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less.
  • the positive photosensitive resin composition preferably contains a photoacid generator.
  • the photoacid generator is a compound capable of generating an acid by being irradiated with radiation such as ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.
  • a compound that is sensitive to active light having a wavelength of 300 nm or more, preferably a wavelength of 300 to 450 nm and generates an acid is preferable.
  • a compound having absorption at a wavelength of 365 nm is more preferable in that the spectral sensitivity is more excellent.
  • a photoacid generator that is not directly sensitive to active light having a wavelength of 300 nm or more can be used as a sensitizer if it is a compound that is sensitive to active light having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. Can be preferably used in combination.
  • the photoacid generator is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and a pKa of 2 or less.
  • a photoacid generator that generates an acid is particularly preferable.
  • the lower limit of the pKa of the acid generated from the photoacid generator is not particularly limited, and is preferably -10 or more, for example.
  • the photoacid generator examples include an ionic photoacid generator and a nonionic photoacid generator. Further, the photoacid generator preferably contains one or more compounds selected from the group consisting of an onium salt compound and an oxime sulfonate compound, and more preferably contains an oxime sulfonate compound, because the photoacid generator is more excellent in sensitivity and resolution. preferable.
  • Examples of the ionic photoacid generator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.
  • onium salt compounds are preferable, and diaryliodonium salts or triarylsulfonium salts are more preferable.
  • the ionic photoacid generator described in paragraphs 0114 to 0133 of JP-A-2014-85643 can also be preferably used.
  • nonionic photoacid generator examples include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, oxime sulfonate compounds and the like.
  • an oxime sulfonate compound is particularly preferable in that sensitivity, resolution, and adhesion are improved.
  • Specific examples of the trichloromethyl-s-triazines and the diazomethane derivative include the compounds described in paragraphs 0083 to 0088 of Japanese Patent Application Laid-Open No. 2011-22149.
  • oxime sulfonate compound that is, the compound having an oxime sulfonate structure
  • a compound having an oxime sulfonate structure represented by the following formula (B1) is preferable.
  • R 21 represents an alkyl group or an aryl group
  • * represents a binding site with another atom or another group.
  • the compound having an oxime sulfonate structure represented by the formula (B1) may be substituted with any group, and the alkyl group at R 21 may be linear, branched chain, or cyclic. .. Acceptable substituents are described below.
  • alkyl group represented by R 21 a linear or branched alkyl group having 1 to 10 carbon atoms is preferable.
  • the alkyl group represented by R 21 has an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group (for example, a 7,7-dimethyl-2-oxonorbornyl group and the like). It may be substituted with a bridge-type alicyclic group, preferably a bicycloalkyl group or the like), or a halogen atom.
  • aryl group in R 21 an aryl group having 6 to 18 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable.
  • the aryl group in R 21 may be substituted with one or more groups selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, alkoxy groups, and halogen atoms.
  • the compound having an oxime sulfonate structure represented by the formula (B1) is preferably the oxime sulfonate compound described in paragraphs 0078 to 0111 of JP-A-2014-85643.
  • the photoacid generator may be used alone or in combination of two or more.
  • the content of the photoacid generator in the positive photosensitive resin composition is preferably 0.1 to 10% by mass, preferably 0.1 to 10% by mass, based on the total mass of the composition, in that the sensitivity and resolution are more excellent. More preferably, it is 2 to 5% by mass.
  • the positive photosensitive resin composition may contain a solvent.
  • Examples of the solvent include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, and diethylene glycol dialkyl.
  • Examples thereof include ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, lactones and the like. ..
  • examples of the solvent include the solvents described in paragraphs 0174 to 0178 of JP-A-2011-22149, and the contents thereof are incorporated in the present disclosure.
  • the positive photosensitive resin composition further comprises benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, and capron, if necessary. It may contain solvents such as acid, capric acid, 1-octanol, 1-nonal, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, and propylene carbonate.
  • solvents such as acid, capric acid, 1-octanol, 1-nonal, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, and propylene carbonate.
  • the solvent is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof.
  • Examples of the solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C. include propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.). And propylene glycol methyl-n-propyl ether (boiling point 131 ° C.) and the like.
  • Examples of the solvent having a boiling point of 160 ° C. or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C.), diethylene glycol methyl ethyl ether (boiling point 176 ° C.), propylene glycol monomethyl ether propionate (boiling point 160 ° C.), and dipropylene glycol methyl.
  • Ether acetate (boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether Examples thereof include acetate (boiling point 220 ° C.), dipropylene glycol dimethyl ether (boiling point 175 ° C.), and 1,3-butylene glycol diacetate (boiling point 232 ° C.).
  • solvent examples include esters, ethers, ketones and the like.
  • esters examples include ethyl acetate, propyl acetate, isobutyl acetate, sec-butyl acetate, t-butyl acetate, isopropyl acetate, n-butyl acetate and the like.
  • ethers include diisopropyl ether, 1,4-dioxane, 1,2-dimethoxyethane, 1,3-dioxolane, propylene glycol dimethyl ether, propylene glycol monoethyl ether and the like.
  • ketones examples include methyl n-butyl ketone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, methyl n-propyl ketone, methyl isopropyl ketone and the like.
  • solvent toluene, acetonitrile, isopropanol, 2-butanol, isobutyl alcohol and the like may be used.
  • the solvent may be used alone or in combination of two or more.
  • the content of the solvent in the positive photosensitive resin composition is preferably 50 to 1,900 parts by mass, preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition. More preferred.
  • the positive photosensitive resin composition may further contain other additives, if necessary, in addition to the polymer A and the photoacid generator.
  • the positive photosensitive resin composition preferably contains a basic compound.
  • the basic compound include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids. Specific examples of these include the compounds described in paragraphs 0204 to 0207 of JP-A-2011-22149, the contents of which are incorporated in the present disclosure.
  • Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine and dicyclohexylamine. , And dicyclohexylmethylamine and the like.
  • aromatic amines examples include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
  • heterocyclic amine examples include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, and the like.
  • Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.
  • Examples of the quaternary ammonium salt of the carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.
  • the basic compound may be used alone or in combination of two or more.
  • the content of the basic compound in the positive photosensitive resin composition is preferably 0.001 to 5% by mass, preferably 0.005 to 3% by mass, based on the total mass of the composition. More preferred.
  • the positive photosensitive resin composition preferably contains a liquid repellent from the viewpoint of further improving the uniformity of thickness and further reducing the defective rate of the conductive substrate to be formed.
  • a liquid repellent a compound containing at least one of a fluorine atom and a silicon atom is preferable, a fluorine atom-containing compound is more preferable, a fluorine atom-containing surfactant is further preferable, and a fluorine atom-containing nonionic surfactant is particularly preferable.
  • a liquid repellent having a polymerizable group hereinafter, also referred to as “polymerizable group-containing liquid repellent” can be used as the polymerizable group. Examples of the polymerizable group include an epoxy group and an ethylenically unsaturated group.
  • a compound represented by the general formula (1) of JP2013-209636A can also be used.
  • a fluorine atom-containing nonionic surfactant is preferable.
  • a preferable example of the fluorine atom-containing nonionic surfactant is measured by gel permeation chromatography containing the structural unit SA and the structural unit SB represented by the following formula I-1 and using tetrahydrofuran (THF) as a solvent.
  • THF tetrahydrofuran
  • examples thereof include copolymers having a polystyrene-equivalent weight average molecular weight (Mw) of 1,000 to 10,000.
  • R 401 and R 403 independently represent a hydrogen atom or a methyl group, respectively.
  • R 402 represents a linear alkylene group having 1 to 4 carbon atoms.
  • R 404 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • L represents an alkylene group having 3 to 6 carbon atoms.
  • p and q are mass percentages representing the polymerization ratio.
  • p represents a numerical value of 10 to 80% by mass
  • q represents a numerical value of 20 to 90% by mass.
  • r represents an integer from 1 to 18.
  • s represents an integer from 1 to 10. * Represents a binding site with another structure.
  • L is preferably a branched alkylene group represented by the following formula I-2.
  • R405 in the formula I-2 represents an alkyl group having 1 to 4 carbon atoms, and an alkyl group having 1 to 3 carbon atoms is preferable in terms of compatibility and wettability to the surface to be coated, and the alkyl group has 2 or 3 carbon atoms. Alkyl groups are more preferred.
  • the weight average molecular weight (Mw) of the copolymer containing the structural unit SA and the structural unit SB represented by the formula I-1 is preferably 1,500 to 5,000.
  • liquid repellent other than the above-mentioned copolymer
  • fluorine atom-containing compound examples include perfluoroalkyl sulfonic acid, perfluoroalkylcarboxylic acid, perfluoroalkylalkylene oxide adduct, perfluoroalkyltrialkylammonium salt, oligomer containing perfluoroalkyl group and hydrophilic group, and perfluoro.
