CN117476271A - Laminate and method for producing laminate - Google Patents

Laminate and method for producing laminate Download PDF

Info

Publication number
CN117476271A
CN117476271A CN202310938196.8A CN202310938196A CN117476271A CN 117476271 A CN117476271 A CN 117476271A CN 202310938196 A CN202310938196 A CN 202310938196A CN 117476271 A CN117476271 A CN 117476271A
Authority
CN
China
Prior art keywords
resin layer
mass
photosensitive resin
layer
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202310938196.8A
Other languages
Chinese (zh)
Inventor
两角一真
片山晃男
有富隆志
佐藤守正
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
Original Assignee
Fujifilm Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Publication of CN117476271A publication Critical patent/CN117476271A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Materials For Photolithography (AREA)
  • Non-Insulated Conductors (AREA)

Abstract

The invention provides a laminate which is excellent in lamination suitability and is suppressed in migration, and a method for producing the laminate. A laminate and a method for producing a laminate, wherein the laminate comprises a substrate and a conductive portion, the conductive portion has adjacent regions via a resin layer, and the thickness M of the conductive portion and the thickness R of the resin layer satisfy the following formula (1), wherein 0 < R/M < 1/2 (1).

Description

Laminate and method for producing laminate
Technical Field
The present invention relates to a laminate and a method for manufacturing the laminate.
Background
In a display device (for example, an organic Electroluminescence (EL) display device or a liquid crystal display device) including a touch panel such as a capacitive input device, a conductive pattern such as an electrode pattern of a sensor corresponding to a visual recognition portion, wiring of a peripheral wiring portion, wiring of a take-out wiring portion, or the like is provided in the touch panel.
Generally, a method of exposing a layer of a photosensitive resin composition provided on an arbitrary substrate using a photosensitive transfer material through a mask having a desired pattern and then developing the exposed layer is widely used because the number of steps for obtaining a desired pattern shape is small when forming a patterned layer.
Further, the formation of conductive patterns by printing has been conventionally performed, and the conductive patterns based on printing have been widely used in various fields as various sensors such as pressure sensors and biosensors, printed circuit boards, solar cells, capacitors, electromagnetic wave shields, touch panels, antennas, and the like.
In addition, a dry film resist is used for forming the conductive pattern. As a conventional dry film resist, for example, patent document 1 discloses a dry film resist having a multilayer structure, which is characterized in that a photosensitive layer is provided on a support layer, and an overcoat layer having no photoreactivity is provided between the photosensitive layer composed of a photoreactive composition and the support layer.
Patent document 1: japanese patent laid-open No. 11-15150
Disclosure of Invention
An object of an embodiment of the present invention is to provide a laminate which is excellent in lamination suitability and in which migration is suppressed.
Another object of another embodiment of the present invention is to provide a method for producing a laminate which is excellent in lamination suitability and in which migration is suppressed.
Specific embodiments for solving the above problems include the following embodiments.
[1] A laminate having a substrate and a conductive portion,
The conductive portion has a region adjacent to each other via a resin layer,
the thickness M of the conductive portion and the thickness R of the resin layer satisfy the following formula (1),
0＜R/M＜1/2 (1)，
[2] the laminate according to [1], wherein,
the thickness M of the conductive portion and the thickness R of the resin layer satisfy the following formula (1-2),
1/10＜R/M＜1/3 (1-2)
[3] the laminate according to [1] or [2], wherein,
the thickness M of the conductive part is 0.1 μm to 2.0 μm.
[4] The laminate according to any one of [1] to [3], wherein,
the conductive part comprises at least one of a metal monomer and a metal alloy,
the metal monomer is at least 1 selected from gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc and manganese,
the metal alloy is an alloy composed of 2 or more metal elements selected from gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc and manganese.
[5] The laminate according to any one of [1] to [4], wherein,
the conductive part comprises at least one of metal monomer and metal alloy and resin,
the metal monomer is at least 1 selected from gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc and manganese,
the metal alloy is an alloy composed of 2 or more metal elements selected from gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc and manganese.
[6] The laminate according to any one of [1] to [5], wherein,
the conductive part has a linear pattern,
the distance L between the linear patterns is 1-20 μm.
[7] The laminate according to any one of [1] to [6], wherein,
the conductive part has a linear pattern,
the distance L between the linear patterns and the thickness R of the resin layer satisfy the following formula (2),
0＜L×R＜10 (2)
[8] the laminate according to any one of [1] to [7], wherein,
the conductive portion includes the same resin as the resin included in the resin layer.
[9] A laminate having a substrate and a conductive portion,
the conductive portion has a region adjacent to each other via a resin layer,
the thickness M of the conductive portion and the thickness R of the resin layer satisfy the following formula (1),
the thickness M of the conductive part is 0.1 μm to 2.0 μm,
the conductive part comprises at least one of a metal monomer and a metal alloy,
the metal monomer is at least 1 selected from gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc and manganese,
the metal alloy is an alloy composed of at least 2 metal elements selected from the group consisting of gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc and manganese,
the conductive portion includes the same resin as the resin included in the resin layer,
The conductive part has a linear pattern,
the distance L between the linear patterns is 1-20 μm,
the distance L between the linear patterns and the thickness R of the resin layer satisfy the following formula (2),
0＜R/M＜1/2 (1)
0＜L×R＜10 (2)
[10] the method for producing a laminate according to any one of [1] to [9], which comprises, in order:
a step of preparing a substrate having a layer A containing a metal nano-body and a resin;
forming a resist on the layer a;
patterning the resist;
etching the layer a so that at least a part of the resin contained in the layer a remains with the patterned resist as a mask; and
And removing the patterned resist to form a conductive portion.
[11] The method for producing a laminate according to any one of [1] to [9], which comprises, in order:
a step of preparing a substrate having a layer B containing a metal;
forming a resist on the layer B;
patterning the resist;
etching the layer B using the patterned resist as a mask;
removing the patterned resist to form a conductive portion;
forming a negative photosensitive resin layer between adjacent conductive portions; and
And exposing the negative photosensitive resin layer.
[12] The method for producing a laminate according to [11], wherein,
the step of forming a negative photosensitive resin layer between the conductive portions is a step of forming a negative photosensitive resin layer between the conductive portions on the side opposite to the base material and the adjacent conductive portions,
the step of exposing the negative photosensitive resin layer is a step of exposing the substrate from a side opposite to the side having the conductive portion with the conductive portion as a mask,
the method for producing a laminate further includes a step of removing the unexposed negative photosensitive resin layer.
Effects of the invention
According to an embodiment of the present invention, a laminate excellent in lamination suitability and suppressed in migration can be provided.
According to another embodiment of the present invention, a method for manufacturing a laminate having excellent lamination suitability and suppressed migration can be provided.
Drawings
Fig. 1 is a schematic cross-sectional view showing an example of a laminate according to the present invention.
Fig. 2 is a schematic plan view showing the pattern a.
Fig. 3 is a schematic plan view showing the pattern B.
Detailed Description
The present invention will be described in detail below. The following description of the elements is sometimes based on the representative embodiments of the present invention, but the present invention is not limited to such embodiments, and can be implemented with appropriate modifications within the scope of the object of the present invention.
In the present invention, the numerical range indicated by the term "to" refers to a range in which numerical values described before and after the term "to" are included as a lower limit value and an upper limit value, respectively.
In the present invention, the upper limit value or the lower limit value of a numerical range described in stages may be replaced with the upper limit value or the lower limit value of a numerical range described in other stages. In the numerical ranges described in the present invention, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value described in the examples.
In the present invention, in the case where the amounts of the respective components in the composition are mentioned, when a plurality of substances corresponding to the respective components are present in the composition, the total amount of the plurality of components present in the composition is referred to unless specified otherwise.
In the present invention, a combination of 2 or more preferred embodiments is a more preferred embodiment.
In the present invention, the term "process" includes not only an independent process but also a process which cannot be clearly distinguished from other processes, as long as the intended purpose of the process can be achieved.
In the present invention, "transparent" means that the average transmittance of visible light having a wavelength of 400nm to 700nm is 80% or more, preferably 90% or more.
In the present invention, the "average transmittance of visible light" is a value measured using a spectrophotometer. As the spectrophotometer, for example, a spectrophotometer manufactured by Hitachi, ltd (model: U-3310) can be used. However, the spectrophotometer is not limited thereto.
In the present invention, unless otherwise specified, the molecular weight of the compound having a molecular weight distribution is the weight average molecular weight (Mw; the same applies hereinafter).
In the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured by Gel Permeation Chromatography (GPC) unless otherwise specified.
The values measured by GPC were the following values: TSKgel (registered trademark) GMHxL, TSKgel (registered trademark) G4000HxL, or TSKgel (registered trademark) G2000HxL (all product names manufactured by TOSOH CORPORATION) were used as a column, tetrahydrofuran (THF) was used as an eluent, a differential refractometer was used as a detector, polystyrene was used as a standard substance, and the polystyrene conversion value was measured by a GPC analysis device.
In the present invention, "water-soluble" means that the solubility in 100g of water having a liquid temperature of 22℃and a pH of 7.0 is 0.1g or more, and for example, "water-soluble resin" means a resin satisfying the above solubility condition.
In the present invention, "solid component" in the composition means a component forming a composition layer formed using the composition, and in the case where the composition contains a solvent, means all components excluding the solvent. In addition, as the component forming the composition layer, a liquid component other than the solvent is also regarded as a solid component. In the present invention, "solvent" means water and an organic solvent.
In the present invention, unless otherwise specified, "exposure" includes exposure using light and drawing using particle rays such as electron beams and ion beams. The light used for exposure includes, in general, an open line spectrum of a mercury lamp, extreme ultraviolet rays typified by excimer laser, extreme ultraviolet rays (EUV light), activation rays (active energy rays) such as X-rays and electron beams, and the like.