  • Examples thereof include oligomers containing alkyl and lipophilic groups, oligomers containing perfluoroalkyl groups and hydrophilic groups and lipophilic groups, urethanes containing perfluoroalkyl and hydrophilic groups, perfluoroalkyl esters, perfluoroalkyl phosphate esters and the like. ..
  • fluorine atom-containing compounds include "DEFENSAMCF-300”, “DEFENSAMCF-310”, “DEFENSAMCF-312”, “DEFENSAMCF-323”, and "Megafuck RS-72-K” (all manufactured by DIC).
  • Fluorine atom-containing surfactant can also be used.
  • Florard FC430, FC431, and FC171 all manufactured by Sumitomo 3M Ltd.
  • Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40 aboveve, manufactured by AGC Inc.
  • PolyFox PF636, PF656, PF6320, PF6520, and PF7002 aboveve, manufactured by OMNOVA
  • Futergent 710FL, 710FM can also be used.
  • 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, and 683 (all manufactured by NEOS Co., Ltd.) and the like can also be used. ..
  • a fluorine atom-containing nonionic surfactant such as Futergent 250 and Futergent 251 manufactured by Neos Co., Ltd. can also be used.
  • the fluorine atom-containing compound the surfactants described in paragraphs 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of Japanese Patent Application Laid-Open No. 2009-237362 can also be used.
  • fluorine-based surfactant from the viewpoint of improving environmental suitability, compounds having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), are used. It is preferably a surfactant derived from an alternative material.
  • PFOA perfluorooctanoic acid
  • PFOS perfluorooctanesulfonic acid
  • silicon atom-containing compounds examples include silicone-based surfactants such as the SILFOAM® series (for example, SD100TS, SD670, SD850, SD860, SD882) manufactured by Wacker Chemie.
  • SILFOAM® series for example, SD100TS, SD670, SD850, SD860, SD882 manufactured by Wacker Chemie.
  • the liquid repellent may be used alone or in combination of two or more.
  • the lower limit of the content of fluorine atoms in the liquid repellent is preferably 1% by mass or more, more preferably 5% by mass or more.
  • the upper limit value is preferably 50% by mass or less, more preferably 25% by mass or less.
  • the content of the liquid repellent in the positive photosensitive resin composition is, for example, 0.01 to 10% by mass, preferably 0.05 to 5% by mass, based on the total solid content of the composition.
  • the positive photosensitive resin composition preferably contains a surfactant from the viewpoint of further improving the uniformity of thickness.
  • the surfactant referred to here does not include the above-mentioned surfactant-based liquid repellent.
  • any of anionic surfactant, cationic surfactant, nonionic (nonionic) surfactant, and amphoteric surfactant can be used. Of these, nonionic surfactants are preferable.
  • nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, and polyoxyethylene glycol higher fatty acid diesters. Specific examples of the nonionic surfactant include the nonionic surfactant described in paragraph 0120 of International Publication No. 2018/179640.
  • the surfactant may be used alone or in combination of two or more.
  • the content of the surfactant in the positive photosensitive resin composition is preferably 10% by mass or less, more preferably 0.001 to 10% by mass, based on the total mass of the composition. It is more preferably 0.01 to 3% by mass.
  • the positive photosensitive resin composition may contain a plasticizer for the purpose of improving plasticity.
  • the plasticizer is not particularly limited, and a known plasticizer can be applied. Examples of the plasticizer include the plasticizers described in paragraphs 097 to 0103 of International Publication No. 2018/179640.
  • the positive photosensitive resin composition may contain a sensitizer.
  • the sensitizer is not particularly limited, and a known sensitizer can be applied. Examples of the sensitizer include the sensitizers described in paragraphs 0104 to 0107 of International Publication No. 2018/179640.
  • the positive photosensitive resin composition may contain a heterocyclic compound.
  • the heterocyclic compound is not particularly limited, and known heterocyclic compounds can be applied. Examples of the heterocyclic compound include the heterocyclic compounds described in paragraphs 0111 to 0118 of International Publication No. 2018/179640.
  • the positive photosensitive resin composition may contain an alkoxysilane compound.
  • the alkoxysilane compound is not particularly limited, and a known alkoxysilane compound can be applied. Examples of the alkoxysilane compound include the alkoxysilane compound described in paragraph 0119 of International Publication No. 2018/179640.
  • Positive photosensitive resin compositions include metal oxide particles, antioxidants, dispersants, acid growth agents, development accelerators, conductive fibers, colorants, thermal radical polymerization initiators, and thermoacid generators. , UV absorbers, thickeners, cross-linking agents, and known additives such as organic or inorganic precipitation inhibitors may be further included. Preferred embodiments of the other components are described in paragraphs 0165 to 0184 of JP2014-85643, respectively, and the contents of this publication are incorporated in the present specification.
  • Method for preparing composition examples include a method in which the above components and a solvent are mixed at an arbitrary ratio and dissolved by stirring. Further, a positive photosensitive resin composition can be prepared by dissolving each of the above components in a solvent in advance to prepare a solution, and then mixing the obtained solutions in a predetermined ratio. The prepared positive photosensitive resin composition may be used after being filtered using a filter having a pore size of 0.2 ⁇ m or the like.
  • the photosensitive transfer member has a temporary support and a photosensitive resin layer formed from the above-mentioned positive photosensitive resin composition arranged on the temporary support. Further, the photosensitive transfer member may have a protective film on the surface of the photosensitive resin layer opposite to the temporary support.
  • Examples of the temporary support include a glass base material and a resin film.
  • the temporary support may have a single-layer structure consisting of only one layer, or may have a multi-layer structure including two or more layers.
  • the thickness of the temporary support is not particularly limited, and is, for example, 6 to 150 ⁇ m, preferably 12 to 50 ⁇ m.
  • the photosensitive transfer member has a photosensitive resin layer formed from the above-mentioned positive photosensitive resin composition on a temporary support.
  • the lower limit of the thickness of the photosensitive resin layer is preferably 1.0 ⁇ m or more from the viewpoint of transferability and resolvability.
  • the upper limit value is, for example, 30.0 ⁇ m or less, preferably 15.0 ⁇ m or less, more preferably 10.0 ⁇ m or less, and further preferably 5.0 ⁇ m or less.
  • Examples of the method for forming the photosensitive resin layer include a method in which a positive photosensitive resin composition is applied onto a temporary support to form a coating film, and then the coating film is dried.
  • Examples of the coating method include known methods such as slit coating, spin coating, curtain coating, and inkjet coating.
  • the drying temperature is not particularly limited, and is, for example, 80 to 150 ° C.
  • the drying time is not particularly limited, and is, for example, 3 to 60 minutes.
  • another layer such as an intermediate layer may be provided on the temporary support. When another layer such as an intermediate layer is arranged on the temporary support, a photosensitive resin layer is formed on the other layer. Examples of other layers include the layers described in paragraphs 0131 to 0134 of International Publication No. 2018/179640.
  • the substrate is not particularly limited, but a glass substrate or a resin substrate is preferable, and a resin substrate is more preferable.
  • the resin constituting the resin substrate include polycarbonate (PC), acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), polypropylene (PP), polyethylene (PE), and polyamide ( PA), polyacetal (POM), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyphenylene sulfide (PPS), polyetheretherketone (PEEK), polystyrene (PS), polymethylmethacrylate (PMMA), polyphenylene ether ( Examples thereof include resins such as PPE), polysulfone (PSF), polyethersulfone (PES), polyamideimide (PAI), polyetherimide (PEI), polyimide (PI), and polyvinyl chloride (PVC).
  • PC polycarbon
  • the surface of the substrate may be subjected to surface treatment such as hydrophilic treatment for the purpose of improving the adhesion to the conductive layer.
  • the substrate is preferably transparent in that it facilitates exposure of the photosensitive resin layer from the surface of the substrate opposite to the side having the photosensitive resin layer (back surface of the substrate) via the substrate in step X6. ..
  • the light transmittance in the visible region of 400 to 700 nm is preferably 50% or more, and the light transmittance in the 400 to 450 nm is more preferably 10% or more.
  • the thickness of the substrate is preferably 10 to 200 ⁇ m, more preferably 20 to 150 ⁇ m, and even more preferably 30 to 100 ⁇ m.
  • step X1A the substrate and the photosensitive transfer member are bonded to each other by bringing the surface of the photosensitive resin layer on the side opposite to the temporary support side into contact with the substrate.
  • the protective film is provided on the surface of the photosensitive resin layer opposite to the temporary support side, the substrate and the photosensitive transfer member are bonded together after removing the protective film from the photosensitive transfer member.
  • a known laminator such as a laminator, a vacuum laminator, or an auto-cut laminator that can further increase productivity can be used for bonding the substrate and the photosensitive transfer member.
  • a laminator such as a laminator, a vacuum laminator, or an auto-cut laminator that can further increase productivity
  • the laminated body 20 shown in FIG. 2 can be obtained.
  • the laminate 20 has a substrate 1, a photosensitive resin layer 3 and a temporary support 5 on the substrate 1.