In the present invention, "(meth) acrylic acid" is a term including both "acrylic acid" and "methacrylic acid", "(meth) acrylic acid ester" is a term including both "acrylic acid ester" and "methacrylic acid ester", and "(meth) acryl" is a term including both "acryl" and "methacryl".
In the labeling of the group (atomic group) in the present invention, the label which is not labeled with a substituent and is unsubstituted includes a group having no substituent, and also includes a group having a substituent. For example, an "alkyl group" is a group including not only an alkyl group having no substituent (also referred to as an "unsubstituted alkyl group") but also an alkyl group having a substituent (also referred to as a "substituted alkyl group").
The chemical structural formula in the present invention is sometimes described by a simple general structural formula in which the hydrogen atom is omitted.
In the present invention, "mass%" has the same meaning as "weight%", and "part by mass" has the same meaning as "part by weight".
[ laminate ]
The laminate according to the present invention is a laminate comprising: the conductive part has adjacent regions through the resin layer, and the thickness M of the conductive part and the thickness R of the resin layer satisfy the following formula (1).
0＜R/M＜1/2 (1)
Conventionally, a technique for forming a circuit wiring by etching a metal layer such as copper using a wiring pattern formed by a resist (etching resist) as a mask is known (refer to patent document 1, etc.). With regard to the wiring pattern obtained by such a process, having a conductive portion formed of a residual metal layer, a non-conductive portion is made into a concave shape from which the metal layer is removed by etching, and is formed into a shape having irregularities of a thickness component of the conductive portion on a circuit face.
In protecting wiring patterns on a wiring board, it is common to laminate an optical film (for example, OCA (Optical Clear Adhesive, optically clear adhesive) film) having adhesiveness on a circuit surface and laminate a protective film. However, if the irregularities are present on the circuit surface, air may be mixed during lamination, and air bubbles may be generated between the optical film and the wiring board. The bubbles may not only affect visibility, but also cause malfunction.
In contrast, in the laminate according to the present invention, the conductive portions have adjacent regions via the resin layer, in other words, the resin layer is provided between the conductive portions, so that the optical film tends to adhere to the resin layer during lamination. It is considered that if the optical film is adhered to the resin layer, air is hardly mixed, and even if air is mixed, air is easily escaped, so that bubbles are hardly generated. In the laminate according to the present invention, the resin layer is provided between the conductive portions, and the thickness M of the conductive portions and the thickness R of the resin layer satisfy the above formula (1), and the difference between the irregularities is small compared with the irregularities. Therefore, it is considered that air mixing is suppressed at the time of lamination, and air bubbles are hardly generated. From the above, it is assumed that the laminate according to the present invention is excellent in lamination suitability. From the viewpoint of excellent lamination suitability, the region where the conductive portions are adjacent via the resin layer is preferably 50% or more, more preferably 70% or more, of the total length of the conductive portions. The area where the conductive portions are adjacent via the resin layer can be set to 100% or less of the total length of the conductive portions.
On the other hand, the resin layer existing between the conductive portions may become a cause of migration. This is because when a resin layer is present between the conductive portions, when a current is applied to the conductive portions, ionized metal may move in the resin layer and be easily diffused. Migration causes a change in the size of the conductive pattern, and thus becomes a cause of short circuit.
On the other hand, it is assumed that the laminate according to the present invention has the resin layer between the conductive portions and the occurrence of migration is suppressed because the thickness M of the conductive portions and the thickness R of the resin layer satisfy the above formula (1).
The laminate according to the present invention is not limited to the above-described estimation, but will be described as an example.
The laminate according to the present invention will be described in detail below.
An example of the laminate according to the present invention will be described below with reference to the drawings.
Fig. 1 is a schematic cross-sectional view showing an example of a laminate according to the present invention.
However, the laminate according to the present invention is not limited to the laminate having the structure shown in fig. 1.
The laminate 100 shown in fig. 1 includes a base material 30 and conductive portions 40 provided on the base material 30, and a resin layer 50 is provided between adjacent conductive portions 40.
Relation between thickness M of conductive portion and thickness R of resin layer
The thickness M of the conductive portion and the thickness R of the resin layer of the laminate according to the present invention satisfy the following formula (1).
R/M exceeding 0 means that a resin layer is provided between the conductive portions.
If R/M is less than 1/2, migration can be suppressed.
From the viewpoints of lamination suitability and suppression of occurrence of migration, the laminate according to the present invention preferably satisfies the following formula (1-1), more preferably the following formula (1-2), and even more preferably the following formula (1-3).
0＜R/M＜1/2 (1)
1/20≤R/M≤1/2.5 (1-1)
1/10＜R/M＜1/3 (1-2)
1/10＜R/M＜1/3.5 (1-3)
The thickness M of the conductive portion is not particularly limited, but is preferably 0.01 μm to 10.0 μm, more preferably 0.05 μm to 5.0 μm, still more preferably 0.08 μm to 3.0 μm, and particularly preferably 0.1 μm to 2.0 μm, from the viewpoints of conductivity and film formability, for example.
The thickness M of the conductive portion of the laminate according to the present invention can be measured by the following method.
The laminate was cut using an ultra-thin microtome to prepare a pattern section of the conductive portion and the resin layer. In the production, the laminate is cut so that the cross section is substantially perpendicular to the longitudinal direction of the pattern. The thickness of the center portion in the width direction of the pattern of the conductive portion in the cross section was measured by observing the cross section of the fabricated pattern using a Scanning Electron Microscope (SEM) under an acceleration voltage of 5 kV. The above-described production and measurement (in other words, 5 cross sections were produced, and the thickness of the center portion in the width direction of the pattern of the conductive portion in each cross section was measured) were repeated 5 times, and the obtained 5 measured values were arithmetically averaged. The value obtained by the above method is taken as the thickness M of the conductive portion.
As the scanning electron microscope, a scanning electron microscope manufactured by JEOL co., ltd (model: JSM-7200F) can be suitably used. However, the scanning electron microscope is not limited thereto.
The thickness R of the resin layer is not particularly limited, but is preferably 0.01 μm to 5.0 μm, more preferably 0.05 μm to 2.5 μm, still more preferably 0.08 μm to 1.5 μm, and particularly preferably 0.1 μm to 1.0 μm, from the viewpoint of suppressing occurrence of migration and film formability, for example.
When the thickness R of the resin layer is 5.0 μm or less, migration tends to be more suppressed.
The thickness R of the resin layer of the laminate according to the present invention can be measured by the following method.
The laminate was cut using an ultra-thin microtome to prepare a pattern section of the conductive portion and the resin layer. In the production, the laminate is cut so that the cross section is substantially perpendicular to the longitudinal direction of the pattern. To impart conductivity, the resin layer portion of the cross section of the produced pattern is carbon-coated. The thickness of the center portion in the width direction of the pattern of the resin layer in the cross section was measured by observing the cross section of the fabricated pattern using a Scanning Electron Microscope (SEM) under an acceleration voltage of 5 kV. The above-described production and measurement were repeated 5 times (in other words, 5 sections were produced, and the resin layer portion of each produced section was carbon-coated, and then the thickness in the widthwise central portion of the pattern of the resin layer in each section was measured), and the obtained 5 measured values were arithmetically averaged. The value obtained by the above method was taken as the thickness R of the resin layer.
As the scanning electron microscope, a scanning electron microscope manufactured by JEOL co., ltd (model: JSM-7200F) can be suitably used. However, the scanning electron microscope is not limited thereto.
Distance L between Linear patterns
The conductive portion in the laminate according to the present invention preferably has a linear pattern.
In the present invention, the distance between the linear patterns of the conductive portion is referred to as "distance L between the linear patterns".
The distance L between the linear patterns is not particularly limited, but is preferably 1 μm to 20 μm, more preferably 5 μm to 20 μm, still more preferably 10 μm to 20 μm, and particularly preferably 10 μm to 15 μm from the viewpoints of lamination suitability and suppression of occurrence of migration.
If the distance L between the linear patterns is 1 μm or more, ionized metal tends to be more difficult to move, and migration tends to be more suppressed. When the distance L between the linear patterns is 1 μm or more, air is more difficult to mix in during lamination and lamination suitability is more excellent.
If the distance L between the linear patterns is 20 μm or less, for example, when the conductive portion in the laminate according to the present invention is used as a peripheral wiring, a pickup wiring, or the like of a touch panel, the wiring tends to be more dense.
Relation between distance L between line patterns and thickness R of resin layer
From the viewpoints of lamination suitability and suppression of migration, the distance L between linear patterns of the laminate according to the present invention and the thickness R of the resin layer preferably satisfy the following formula (2), more preferably the following formula (2-1), and even more preferably the following formula (2-2).
0＜L×R＜10 (2)
0.5＜L×R＜8 (2-1)
1＜L×R＜6 (2-2)
In the laminate according to the present invention, the distance between the conductive portions having the linear patterns (i.e., the distance L between the linear patterns) can be measured by the following method.
The laminate was cut using an ultra-thin microtome to prepare a pattern section of the conductive portion and the resin layer. In the production, the laminate is cut so that the cross section is substantially perpendicular to the longitudinal direction of the pattern. To impart conductivity, the resin layer portion of the cross section of the produced pattern is carbon-coated. The cross section of the fabricated pattern was observed under an acceleration voltage of 5kV using a Scanning Electron Microscope (SEM), and the width of the resin layer present between the conductive portions in the cross section was measured. The above-described production and measurement were repeated 5 times (in other words, 5 sections were produced, carbon coating was performed on the resin layer portion of each produced section, and then the width of the resin layer present between the conductive portions in each section was measured), and the obtained 5 measured values were arithmetically averaged. The value obtained by the above method is taken as the distance L between the line patterns.
As the scanning electron microscope, a scanning electron microscope manufactured by JEOL co., ltd (model: JSM-7200F) can be suitably used. However, the scanning electron microscope is not limited thereto.
[ conductive part ]
The laminate according to the present invention has a conductive portion.