  • the step X2 is a step of exposing the photosensitive resin layer 3 of the laminate 20 obtained through the step X1 in a pattern.
  • FIG. 3 schematically shows an example of the exposure process.
  • the mask 6 having the opening 6a is arranged so as to be in close contact with the temporary support 5, and the photosensitive resin layer 3 of the laminated body 20 is exposed in a pattern through the temporary support 5.
  • step X2 the acid-degradable resin in the exposed portion (position corresponding to the opening 6a) of the photosensitive resin layer 3 is deprotected by the action of the acid and dissolved in the alkaline developer. Increases sex.
  • step X2 the exposed portion of the photosensitive resin layer 3 is removed in the subsequent developing step of step X3.
  • the position and size of the opening of the mask are not particularly limited.
  • the opening is opened from the viewpoint of improving the display quality of the display device and minimizing the area occupied by the take-out wiring.
  • the shape is a fine line, and the width thereof is preferably 100 ⁇ m or less, more preferably 70 ⁇ m or less.
  • any light source that irradiates the photosensitive resin layer with light in a wavelength range that can be exposed can be appropriately selected.
  • Specific examples thereof include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (Light Emitting Diodes).
  • LEDs Light Emitting Diodes
  • the exposure amount is preferably 5 ⁇ 1000mJ / cm 2, more preferably 100 ⁇ 1000mJ / cm 2, more preferably 100 ⁇ 500mJ / cm 2.
  • the exposure treatment may be performed after the temporary support 5 is peeled off from the photosensitive resin layer 3.
  • the pattern exposure may be an exposure through a mask or a direct exposure using a laser or the like.
  • Step X3 is a step of developing the photosensitive resin layer exposed in the pattern obtained in step X2 with an alkaline developer to form an opening penetrating the photosensitive resin layer.
  • the temporary support 5 is peeled off from the laminated body 20.
  • the laminate 30 obtained through the development process of step X3 has a substrate 1 and a photosensitive resin layer 3A arranged on the substrate 1 and having an opening 7 penetrating through the layer. Have. That is, the photosensitive resin layer 3A has an opening 7 in which the substrate 1 is exposed. The position of the opening 7 penetrating the photosensitive resin layer 3A coincides with the position of the opening (opening 6a in FIG.
  • step X4 which will be described later, the conductive composition is supplied to the opening 7.
  • the alkaline aqueous solution-based developer may further contain a water-soluble organic solvent, a surfactant, and the like.
  • the alkaline aqueous solution-based developer for example, the developer described in paragraph 0194 of International Publication No. 2015/093271 is preferable.
  • the development method is not particularly limited, and any of paddle development, shower development, spin development, dip development, etc. may be used.
  • shower development will be described.
  • the liquid temperature of the alkaline developer is preferably 20 to 40 ° C.
  • Step X3 may further include a post-baking step of heat-treating the developed photosensitive resin layer.
  • Post-baking is preferably carried out in an environment of 8.1 to 121.6 kPa, and more preferably carried out in an environment of 50.66 kPa or more. On the other hand, it is more preferably carried out in an environment of 111.46 kPa or less, and further preferably carried out in an environment of 101.3 kPa or less.
  • the post-baking temperature is preferably 80 to 250 ° C, more preferably 110 to 170 ° C, and even more preferably 130 to 150 ° C.
  • the post-baking time is preferably 1 to 30 minutes, more preferably 2 to 10 minutes, still more preferably 2 to 4 minutes. Post-baking may be performed in an air environment or a nitrogen substitution environment.
  • Step X4 is a step of supplying the conductive composition to the opening 7 of the photosensitive resin layer 3A of the laminate 30 shown in FIG.
  • FIG. 5 shows the laminated body 40 obtained through the step X4.
  • the laminate 40 has a conductive composition layer 8A formed from the conductive composition in the opening 7 of the photosensitive resin layer 3A.
  • the conductive composition is in a region other than the opening 7 (for example, the photosensitive resin layer 3A). It may adhere to the upper surface of the). Therefore, as a method of supplying the conductive composition, a method of applying the conductive composition to the entire surface of the photosensitive resin layer 3A may be used.
  • step X4 a conductive composition that does not substantially dissolve the photosensitive resin layer is used. That is, in step X4, the photosensitive resin layer is substantially insoluble in the conductive composition. Whether or not the conductive composition does not substantially dissolve the photosensitive resin layer is determined by the following method.
  • the positive photosensitive resin composition used in step X1 is applied onto the surface of the substrate so that the dry thickness is 3 ⁇ m to form a coating film.
  • the coating film is dried with warm air at 90 ° C. for 0.5 hour to prepare a test substrate having a photosensitive resin layer formed on the substrate.
  • a polyethylene terephthalate film is preferable.
  • the thickness of the photosensitive resin layer in the test substrate is measured. Specifically, a scanning electron microscope (SEM) is used to observe a cross section including a direction perpendicular to the main surface of the layer, and the thickness of the layer is increased to 10 points or more based on the obtained observation image. The measurement is performed, and the average value T1 ( ⁇ m) is calculated.
  • test substrate is immersed in the conductive composition (temperature: 30 ° C.) used in step X4 for 5 minutes. After immersion for a predetermined time, the test substrate is removed from the conductive composition and dried at 90 ° C.
  • the thickness of the photosensitive resin layer in the test substrate after the dipping treatment is measured. Specifically, the cross section including the direction perpendicular to the main surface of the layer is observed using SEM, the thickness of the layer is measured at 10 points or more based on the obtained observation image, and the average value T2 ( ⁇ m) is measured. Is calculated.
  • the contact angle of the surface of the photosensitive resin layer 3A with respect to the conductive composition is preferably larger than the contact angle of the surface of the substrate 1 with respect to the conductive composition. That is, it is preferable that the conductive composition exhibits better wettability with respect to the surface of the substrate 1 than with respect to the surface of the photosensitive resin layer 3A.
  • the contact angle of the surface of the photosensitive resin layer 3A with respect to the conductive composition is smaller than the contact angle of the surface of the substrate 1 with respect to the conductive composition, as shown in FIG.
  • the opening 7 of the photosensitive resin layer 3A The conductive composition supplied to the above may easily crawl up the side surface of the photosensitive resin layer 3A and exude to the upper surface of the photosensitive resin layer 3A (see the conductive composition layer 8B in FIG. 6). As a result, defects such as short circuits tend to occur easily in the conductive layer 2 of the conductive substrate to be formed. Therefore, as described above, the contact angle of the surface of the photosensitive resin layer 3A with respect to the conductive composition is preferably larger than the contact angle of the surface of the substrate 1 with respect to the conductive composition.
  • the surface of the photosensitive resin layer 3A preferably has a liquid-repellent property (repellent property) with respect to the conductive composition, and the surface of the substrate 1 is liquid-friendly to the conductive composition. It is preferable to have it.
  • the liquid repellency and liquid friendship of the conductive composition can be evaluated by the following methods. A droplet of the conductive composition is deposited on the evaluation target, and the evaluation is performed based on the behavior of the droplet. When the surface area of the droplet decreases with respect to the amount of the droplet at the time of landing, the evaluation object has liquid repellency. On the other hand, when the surface area of the droplet increases with respect to the amount of the droplet at the time of drip, the evaluation object has positivity.
  • the contact angle of the conductive composition with respect to the surface of the photosensitive resin layer 3A is preferably 30 ° or more, and the conductive composition with respect to the surface of the substrate 1 can be further reduced from the defect rate of the conductive substrate to be formed.
  • the contact angle of is preferably less than 30 °.
  • step X4 the procedure will be described after explaining the materials used in step X4.
  • the conductive composition includes a conductive material.
  • the conductive material is intended to include both a material that exhibits conductivity by itself and a material that can form a conductive layer after being sintered.
  • the conductive material is a conductive material that exhibits conductivity by itself and can form a conductive layer having a sheet resistivity of less than 10 ⁇ / ⁇ at 23 ° C., or a sheet at 23 ° C. after being sintered.
  • a conductive material capable of forming a conductive layer having a resistivity of less than 10 ⁇ / ⁇ is preferable.
  • the conductive composition is not particularly limited, but for example, a composition in which a conductive material is dissolved or dispersed in a solvent, or a composition containing a conductive material and a binder polymer is preferable, and the conductive material is dispersed in a solvent.
  • a composition hereinafter, also referred to as “composition C1”) or a composition containing a conductive material and a binder polymer (hereinafter, also referred to as “composition C2”) is more preferable, and the conductive material is dispersed in a solvent.
  • composition C1 a composition containing a conductive material and a binder polymer
  • composition C1 a composition containing a conductive material and a binder polymer
  • the prepared composition is more preferable.
  • As the conductive composition known conductive pastes and conductive inks, and plating-forming inks described later can also be used.
  • the conductive material is not particularly limited, and examples thereof include those shown below, and (a) is preferable.