In the present invention, "conductive portion" means a region having conductivity (so-called conductive region), and "conductivity" means a volume resistivity of less than 1×10 6 Properties of Ω cm. The volume resistivity of the conductive region is preferably less than 1×10 4 Omega cm. In addition, "non-conductive" means that the volume resistivity is 1X 10 6 And omega cm or more.
The volume resistivity can be measured by a commercially available resistivity measuring instrument (for example, nittoseiko Analytech co., ltd. Loresta GX MCP-T700 (product name)).
The conductive portion preferably has a linear pattern. That is, the conductive portion is preferably formed with a conductive pattern such as a wiring pattern.
The line width of the conductive portion (so-called conductive pattern) having the linear pattern is not particularly limited, but is, for example, preferably 1 μm to 20 μm, more preferably 5 μm to 20 μm, still more preferably 10 μm to 20 μm, and particularly preferably 10 μm to 15 μm.
The material of the conductive portion is not particularly limited as long as it has conductivity.
The conductive portion preferably contains at least 1 selected from the group consisting of a metal monomer, a metal alloy, and a metal oxide.
The conductive portion may be formed of at least 1 selected from the group consisting of a metal monomer, a metal alloy, and a metal oxide, or may include a resin and at least 1 selected from the group consisting of a metal monomer, a metal alloy, and a metal oxide.
And, the conductive portion may include conductive silicon dioxide.
Examples of the metal monomer include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, nickel, platinum, palladium, and manganese.
The metal monomer is preferably at least 1 selected from gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, more preferably at least 1 selected from silver and copper, and still more preferably silver.
Examples of the metal alloy include alloys composed of 2 or more metal elements selected from gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, nickel, platinum, palladium, and manganese.
The metal alloy is preferably an alloy composed of 2 or more metal elements selected from gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, and more preferably an alloy of silver and copper.
Examples of the metal Oxide include ITO (Indium Tin Oxide,
indium tin oxide) and IZO (Indium Zinc Oxide ).
Preferably, the conductive portion includes at least one of a metal monomer and a metal alloy, and the metal monomer is at least 1 selected from gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, and the metal alloy is an alloy composed of 2 or more metal elements selected from gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese. Further, it is also preferable that the conductive portion includes at least one of a metal monomer and a metal alloy, and the metal monomer is at least 1 selected from gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, and the metal alloy is preferably an alloy composed of 2 or more metal elements selected from gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese.
The conductive portion may include a metal nano-body and a resin.
The shape of the metal nano-body is not particularly limited as long as it is a known shape.
The metal nano-bodies are preferably metal nano-particles or metal nanowires, more preferably metal nano-particles.
The metal nanoparticles may be spherical particles, plate-like particles, or irregularly shaped particles.
The average primary particle diameter of the metal nanoparticles is preferably 0.1nm to 500nm, more preferably 1nm to 200nm, and even more preferably 1nm to 100nm from the viewpoints of stability and fusion temperature.
The average primary particle diameter of the metal nanoparticles in the present invention can be obtained as follows: a scanning electron microscope photograph (SEM image) of 100 particles was taken using a scanning electron microscope (for example, S-3700N (model) manufactured by Hitachi High-Technologies Corporation), and the particle diameter of the particles was measured using an image processing measuring device (for example, LUZEX AP manufactured by NIRECO), to obtain an arithmetic average value. That is, the particle diameter described in the present invention is expressed by the diameter of a particle when the projected shape of the particle is a circle, and by the diameter of a circle having the same area as the projected area of the particle when the particle is an irregular shape other than a sphere.
From the viewpoint of conductivity, the metal nanoparticles preferably contain a metal more noble than silver, and in this case, flat particles at least a part of which is coated with gold are more preferably contained.
"a metal that is more noble than silver" means "a metal having a standard electrode potential higher than that of silver".
The ratio of the metal noble than silver to silver in the metal nanoparticle is preferably 0.01 atomic% to 5 atomic%, more preferably 0.1 atomic% to 2 atomic%, and even more preferably 0.2 atomic% to 0.5 atomic%.
The content of the metal more noble than silver can be measured by, for example, high-frequency inductively coupled plasma (ICP: inductively Coupled Plasma) emission spectrometry after dissolving the sample with an acid or the like.
Examples of the shape of the metal nanowire include a columnar shape, a rectangular parallelepiped shape, and a columnar shape having a polygonal cross section.
In applications requiring high transparency, the metal nanowire preferably has at least one of a columnar shape and a columnar shape having a polygonal cross section.
The cross-sectional shape of the metal nanowire can be observed using, for example, a Transmission Electron Microscope (TEM).
The diameter (so-called short axis length) of the metal nanowire is not particularly limited, but is preferably 50nm or less, more preferably 35nm or less, and further preferably 20nm or less, for example, from the viewpoint of transparency.
For example, the lower limit of the diameter of the metal nanowire is preferably 5nm or more from the viewpoints of oxidation resistance and durability.
The length of the metal nanowire (so-called long axis length) is not particularly limited, but is preferably 5 μm or more, more preferably 10 μm or more, and further preferably 30 μm or more, for example, from the viewpoint of conductivity.
For example, from the viewpoint of suppressing the formation of aggregates during the production process, the upper limit of the length of the metal nanowire is preferably 1mm or less.
The diameter and length of the metal nanowires can be measured using, for example, a Transmission Electron Microscope (TEM) or an optical microscope.
Specifically, measurement was performed of diameters and lengths of 300 metal nanowires arbitrarily selected from among metal nanowires observed using a Transmission Electron Microscope (TEM) or an optical microscope in magnification. The measured values were arithmetically averaged, and the obtained values were set as the diameter and length of the metal nanowire.
From the viewpoints of dispersibility and conductivity, the metal nanoparticle is preferably a nanoparticle having an aspect ratio of 1:1 to 1:10 and a sphere equivalent diameter of 1nm to 200 nm.
When the conductive portion includes metal nano-bodies, the conductive portion may include only 1 kind of metal nano-bodies, or may include 2 or more kinds of metal nano-bodies.
When the conductive portion includes a metal nano-body, the content of the metal nano-body in the conductive portion is preferably 1 to 99 mass%, more preferably 1 to 95 mass%, and even more preferably 1 to 90 mass% with respect to the total mass of the conductive portion from the viewpoints of conductivity and dispersion stability.
In the case where the conductive portion includes a resin, the resin is preferably a binder polymer from the viewpoint of durability.
Examples of the resin include, but are not particularly limited to, acrylic resins [ e.g., benzyl methacrylate/methacrylic acid/acrylic acid copolymer ], polyester resins [ e.g., polyethylene terephthalate (PET) ], polycarbonate resins, polyimide resins, polyamide resins, polyurethane resins, polyolefin resins (e.g., polypropylene), polynorbornene, and cellulose resins [ e.g., as cellulose resins, e.g., hydroxypropyl methylcellulose (HPMC), hydroxyethyl cellulose (HEC), methylcellulose (MC), hydroxypropyl cellulose (HPC), carboxymethyl cellulose (CMC), cellulose ], polyvinyl alcohol (PVA), and polyvinylpyrrolidone.
The resin may be a conductive polymer material.
Examples of the conductive polymer material include polyaniline and polythiophene.
From the viewpoint of durability, the resin preferably contains at least 1 selected from the group consisting of acrylic resins and urethane resins.
The glass transition temperature (Tg) of the resin is not particularly limited, but is, for example, preferably 180 ℃ or lower, more preferably 40 to 160 ℃, and still more preferably 60 to 150 ℃.
In the present invention, the glass transition temperature of the resin can be measured by Differential Scanning Calorimetry (DSC). Specifically, according to JIS K7121: 1987 or JIS K6240: 2011, the glass transition temperature of the resin is measured. The glass transition temperature in the present invention uses an extrapolated glass transition onset temperature (also referred to as "Tig").
The method of measuring the glass transition temperature is described more specifically.
In the case of determining the glass transition temperature, the temperature is kept about 50 ℃ lower than the Tg of the predicted resin until the device is stabilized, and then the heating rate is increased: 20 ℃ per minute, heated to a temperature about 30 ℃ higher than the temperature at which the glass transition ends, and a Differential Thermal Analysis (DTA) curve or DSC curve is plotted.
The extrapolated glass transition onset temperature (Tig), that is, the glass transition temperature Tg in the present invention, is obtained as the temperature at which the intersection of a straight line obtained by extending the low-temperature side base line to the high temperature side in the DTA curve or DSC curve and a tangential line drawn at the point where the slope of the curve of the stepwise change portion of the glass transition becomes maximum.
The weight average molecular weight of the resin is not particularly limited, but is, for example, preferably 1,000 ～ 2,000,000, more preferably 10,000 ～ 1,200,000.
When the conductive portion contains a resin, 1 kind of resin may be contained, or 2 or more kinds may be contained.
When the conductive portion contains a resin, the content of the resin in the conductive portion is preferably 1 to 90% by mass, more preferably 5 to 80% by mass, and even more preferably 10 to 70% by mass, relative to the total mass of the conductive portion, from the viewpoints of the formability and conductivity of the conductive portion.
When the conductive portion includes a resin, the resin included in the conductive portion may be the same as or different from the resin included in the resin layer described later.
When the conductive portion includes a resin, the conductive portion preferably includes the same resin as the resin included in the resin layer described later, from the viewpoint of lamination suitability.
The conductive portion may contain various additives.
The additive may be a known additive such as a surfactant.
Examples of the surfactant include RADISOL (registered trademark) A-90 [ solid content concentration: 1% by mass, NOF CORPORATION, and naroacy (registered trademark) CL-95 (solid content concentration): 1 mass%, sanyo Chemical Industries, ltd.
Also, the conductive portion may contain inorganic particles.
Examples of the inorganic particles include silica particles, mullite particles, and alumina particles.
In the case where a plurality of stacked bodies according to the present invention have conductive portions, the plurality of conductive portions may be conductive portions of the same material or conductive portions of different materials.
[ resin layer ]
In the laminate according to the present invention, the conductive portion has been described as having adjacent regions via the resin layer. In other words, the laminate according to the present invention has a resin layer between adjacent conductive portions.