  • Metal oxide particles (c) Conductive organic materials such as conductive polymer particles, and superconductivity Elementary particles (d) Organometallic compounds (e) Other conductive materials other than the above-mentioned (a) to (e)
  • metal unit and alloy a metal unit selected from the group consisting of gold, silver, copper, nickel, aluminum, gold, platinum, and palladium, or an alloy composed of two or more of these metals is preferable, and the resistance value, Gold, silver, copper, or alloys thereof are more preferable from the viewpoint of cost, sintering temperature, and the like, and silver is preferable from the viewpoint of sintering temperature and oxidation suppression.
  • metal single body or alloy in the shape of particles, clusters, crystals, tubes, fibers, wires, rods, films and the like described above, gold nanoparticles, silver nanoparticles, or copper nanoparticles are preferable, and silver is preferable. Nanoparticles are more preferred.
  • the "metal oxide” is a compound that does not substantially contain an unoxidized metal. Specifically, a peak derived from an oxidized metal is detected in a crystal analysis by X-ray diffraction, and the metal. Refers to a compound in which no peak of origin is detected. It is not particularly limited that the unoxidized metal is not substantially contained, but it means that the content of the unoxidized metal is 1% by mass or less with respect to the metal oxide particles.
  • the metal oxide in the metal oxide particles include oxides such as copper, silver, nickel, gold, platinum, palladium, indium, and tin.
  • the metal oxide species may be one kind or a mixture of two or more kinds.
  • an oxide of copper, silver, nickel, or tin is preferable, an oxide of copper or silver is more preferable, and an oxide of copper is further preferable.
  • an oxide of copper copper (I) oxide or copper (II) oxide is preferable, and copper (II) oxide is more preferable because it can be obtained at low cost.
  • the upper limit of the average particle size of the metal oxide particles is preferably less than 1 ⁇ m, more preferably less than 200 nm. The lower limit is preferably 1 nm or more.
  • the average particle size of the metal oxide particles refers to the number average value of the particle size of the primary particles of 100 metal oxide particles randomly selected by observation with a scanning electron microscope (SEM).
  • Conductive organic materials such as conductive polymers and superconductors
  • conductive organic materials and superconductors include polyaniline, polythiophene, polyphenylene vinylene and the like.
  • examples of the conductive organic material include PEDOT (polyethylene dioxythiophene) (PEDOT / PSS) doped with PPS (polystyrene sulfonic acid).
  • Organometallic compound refers to a compound in which a metal is precipitated by decomposition by heating.
  • organometallic compound examples include chlorotriethylphosphine gold, chlorotrimethylphosphine gold, chlorotriphenylphosphine gold, silver 2,4-pentandionato complex, trimethylphosphine (hexafluoroacetylacetonate) silver complex, and copper hexafluoropentaneo. Examples thereof include a natocyclooctadiene complex.
  • Examples of the conductive material other than the above-mentioned (a) to (e) include a resist material, an acrylic resin as a linear insulating material, and a silane compound which becomes silicon by heating. These may be dispersed as particles in a solvent or may be dissolved and exist. Examples of the silane compound that becomes silicon by heating include trisilane, pentasilane, cyclotrisilane, and 1,1′-biscyclobutasilane.
  • the conductive composition preferably contains a solvent and the main component thereof is water in that the defect rate of the conductive substrate to be formed is further reduced.
  • the "main component” refers to the component having the largest amount (mass ratio) of the solvents contained in the conductive composition.
  • the content of water is preferably more than 50% by mass, more preferably 55% by mass or more, based on the total mass of the solvent contained in the conductive composition. It is more preferably 60% by mass or more, particularly preferably 80% by mass or more, and most preferably 90% by mass or more.
  • the upper limit of the water content is, for example, 100% by mass or less with respect to the total mass of the solvent contained in the composition C1.
  • composition C1 preferably contains a conductive material, a solvent, and a dispersant.
  • the composition C1 may further contain other components such as a polymerizable compound having an ethylene unsaturated group and a polymerization initiator.
  • the conductive material contained in the composition C1 include the conductive materials described above.
  • the composition C1 preferably has a viscosity of 1 to 20 mPa ⁇ s.
  • the composition C1 is preferably a colloidal liquid in which a conductive material is dispersed in a dispersion medium.
  • the conductive material contained in the composition C1 conductive particles are preferable, and silver nanoparticles are more preferable.
  • the average particle size of the conductive particles is preferably 0.1 to 50 nm, more preferably 1 to 20 nm, from the viewpoint of stability and fusion temperature.
  • the average particle size of the conductive particles refers to the number average value of the particle sizes of the primary particles of 100 conductive particles randomly selected.
  • the content of the conductive material in the composition C1 is such that the dispersion stability and the metal film forming property in the step of sintering the conductive composition layer in the step X8 described later are more excellent. It is preferably 10 to 95% by mass, more preferably 30 to 80% by mass, based on the total mass.
  • the composition C1 preferably contains silver colloidal particles in which silver nanoparticles form a colloidal state, in that the conductive layer to be formed is less likely to be oxidized and the volume resistance value is less likely to decrease.
  • the form of the silver colloidal particles is not particularly limited, and for example, a form in which a dispersant is attached to the surface of silver nanoparticles, a form in which silver nanoparticles are used as a core and the surface thereof is coated with a dispersant, and a form in which the surface is coated with a dispersant, and Examples thereof include a form in which silver particles and a dispersant are uniformly mixed, and among them, a form in which silver nanoparticles are used as a core and the surface thereof is coated with a dispersant, or silver particles and a dispersant. Is preferably a form in which is uniformly mixed.
  • the silver colloidal particles having each of the above-mentioned forms can be appropriately prepared by a known method.
  • the average particle size of the silver colloidal particles is preferably 1 to 400 nm because the dispersibility in the composition with time is more excellent and / or the resistance value of the conductive layer to be formed is further reduced. 1 to 70 nm is more preferable.
  • the average particle size of the silver colloidal particles can be measured as a median diameter (D50) with the particle size as the volume standard by using the dynamic light scattering method (Doppler scattered light analysis).
  • the composition C1 contains silver nanoparticles
  • the composition C1 has a submicron size silver having a larger average particle size (for example, an average particle size of 1 ⁇ m or less) than the silver nanoparticles in addition to the silver nanoparticles. It may contain submicron particles.
  • the silver nanoparticles have a melting point drop around the silver submicron particles, so that a good conductive path can be easily obtained.
  • the composition C1 contains silver nanoparticles
  • the composition C1 contains metal particles other than silver (hereinafter, “other metal particles”) in addition to the silver nanoparticles in that migration of the conductive layer can be suppressed.
  • other metal particles metal particles other than silver
  • a mixed colloidal solution of silver nanoparticles and other metal particles is more preferable.
  • the metal other than silver a metal having an ionization series noble than hydrogen is preferable.
  • gold, copper, platinum, palladium, rhodium, iridium, osmium, ruthenium, or renium is preferable, and gold, copper, platinum, or palladium is more preferable.
  • composition C1 is a mixed colloidal liquid
  • silver and other metals may form alloy colloidal particles, or may form colloidal particles having a structure such as a core-shell structure and a multilayer structure.
  • the metal particles other than silver may be nano-sized particles or submicron-sized particles.
  • Examples of the solvent contained in the composition C1 include water and an organic solvent, and water is preferable.
  • the organic solvent is not particularly limited, and for example, hydrocarbons such as toluene, dodecane, tetradecane, cyclododecene, n-heptane, and n-undecane: saturated aliphatic monohydric alcohols such as ethanol, isopropyl alcohol, and butanol: Alkanediols such as propanediol, butanediol, and pentanediol: alkylene glycols such as ethylene glycol ,: diethylene glycol monoisobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol isopropyl ether, ethylene glycol monomethyl ether, And glycol monoethers such as diethylene glycol monobutyl ether: glycerin and the like can be mentioned.
  • the composition C1 preferably contains a solvent and the main component thereof is water in that the defect rate of the conductive substrate to be formed is further reduced.
  • the "main component” refers to the component having the largest amount (mass ratio) of the solvents contained in the composition C1.
  • the content of water is preferably more than 50% by mass, more preferably 55% by mass or more, and more preferably 60% by mass, based on the total mass of the solvent contained in the composition C1. % Or more is more preferable, 80% by mass or more is particularly preferable, and 90% by mass or more is most preferable.
  • the upper limit of the water content is, for example, 100% by mass or less with respect to the total mass of the solvent contained in the composition C1.
  • the content of the solvent is preferably 2 to 98% by mass, preferably 25 to 80% by mass, based on the total mass of the composition, in that the dispersibility stability of the conductive material is more excellent. It is more preferably by mass, more preferably 50 to 80% by mass, and particularly preferably 55 to 80% by mass.
  • composition C1 contains water, as a dispersion medium other than water, from the group consisting of diethylene glycol monoisobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol isopropyl ether, ethylene glycol monomethyl ether, and diethylene glycol monobutyl ether. It is also preferable to use one or more selected solvents in combination. In addition to this, it is also preferable to further use one or more solvents selected from the group consisting of butanol, propanediol, butanediol, pentanediol, ethylene glycol, and glycerin.
  • the composition C1 may contain a dispersant as described above.
  • the dispersant has a carboxy group and a hydroxyl group in that the dispersion stability of the conductive particles (particularly silver colloidal particles) in the composition is more excellent, and the number of carboxy groups contained in the molecule ⁇ the molecule. Hydroxylic acid or a salt thereof, which is the number of hydroxyl groups contained therein, is preferable.
  • Examples of the hydroxy acid or a salt thereof include organic acids such as citric acid, malic acid, tartaric acid, and glycolic acid; trisodium citrate, tripotassium citrate, trilithium citrate, monopotassium citrate, and hydrogen citrate.
  • Ionic compounds such as disodium, potassium dihydrogen citrate, disodium malate, disodium tartrate, potassium tartrate, potassium sodium tartrate, potassium hydrogen tartrate, sodium hydrogen tartrate, and sodium glycolate; and hydrates thereof. And so on.
  • trisodium citrate, tripotassium citrate, trilithium citrate, disodium malate, disodium tartrate, or hydrates thereof are preferable. Only one type of dispersant may be used alone, or two or more types may be used in combination.
  • the point that the storage stability of the conductive particles is more excellent with respect to the total mass of the composition and the resistance value of the conductive layer to be formed are more.
  • 0.5 to 30% by mass is preferable, 1 to 20% by mass is more preferable, and 1 to 10% by mass is further preferable.
  • the composition C1 may contain a polymerizable compound having an ethylene unsaturated group (hereinafter, also referred to as “ethylene unsaturated polymerizable compound”).
  • ethylene unsaturated polymerizable compound is preferably a compound containing two or more ethylene unsaturated groups in the molecule (polyfunctional ethylenically unsaturated compound) in that it is more excellent in curability and strength, and is preferable in the molecule. More preferably, it is a compound containing 3 or more ethylene unsaturated groups.
  • a (meth) acrylate compound As the ethylene unsaturated polymerizable compound, a (meth) acrylate compound, a vinylbenzene compound, a bismaleimide compound and the like are preferable, and a polyvalent (meth) acrylate compound is more preferable.
  • the polyvalent (meth) acrylate compound include an ester compound of a polyhydric alcohol and acrylic acid or methacrylic acid.
  • Examples of the polyfunctional (meth) acrylate compound include a polyfunctional (meth) acrylate compound having 3 to 6 (meth) acryloyloxy groups in the molecule.
  • Examples of the polyfunctional (meth) acrylate compound having three or more (meth) acryloyloxy groups in the molecule include trimethylpropantri (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, and pentaerythritol tri (meth) acrylate.
  • Pentaerythritol tetra (meth) acrylate dipentaerythritol penta (meth) acrylate
  • polyol poly (meth) acrylates such as dipentaerythritol hexa (meth) acrylate
  • polyisocyanate and hydroxyethyl (meth) acrylate examples thereof include urethane (meth) acrylate obtained by the reaction of the hydroxyl group-containing (meth) acrylate.
  • the content of the ethylene unsaturated polymerizable compound in the composition C1 is preferably 5 to 80% by mass, more preferably 10 to 50% by mass, based on the total solid content of the composition.
  • the composition C1 may contain a polymerization initiator.
  • the polymerization initiator may be either a thermal polymerization initiator or a photopolymerization initiator.
  • thermal polymerization initiator include thermal radical generators. Specific examples thereof include benzoyl peroxide, peroxide initiators such as azobisisobutyronitrile, and azo-based initiators.
  • photopolymerization initiator include photoradical generators. Specifically, (a) aromatic ketones, (b) onium salt compounds, (c) organic peroxides, (d) thio compounds, (e) hexaarylbiimidazole compounds, (f) ketooxime ester compounds. , (G) borate compound, (h) azinium compound, (i) active ester compound, (j) compound having a carbon halogen bond, (k) pyridium compound and the like.
  • the content of the polymerization initiator in the composition C1 is preferably 0.1 to 50% by mass, more preferably 1.0 to 30.0% by mass, based on the total solid content of the composition.
  • composition C1 may further contain a high-viscosity substance in order to suppress fluidity.
  • the composition C1 may further contain a reducing agent.
  • a reducing agent for example, tannic acid or hydroxy acid is preferable.
  • the tannic acid also includes, for example, gallotannin acid, rhus chinensis tannin and the like.
  • the reducing agent may be used alone or in combination of two or more.
  • the content of the reducing agent is preferably 0.01 to 6 g, preferably 0.02 to 1.5 g, with respect to 1 g of the conductive particles.
  • composition C2 preferably contains a conductive material and a binder polymer.
  • the conductive material contained in the composition C2 include the conductive materials described above.
  • conductive particles are preferable, and silver nanoparticles are more preferable.
  • the above-mentioned conductive particles and silver nanoparticles that can be contained in the composition C2 include the same conductive particles and silver nanoparticles that can be contained in the composition C1.
  • the binder polymer contained in the composition C2 is not particularly limited, and a known binder polymer can be used.
  • the binder polymer include thermoplastic resins such as polyester resin, (meth) acrylic resin, polyethylene resin, polystyrene resin, and polyamide resin. Further, it may be a thermosetting resin such as an epoxy resin, an amino resin, a polyimide resin, and a (meth) acrylic resin.
  • the compounding ratio (mass ratio) of the conductive material and the binder polymer in the composition C2 is not particularly limited, and is, for example, 10/90 to 90/10, preferably 20/80 to 80/20.
  • the composition C2 may further contain a solvent for the purpose of adjusting the viscosity.
  • the solvent is not particularly limited as long as it can dissolve the components of the composition C2, but it is preferable that the main component is water in terms of further reducing the defect rate of the conductive substrate to be formed.
  • the "main component” refers to the component having the largest amount (mass ratio) of the solvents contained in the composition C2.
  • the content of water is preferably more than 50% by mass, more preferably 55% by mass or more, and more preferably 60% by mass, based on the total mass of the solvent contained in the composition C2. % Or more is more preferable, 80% by mass or more is particularly preferable, and 90% by mass or more is most preferable.
  • the upper limit of the water content is, for example, 100% by mass or less with respect to the total mass of the solvent contained in the composition C1.
  • a plating-forming ink may be used as the conductive composition.
  • the plating-forming ink is an ink composed of a composition for forming a layer to be plated and a plating solution, and a metal layer (conductive layer) is formed by electroless plating on the layer to be plated formed from the composition for forming a layer to be plated. Is intended as an ink capable of forming.
  • the composition for forming a layer to be plated contains an electroless plating catalyst or a precursor thereof, or is electroless, in order to enable electroless plating on the layer to be plated formed from the composition for forming a layer to be plated.
  • the composition for forming a layer to be plated preferably contains a compound having an interacting group and a solvent.
  • the composition for forming the layer to be plated preferably further contains a polymerization initiator and a polymerizable compound.
  • the description of publicly known documents such as the pamphlet of International Publication No. 2016/159136 can be referred to.
  • the method of supplying the conductive composition to the opening 7 of the photosensitive resin layer 3A of the laminate 30 shown in FIG. 4 is not particularly limited, and for example, rotary coating using a spinner, spray coating, inkjet, and roll coating. , Screen printing, offset printing, gravure printing, letterpress printing, flexographic printing, blade coater, die coater, calendar coater, meniscus coater, and various coating methods using a bar coater.
  • Step X5 is a step of drying the conductive composition layer formed on the substrate 1 in step X4 by heating.
  • the drying method include heat drying using an oven, an electromagnetic wave ultraviolet lamp, an infrared heater, a halogen heater, and the like, vacuum drying, and the like.
  • the lower limit of the drying temperature is, for example, 40 ° C. in that the drying proceeds sufficiently.
  • the upper limit of the drying temperature is, for example, 150 ° C., and is preferably less than 120 ° C. in terms of further reducing the defect rate of the conductive substrate to be formed.
  • the drying temperature is preferably 50 ° C. or higher and lower than 120 ° C.
  • the drying time is preferably 1 minute to several hours.
  • the thickness (dry thickness) of the conductive composition layer obtained through step X5 is such that the defective rate of the conductive substrate to be formed is lower, for example, 5.0 ⁇ m or less and 3.0 ⁇ m or less. Is preferable, and 2.5 ⁇ m or less is more preferable.
  • the lower limit is, for example, 0.1 ⁇ m or more, preferably 0.2 ⁇ m or more.
  • Step X6 is a step of exposing the photosensitive resin layer 3A (the photosensitive resin layer obtained in the above step X5) to which the conductive composition is supplied to the opening 7. As shown in FIG. 7, in the step X6, the exposure (preferably the entire surface) is performed from the surface of the substrate 1 opposite to the photosensitive resin layer 3A (the back surface of the substrate 1). By carrying out step X6, the acid-degradable groups in the acid-degradable resin in the exposed photosensitive resin layer 3A are deprotected by the action of the acid, and the solubility in the alkaline stripping solution is increased. That is, the polarity of the photosensitive resin layer 3A changes. By carrying out the step X6, the exposed photosensitive resin layer 3A is easily peeled off in the peeling step of the subsequent step X7.