The resin layer contains a resin.
From the viewpoint of durability, the resin is preferably a binder polymer.
Examples of the resin include acrylic resins [ e.g., benzyl methacrylate/methacrylic acid/acrylic acid copolymer ], polyester resins [ e.g., polyethylene terephthalate (PET) ], polycarbonate resins, polyimide resins, polyamide resins, polyurethane resins, polyolefins (e.g., polypropylene), polynorbornenes, and cellulose resins [ e.g., as cellulose resins, e.g., hydroxypropyl methylcellulose (HPMC), hydroxyethyl cellulose (HEC), methylcellulose (MC), hydroxypropyl cellulose (HPC), carboxymethyl cellulose (CMC), and cellulose ], polyvinyl alcohol (PVA), and polyvinylpyrrolidone.
From the viewpoint of migration resistance, the resin preferably contains at least 1 selected from the group consisting of acrylic resins and urethane resins.
The glass transition temperature (Tg) of the resin is not particularly limited, but is, for example, preferably 180 ℃ or lower, more preferably 40 to 160 ℃, and still more preferably 60 to 150 ℃.
The weight average molecular weight of the resin is not particularly limited, but is, for example, preferably 1,000 ～ 2,000,000, more preferably 10,000 ～ 1,200,000.
The resin layer may contain 1 kind of resin or 2 or more kinds of resin.
The content of the resin in the resin layer is not particularly limited, but is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and even more preferably 80 to 100% by mass, based on the total mass of the resin layer.
The resin layer may contain various additives.
The additive may be a known additive such as a surfactant.
Specific examples of the surfactant in the resin layer are the same as those in the conductive portion, and therefore description thereof is omitted.
Also, the resin layer may contain inorganic particles.
Specific examples of the inorganic particles in the resin layer are the same as specific examples of the inorganic particles in the conductive portion, and therefore, description thereof is omitted.
The resin layer preferably has high transparency.
The transmittance of the resin layer with respect to light having a wavelength of 380nm to 780nm is preferably 60% or more, more preferably 70% or more.
The resin layer is preferably non-conductive.
The total content of the metal monomers and the metal alloys in the resin layer is preferably less than 10 mass%, more preferably less than 5 mass%, even more preferably less than 1 mass%, and still more preferably less than 0.1 mass% relative to the total mass of the resin layer. The total content of the metal monomers and the metal alloys in the resin layer may be 0 mass% or more with respect to the total mass of the resin layer.
[ substrate ]
The laminate according to the present invention has a base material.
As the substrate used in the present invention, a known substrate may be used.
The substrate may have any layer having no conductivity as required.
Examples of the substrate include a resin substrate, a glass substrate, and a semiconductor substrate.
A preferred embodiment of the base material is described in paragraph [0140] of international publication No. 2018/155193, for example, and these descriptions are incorporated herein by reference.
Examples of the material constituting the base material include glass, silicon, and resin.
The substrate is preferably transparent.
As the transparent glass substrate, reinforced glass typified by gorilla glass of Corning Incorporated can be given. As the transparent glass substrate, materials used in japanese patent application laid-open publication nos. 2010-86684 and 2010-152809 and 2010-257492 can be used.
When a film substrate is used as the substrate, a film substrate having low optical distortion and/or high transparency is preferably used. Examples of such film substrates include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, polyimide, and cycloolefin polymer.
In the case of roll-to-roll manufacturing, the substrate is preferably a film substrate.
In the case of manufacturing the circuit wiring for touch panel by a roll-to-roll method, the substrate is preferably a sheet-like resin composition.
The substrate may have a conductive layer on only one surface, or may have a conductive layer on both surfaces.
The thickness of the base material is not particularly limited, but is, for example, preferably 50 μm to 300. Mu.m, more preferably 50 μm to 200. Mu.m, still more preferably 50 μm to 150. Mu.m.
The thickness of the substrate refers to the average thickness measured by the following method.
In the cross-sectional view of the substrate in the thickness direction, an arithmetic average value of the thickness of the substrate measured at 10 points selected arbitrarily is obtained, and the obtained value is taken as the average thickness of the substrate. The cross-sectional view image of the substrate in the thickness direction can be obtained by a Scanning Electron Microscope (SEM).
Preferred embodiments of laminate
From the viewpoints of lamination suitability and suppression of occurrence of migration, the following embodiments are preferable as embodiments of the laminate according to the present invention: a laminate comprising a substrate and a conductive portion, wherein the conductive portion has adjacent regions via a resin layer, the thickness M of the conductive portion and the thickness R of the resin layer satisfy the following formula (1), the thickness M of the conductive portion is 0.1 [ mu ] M to 2.0 [ mu ] M, the conductive portion comprises at least one of a metal monomer and a metal alloy, the metal monomer is at least 1 selected from gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc and manganese, the metal alloy is an alloy composed of 2 or more metal elements selected from gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc and manganese, the conductive portion comprises the same resin as the resin contained in the resin layer, the conductive portion has a linear pattern, the distance L between the linear patterns is 1 [ mu ] M to 20 [ mu ] M, and the distance L between the linear patterns and the thickness R of the resin layer satisfy the following formula (2).