  • the light source used for exposure can be appropriately selected as long as it irradiates the photosensitive resin layer 3A with light in a wavelength range that can be exposed (for example, 365 nm, 405 nm, etc.).
  • a wavelength range that can be exposed for example, 365 nm, 405 nm, etc.
  • Specific examples thereof include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (Light Emitting Diodes).
  • the exposure amount is preferably 5 ⁇ 1000mJ / cm 2, more preferably 100 ⁇ 1000mJ / cm 2, more preferably 300 ⁇ 800mJ / cm 2.
  • the exposure process may be performed from the surface of the substrate 1 opposite to the photosensitive resin layer 3A (the back surface of the substrate 1) via the substrate 1, or the surface of the substrate 1 on the photosensitive resin layer 3A side.
  • the exposure may be performed from (the surface of the substrate 1).
  • Step X7 is a step of removing the photosensitive resin layer exposed by performing step X6 with a stripping solution containing water as a main component.
  • FIG. 8 shows the laminated body 50 obtained through the step X7.
  • the laminate 50 has a substrate 1 and a patterned conductive composition layer 8A on the substrate 1.
  • the stripping liquid contains water as a main component.
  • the "main component” refers to the component having the largest amount (mass ratio) among the components contained in the stripping solution.
  • the content of water in the stripping liquid is preferably more than 50% by mass, more preferably 55% by mass or more, and further preferably 60% by mass or more with respect to the total mass of the stripping liquid. , 80% by mass or more is particularly preferable, and 90% by mass or more is most preferable.
  • the upper limit of the water content is, for example, 100% by mass or less, preferably 95% by mass or less, based on the total mass of the solvent contained in the stripping solution.
  • the stripping liquid preferably further contains organic amines for the purpose of promoting stripping.
  • the organic amines are not particularly limited, but for example, 1st to 3rd grade alkylamines or alkanolamines are preferable, and for example, diethylamine (boiling point: 55.5 ° C.), triethylamine (boiling point: 89 ° C.), monoethanolamine (boiling point). : 170 ° C.), diethanolamine (boiling point: 280 ° C.), N-methyl-ethanolamine (boiling point: 155 ° C.) and the like.
  • the boiling point of the organic amines is, for example, 300 ° C. or lower, and 250 ° C. in order to facilitate volatilization without inhibiting the sintering of the conductive material during sintering of the conductive composition layer in step X8.
  • the following is preferable, 180 ° C. or lower is more preferable, and 100 ° C. or lower is further preferable.
  • the lower limit of the boiling point of the organic amines is not particularly limited, but is, for example, 30 ° C.
  • organic amines 1st to 3rd grade alkylamines or alkanolamines having a boiling point of 180 ° C. or lower are preferable, and diethylamine (boiling point: 55.5 ° C.), triethylamine (boiling point: 89 ° C.), or monoethanolamine. (Boiling point: 170 ° C.) is more preferable, and diethylamine (boiling point: 55.5 ° C.) or triethylamine (boiling point: 89 ° C.) is further preferable.
  • the upper limit of the content of the organic amine in the stripping liquid is preferably less than 50% by mass, more preferably 40% by mass or less, still more preferably 30% by mass or less, based on the total mass of the stripping liquid.
  • the lower limit of the content of the organic amine in the stripping liquid is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, based on the total mass of the stripping liquid.
  • the stripping liquid may further contain a water-soluble organic solvent, a surfactant, and the like.
  • the peeling method is not particularly limited, and any of paddle peeling, shower peeling, spin peeling, dip peeling, and the like may be used.
  • the shower peeling will be described.
  • the liquid temperature of the stripping liquid is, for example, 20 to 60 ° C.
  • the upper limit of the liquid temperature of the stripping liquid is preferably less than 50 ° C. in that the defective rate of the formed conductive substrate is further reduced.
  • the lower limit is preferably 5 ° C. or higher.
  • the step X8 is a step of sintering the patterned conductive composition layer 8A obtained through the step X7.
  • heat sintering or photosintering is preferable in that the resistance value of the conductive layer is further reduced and the production efficiency is more excellent.
  • the heating temperature is such that the heat resistance of the base material is more excellent and the resistance value of the conductive layer in the formed conductive substrate is further reduced.
  • it is 90 ° C. or higher, preferably 100 ° C. or higher, more preferably 120 ° C. or higher, still more preferably 130 ° C. or higher.
  • the upper limit thereof is, for example, 200 ° C. or lower, preferably 180 ° C. or lower, and more preferably 160 ° C. or lower.
  • the heating method is not particularly limited, and examples thereof include a method using a conventionally known gear oven or the like.
  • the heating time is preferably 0.5 to 120 minutes, preferably 1 to 80 minutes, because the production efficiency is more excellent and the resistance value of the conductive layer in the conductive substrate to be formed is further reduced. It is more preferably 1 to 60 minutes, and further preferably 10 to 60 minutes.
  • the type of light rays to be irradiated is not particularly limited as long as the conductive composition layer can be sintered, but light containing ultraviolet rays is preferable. ..
  • the irradiation energy is preferably from 10 ⁇ 10000mJ / cm 2, more preferably from 20 ⁇ 6000mJ / cm 2, even more preferably 30 ⁇ 5000mJ / cm 2.
  • the irradiation time also depends on the irradiation energy, but is not particularly limited, and may be a normal exposure or a flash exposure. When performing flash exposure, the irradiation time is preferably 0.1 to 10 ms (milliseconds), more preferably 0.2 to 5 ms, and even more preferably 0.5 to 4 ms.
  • the sintering treatment of the patterned conductive composition layer 8A is preferably carried out at a temperature higher than the boiling point of the organic amines contained in the stripping solution in that the resistance value of the conductive layer is further reduced.
  • the conductive composition layer 8A is sintered, and the conductive substrate 10 shown in FIG. 1 is obtained.
  • the thickness of the patterned conductive layer 2 obtained through the step X8 is as described above.
  • the sheet resistance value of the patterned conductive layer 2 obtained through the step X8 is preferably less than 10 ⁇ / ⁇ , more preferably less than 5 ⁇ / ⁇ , and less than 2 ⁇ / ⁇ at 23 ° C. Is more preferable.
  • the lower limit is not particularly limited, but is, for example, 10-2 ⁇ / ⁇ or more.
  • the second embodiment of the method for manufacturing a conductive substrate has the following steps X1B, the above steps X2, the above steps X3, the above steps X4, the above steps X5, the above steps X6, the above steps X7, and the above steps X8 in this order. ..
  • Step X1B A step of applying a positive photosensitive resin composition onto a substrate to form a photosensitive resin layer.
  • a second embodiment of the method for manufacturing a conductive substrate is to carry out step X1B instead of step X1A. Except for the points, it is the same as the first embodiment of the above-described method for manufacturing a conductive substrate.
  • the substrate and positive photosensitive resin composition used in step X1B are the same as the substrate and positive photosensitive resin composition used in step X1A.
  • the conductive substrate 10 shown in FIG. 1 is formed according to the second embodiment of the method for manufacturing a conductive substrate.
  • the step X1B is preferably a step of forming a coating film of the positive photosensitive resin composition on the substrate by coating and drying the obtained coating film to form a photosensitive resin layer.
  • the lower limit of the thickness of the photosensitive resin layer is preferably 1.0 ⁇ m or more from the viewpoint of transferability and resolution.
  • the upper limit value is, for example, 30.0 ⁇ m or less, preferably 15.0 ⁇ m or less, more preferably 10.0 ⁇ m or less, and further preferably 5.0 ⁇ m or less.
  • the coating method examples include known methods such as slit coating, spin coating, curtain coating, and inkjet coating.
  • the drying temperature is not particularly limited, and is, for example, 80 to 150 ° C.
  • the drying time is not particularly limited, and is, for example, 1 to 60 minutes.
  • the step X5 is an optional step and is not included in the method for manufacturing the conductive substrate. May be good.
  • the conductive substrate obtained by the above-mentioned method for manufacturing a conductive substrate can be applied to various uses.
  • Applications of the conductive substrate include, for example, a touch panel (touch sensor), an antenna, an electromagnetic wave shielding material, a semiconductor chip, various electric wiring boards, FPC (Flexible printed circuits), COF (Chip on Film), and TAB (Tape Automated Bonding). , Multilayer wiring boards, and motherboards, preferably used as touch sensors, antennas, or electromagnetic shielding materials.
  • the patterned conductive layer of the conductive substrate functions as a detection electrode or a lead-out wiring in the touch sensor.
  • the touch panel is not particularly limited as long as it has the above-mentioned touch sensor.
  • the above-mentioned touch sensor is combined with various display devices (for example, a liquid crystal display device and an organic EL (electro-luminescence) display device).
  • display devices for example, a liquid crystal display device and an organic EL (electro-luminescence) display device.
  • Equipment is mentioned.
  • Examples of the detection method in the touch sensor and the touch panel include known methods such as a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method. Of these, a capacitive touch sensor and a touch panel are preferable.
  • the touch panel type includes a so-called in-cell type (for example, those shown in FIGS. 5, 6, 7, and 8 of Japanese Patent Application Laid-Open No. 2012-517501), and a so-called on-cell type (for example, Japanese Patent Application Laid-Open No. 2013-168125).
  • the ones shown in FIG. 19 and those shown in FIGS. 1 and 5 of JP2012-081020A eg, Japanese Patent Application Laid-Open No. 2012
  • OGS One Glass Solution
  • TOR Touch-on-Lens
  • Examples of the touch panel include those described in paragraph 0229 of JP2017-120345A.
  • the method for manufacturing the touch panel is not particularly limited, and a known method for manufacturing the touch panel may be referred to except that the touch sensor having the conductive substrate is used.
  • AA Acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • ATH 2-tetrahydrofuranyl acrylate (synthetic product)
  • CHA Cyclohexyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • EA Ethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • MAA Methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • PMEA Propylene glycol monomethyl ether acetate (manufactured by Showa Denko KK)
  • TA tert-butyl acrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
  • BMA Benzyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
  • PMPMA 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate
  • the numerical value described for each structural unit is intended to be mass%.
  • the weight average molecular weight of the polymer 1 is 25,000.
  • the glass transition temperature of the polymer 1 is 25 ° C.
  • composition 1 for the intermediate layer was prepared according to the following formulation.
  • -Cellulose resin Methanol (registered trademark) 60SH-03, manufactured by Shin-Etsu Chemical Industry Co., Ltd.): 3.5 parts-Surfactant (Megafuck (registered trademark) F444, manufactured by DIC Corporation): 0.1 parts-Pure Water: 33.7 parts, Methanol: 62.7 parts
  • the intermediate layer composition 1 is dried on a temporary support 1 (polyethylene terephthalate film having a thickness of 12 ⁇ m, Lumirror 12QS62, manufactured by Toray Industries, Inc., haze value 0.43%) using a slit-shaped nozzle.
  • An intermediate layer was formed by applying in an amount of 0 ⁇ m and then drying.
  • the above-mentioned positive photosensitive resin composition 1 has a dry thickness shown in Table 1 (see the “Dry thickness ( ⁇ m)” column of the photosensitive resin layer in Table 1). It was applied to form a coating film.
  • the photosensitive resin layer 1 was formed by drying the coating film with warm air at 90 ° C.
  • a polyethylene film (OSM-N manufactured by Tredegar Co., Ltd.) was pressure-bonded onto the obtained photosensitive resin layer 1 as a protective film to prepare a photosensitive transfer member 1.
  • the photosensitive transfer member 2 was produced by the same production method as the above-mentioned photosensitive transfer member 1 except that the following temporary support 2 was used instead of the temporary support 1.
  • a temporary support 2 having a coating layer on one side of the polyethylene terephthalate film was produced by the following method.
  • a temporary support 2 having a base material (polyethylene terephthalate film) having a thickness of 10 ⁇ m and a coating layer having a thickness of 50 nm was obtained by applying a coating liquid for a coating layer to the obtained unstretched film and sequentially biaxially stretching the film.
  • the coating liquid for the coating layer was applied after the unstretched film was uniaxially stretched in the process of sequentially biaxially stretching the unstretched film.
  • the haze value of the temporary support 2 was 0.31%.
  • the coating liquid for the coating layer was prepared according to the following formulation.
  • ⁇ Coating liquid for coating layer ⁇ -Acrylic polymer AS-563A, manufactured by Daicel FineChem Co., Ltd., solid content 27.5% by mass
  • 167 parts-Nonion-based surfactant Naaro Acty (registered trademark) CL95, manufactured by Sanyo Kasei Kogyo Co., Ltd., solid content 100 Mass%)
  • 0.7 parts-Anionic surfactant Lapisol® A-90, manufactured by Chukyo Yushi Co., Ltd., solid content 1% by mass water-diluted
  • 7 parts carbodiimide compound
  • Carbodilite (registered trademark) V-02-L2 manufactured by Nisshinbo Chemical Co., Ltd., solid content 10% by mass, diluted with water
  • matting agent Snowtex (registere
  • the photosensitive transfer member 3 was produced by the same production method as that of the photosensitive transfer member 1 described above except that the thickness of the intermediate layer was 5.0 ⁇ m.
  • the photosensitive transfer member 4 was formed by the same manufacturing method as the above-mentioned photosensitive transfer member 1 except that the positive-type photosensitive resin composition 1 was directly applied onto the temporary support 1 without providing an intermediate layer. Made.
  • the photosensitive transfer member 5 was produced by the same production method as the above-mentioned photosensitive transfer member 1 except that the following positive photosensitive resin composition 2 was used instead of the positive photosensitive resin composition 1.
  • ⁇ Preparation of positive photosensitive resin composition 2> The following components were mixed to obtain a mixed solution. Next, the above mixture was filtered using a filter made of polytetrafluoroethylene having a pore size of 0.2 ⁇ m to obtain a positive photosensitive resin composition 2.
  • -Acid-degradable resin polymer 2 below: 9.64 parts-Photoacid generator (compound A-2 below): 0.25 parts-Surfactant (surfactant C): 0.01 parts- Additive (Compound D above): 0.1 parts, PGMEA: 90.00 parts
  • Polymer 2 A compound having the structure shown below (the glass transition temperature is 90 ° C., the weight average molecular weight is 20,000. The numerical value described in each of the following structural units means mass%. )
  • Compound A-2 Compound with the structure shown below
  • Step X1A Step of forming a photosensitive resin layer on a substrate
  • a photosensitive transfer member Laminated by laminating the above-mentioned photosensitive transfer member on a PET film (Cosmoshine A4300 (polyethylene terephthalate film, thickness 38 ⁇ m) manufactured by Toyobo Co., Ltd.) as a substrate while peeling off the protective film. Formed a body.
  • a vacuum laminator manufactured by MCK Co., Ltd. was used, and the substrate temperature was 60 ° C., the roller temperature was 120 ° C., the linear pressure was 0.8 MPa, and the linear velocity was 1.0 m / min.
  • the surface of the photosensitive resin layer exposed by peeling the protective film from the photosensitive transfer member was brought into contact with the surface of the PET film which is a substrate.
  • the light transmittance of the PET film in the visible region of 400 to 700 nm was 92.3%.
  • Step X2 Step of exposing the photosensitive resin layer in a pattern
  • step X2 was carried out according to the following procedure.
  • an ultrahigh pressure mercury lamp (wavelength 365 nm) is used.
  • the photosensitive resin layer was pattern-exposed via an exposure mask and a temporary support (exposure step). Table 1 shows the exposure amount (mJ / cm 2 ).
  • Step X3 A step of forming the exposed photosensitive resin layer by alkaline development to form an opening penetrating the photosensitive resin layer] Then, after the temporary support was peeled off, a shower development was carried out for 30 seconds using a 1.0 mass% sodium carbonate aqueous solution (corresponding to an alkaline aqueous solution) at 25 ° C.
  • step X1A a photosensitive resin layer having an opening penetrating the inside of the layer was formed on the substrate.
  • step X4 which will be described later, conductive ink is supplied to the opening to form a conductive composition layer.
  • the conductive composition shown in Table 1 (see the “Types of Conductive Composition” column in Table 1) is shown in Table 1 on a substrate having a photosensitive resin layer having an opening penetrating the inside of the layer.
  • a coating film (conductive composition layer) was formed by coating with a bar coater so as to have a dry thickness of (see “Dry thickness of conductive composition layer ( ⁇ m)” column in Table 1).
  • the coating film (conductive composition) was dried in an oven controlled to the temperature shown in Table 1 (see the column "Drying temperature (° C.) of the conductive composition layer” in Table 1) for 10 minutes.
  • the conductive compositions A to D shown in Table 1 are as follows. Both the conductive compositions A and D contain a solvent, and the main component of the solvent is water.
  • D Bando Chemical Industries, Ltd. Water-based silver nano ink SW-1020
  • step X1 A positive photosensitive resin composition used in step X1 was applied onto the surface of the polyethylene terephthalate film so that the dry thickness was 3 ⁇ m to form a coating film. Next, the coating film was dried with warm air at 90 ° C. for 0.5 hour to prepare a test substrate having a photosensitive resin layer formed on a polyethylene terephthalate film. Next, the thickness of the photosensitive resin layer in the test substrate was measured.
  • a scanning electron microscope SEM is used to observe a cross section including a direction perpendicular to the main surface of the layer, and the thickness of the layer is increased to 10 points or more based on the obtained observation image. The measurement was performed, and the average value T1 ( ⁇ m) was calculated.
  • test substrate was immersed in the conductive composition (temperature: 30 ° C.) used in step X4 for 5 minutes. After soaking for a predetermined time, the test substrate was taken out from the conductive composition and dried at 90 ° C.
  • the thickness of the photosensitive resin layer in the test substrate after the dipping treatment was measured. Specifically, the cross section including the direction perpendicular to the main surface of the layer is observed using SEM, the thickness of the layer is measured at 10 points or more based on the obtained observation image, and the average value T2 ( ⁇ m) is measured. Was calculated.
  • the exposure methods A to C shown in Table 1 are as follows.
  • Step X7 Peeling step> Next, the exposed laminate was subjected to a stripping solution adjusted to the temperature shown in Table 1 (see the "Temperature of stripping solution” and “Type of stripping solution” columns in Table 1, respectively). The exposed photosensitive resin layer was peeled off to form a patterned conductive composition layer on the substrate.
  • the release liquids A to C shown in Table 1 are as follows. A: 5% by mass triethylamine aqueous solution (boiling point 89 ° C) B: 5% by mass monoethanolamine aqueous solution (boiling point 170 ° C) C: 5% by mass diethanolamine aqueous solution (boiling point 280 ° C)
  • ⁇ Process X8 Sintering process>
  • the laminate obtained through step X7 was subjected to a sintering step by the sintering method shown in Table 1 (see the “Sintering method” column in Table 1) to obtain a conductive substrate.
  • the sintering methods A and B shown in Table 1 are as follows. A: Using a drying oven, the mixture was heated at the sintering temperature shown in Table 1 for 60 minutes.
  • Kyoward 200 filter material, aluminum hydroxide powder, manufactured by Kyowa Chemical Industry Co., Ltd.
  • Kyoward 1000 filter material, hydrotalcite powder, manufactured by Kyowa Chemical Industry Co., Ltd.
  • MEHQ Hydroquinone monomethyl ether
  • HAF tetrahydrofuran-2-yl acrylate
  • the content (mass%: ATH / AA / EA / MMA / CHA) of each structural unit in the polymer 3 is 40/2/20/22/16.
  • ATHF corresponds to a structural unit containing an acid-degradable group
  • AA corresponds to a structural unit containing an acid group.
  • the weight average molecular weight of the polymer 3 is 25,000.
  • the glass transition temperature (Tg) of the polymer 3 is 34 ° C., and the acid value is 15.6 mgKOH / g.
  • ⁇ Preparation of Positive Photosensitive Resin Composition 3> The following components were mixed to obtain a mixture having a solid content concentration of 10% by mass. Next, the above mixture was filtered using a filter made of polytetrafluoroethylene having a pore size of 0.2 ⁇ m to obtain a positive photosensitive resin composition 3.
  • Steps X2 to X8 were carried out according to the procedure shown in Table 1 in the same manner as above, except that step X1B was carried out by the following procedure using the above positive photosensitive resin composition 3.
  • Step X1B Step of forming a photosensitive resin layer on a substrate>
  • a PET film Cosmoshine A4300 (polyethylene terephthalate film, thickness 38 ⁇ m) manufactured by Toyobo Co., Ltd.
  • Table 1 Determination of the photosensitive resin layer ( ⁇ m)” in Table 1 )
  • a positive photosensitive resin composition 3 was applied to form a coating film.
  • the coating film was dried with warm air at 90 ° C. to form a laminate having a photosensitive resin layer on the substrate.
  • the light transmittance of the PET film in the visible region of 400 to 700 nm was 92.3%.
  • the photosensitive transfer member 6 was produced by the same production method as the above-mentioned photosensitive transfer member 1 except that the following positive photosensitive resin composition 4 was used instead of the positive photosensitive resin composition 1.
  • ⁇ Preparation of Positive Photosensitive Resin Composition 4> The following components were mixed to obtain a mixed solution. Next, the above mixture was filtered using a filter made of polytetrafluoroethylene having a pore size of 0.2 ⁇ m to obtain a positive photosensitive resin composition 2.
  • Compound F 1,2,3-benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • the conductive substrate was manufactured by the same method as the method for manufacturing the conductive substrate of Example 7 except that the conditions shown in Table 1 were changed.
  • the content (mass%: TBA / PMPMA / AA / MMA / BMA / EA / CHA) of each structural unit in the polymer 4 is 30/1/3/26/5/25/10.
  • TBA corresponds to a structural unit containing an acid-degradable group
  • AA corresponds to a structural unit containing an acid group.
  • the weight average molecular weight of the polymer 4 is 25,000.
  • the glass transition temperature (Tg) of the polymer 4 is 28 ° C.
  • ⁇ Preparation of Positive Photosensitive Resin Composition 5> The following components were mixed to obtain a mixture having a solid content concentration of 10% by mass. Next, the above mixture was filtered using a filter made of polytetrafluoroethylene having a pore size of 0.2 ⁇ m to obtain a positive photosensitive resin composition 5.
  • W-2 Megafuck R08 (manufactured by Dainippon Ink and Chemicals Co., Ltd.) (fluorine and silicon type)
  • Steps X2 to X8 were carried out according to the procedure shown in Table 1 in the same manner as above, except that step X1B was carried out by the following procedure using the above positive photosensitive resin composition 5.
  • Step X1B Step of forming a photosensitive resin layer on the substrate>
  • a PET film Cosmoshine A4300 (polyethylene terephthalate film, thickness 38 ⁇ m) manufactured by Toyobo Co., Ltd.
  • Table 1 Determination of the photosensitive resin layer ( ⁇ m)” in Table 1 )
  • a positive photosensitive resin composition 6 was applied to form a coating film.
  • the coating film was dried with warm air at 90 ° C. to form a laminate having a photosensitive resin layer on the substrate.
  • the light transmittance of the PET film in the visible region of 400 to 700 nm was 92.3%.
  • the conductive substrate was manufactured by the same method as the method for manufacturing the conductive substrate of Example 2 except that the conditions shown in Table 1 were changed.
  • the conductive substrate was manufactured by the same method as the method for manufacturing the conductive substrate of Example 2 except that the conditions shown in Table 1 were changed.
  • the conductive substrate was manufactured by the same method as the method for manufacturing the conductive substrate of Example 7 except that the conditions shown in Table 1 were changed.
  • the conductive substrate was manufactured by the same method as the method for manufacturing the conductive substrate of Comparative Example 1 except that the conditions shown in Table 1 were changed.
  • the conductivity was evaluated by the sheet resistance value.
  • the sheet resistance value use a resistivity meter (Lorester GX MCP-T700 manufactured by Mitsubishi Chemical Corporation) to bring 4 probes into contact with the conductive film, and use the 4-probe method to determine the sheet resistance value (temperature: 23 ° C). It was measured and evaluated according to the following evaluation criteria.
  • Table 1 is shown below.
  • the case where the conductive composition does not dissolve the photosensitive resin layer is represented by "A”
  • the case where the conductive composition dissolves the photosensitive resin layer is represented by "B”. Is represented by. Whether or not the conductive composition dissolves the photosensitive resin layer is determined by the above method.
  • RT in the column of "Temperature of stripping solution [° C.]” in Table 1 is intended to be room temperature.
  • the "Sintering temperature and temperature of organic amines” column in Table 1 the case where the temperature of the organic amines contained in the stripping solution is lower than the sintering temperature is represented by "A” and is contained in the stripping solution. The case where the temperature of the organic amines is higher than the sintering temperature is represented by "B".
  • the defective rate of the conductive layer in the conductive substrate is reduced according to the method for manufacturing the conductive substrate of the example (see “Pattern defect rate” in the table). .). Further, from the comparison between Example 3 and Example 1, it can be confirmed that when the temperature of the stripping liquid in step X7 is less than 50 ° C., the defective rate of the conductive layer is further reduced. Further, from the comparison between Example 3 and Example 2, Example 4, Example 11, and Example 12, the sintering temperature in step X8 is 100 ° C. or higher (preferably 120 ° C. or higher, more preferably 120 ° C. or higher). When the temperature is 130 ° C. or higher, it can be confirmed that the resistance value of the conductive layer is further reduced.
  • Example 3 and Examples 8 and 9 when the sintering treatment of step X8 is carried out at a temperature higher than the boiling point of the organic amines contained in the stripping liquid, the resistance of the conductive layer It can be confirmed that the value is further reduced. From the comparison between Example 3 and Example 10, it can be confirmed that when the acid-degradable group in the acid-degradable resin in the photosensitive resin layer is an acetal group, the defect rate of the conductive layer is further reduced.
  • Substrate 2 Patterned conductive layer 3, 3A Photosensitive resin layer 5 Temporary support 6 Mask 6a Mask opening 7 Opening 8A, 8B Conductive composition layer 10 Conductive substrate 20, 30, 40, 40', 50 laminated body

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PCT/JP2020/048262 2019-12-25 2020-12-23 導電性基板の製造方法、導電性基板、タッチセンサー、アンテナ、電磁波シールド材料 Ceased WO2021132384A1 (ja)

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