0＜R/M＜1/2 (1)
0＜L×R＜10 (2)
< use >
The laminate of the present invention can be suitably used for circuit wiring of a touch panel, circuit wiring of various electronic devices, and the like. The conductive portion in the laminate according to the present invention can be suitably used as, for example, a peripheral wiring or a pickup wiring of a touch panel.
The laminate according to the present invention can be applied to various devices.
Examples of the applicable device include an input device, preferably a touch panel, and more preferably a capacitive touch panel.
The input device including the laminate according to the present invention can be applied to display devices such as an organic electroluminescence display device and a liquid crystal display device.
The laminate according to the present invention can be suitably used in a flexible display device (for example, a flexible touch panel).
[ method for producing laminate ]
The method for producing a laminate according to the present invention (hereinafter, simply referred to as "production method") is not particularly limited as long as the laminate according to the present invention can be produced.
The manufacturing method according to the present invention is preferably a manufacturing method based on a roll-to-roll method. As the manufacturing method according to the present invention, for example, the manufacturing method according to embodiment 1 or the manufacturing method according to embodiment 2 described below is preferable.
[ method for manufacturing of embodiment 1 ]
The manufacturing method according to embodiment 1 includes, in order: a step of preparing a substrate having a layer a including a metal nano-body and a resin (hereinafter, also referred to as "step 1-1"); a step of forming a resist on the layer a (hereinafter, also referred to as "step 1-2"); a step of patterning the resist (hereinafter, also referred to as "steps 1 to 3"); a step of etching the layer a while leaving at least a part of the resin contained in the layer a with the patterned resist as a mask (hereinafter, also referred to as "step 1-4"); and a step of removing the patterned resist to form a conductive portion (hereinafter, also referred to as "steps 1 to 5").
The steps of the above steps will be described in detail below.
< procedure 1-1>
Step 1-1 is a step of preparing a substrate having a layer A containing a metal nanoparticle and a resin,
as the base material, the above-described base material can be suitably used.
The metal nano-body in the layer a is preferably a metal nano-body in the conductive portion described above.
The layer a may contain 1 kind of metal nano-body or 2 or more kinds.
The content of the metal nanoparticles in the layer a is preferably 1 to 99 mass%, more preferably 1 to 95 mass%, and even more preferably 1 to 90 mass% relative to the total mass of the layer a.
The resin in the layer a is preferably a resin in the conductive portion described above.
The layer a may contain 1 kind of resin or 2 or more kinds of resin.
The content of the resin in the layer a is preferably 1 to 90% by mass, more preferably 5 to 80% by mass, and even more preferably 10 to 70% by mass, based on the total mass of the layer a.
Layer a may further comprise various additives.
Examples of the various additives in the layer a include the various additives in the conductive portion described above.
The thickness M of the layer a is not particularly limited, but is preferably 0.01 μm to 10.0 μm, more preferably 0.05 μm to 5.0 μm, still more preferably 0.08 μm to 3.0 μm, and particularly preferably 0.1 μm to 2.0 μm, from the viewpoints of conductivity and film formability, for example.
The thickness of the layer a is an average value (i.e., average thickness) of the thicknesses of 10 sites measured by observing a cross section in a direction perpendicular to the in-plane direction using a Scanning Electron Microscope (SEM).
The method of forming the layer a is not particularly limited, but is preferably a method of forming by applying conductive ink, which is a material in which a conductive material containing metal nano-bodies is dispersed in a liquid. After the application, drying, calcination, and the like may be performed as needed.
The method of applying the electroconductive ink is not particularly limited, but examples thereof include an inkjet method, a spray method, a roll coating method, a bar coating method, a curtain coating method, and a die coating method (i.e., a slit coating method).
The conductive ink may be a curable ink, for example, a thermosetting ink, a photo-curable ink, or a thermal and photo-curable ink.
The conductive ink preferably contains a metal nanoparticle and a resin.
The metal nano-body in the conductive ink is preferably a metal nano-body in the conductive portion described above.
The conductive ink may contain 1 kind of metal nano-body or 2 or more kinds.
The content of the metal nano-bodies in the conductive ink is preferably 1 to 90 mass%, more preferably 1 to 80 mass%, and even more preferably 1 to 70 mass% relative to the total mass of the conductive ink.
The resin in the conductive ink is preferably a resin in the conductive portion described above.
The conductive ink may contain 1 kind of resin or 2 or more kinds of resin.
The content of the resin in the conductive ink is preferably 0.1 to 90% by mass, more preferably 0.3 to 80% by mass, and even more preferably 0.5 to 70% by mass, based on the total mass of the conductive ink.
The conductive ink may contain a polymerizable compound.
When the conductive ink contains a polymerizable compound, the conductive ink preferably contains a polymerization initiator in addition to the polymerizable compound.
From the viewpoint of the strength of the layer a, the polymerizable compound is preferably an ethylenically unsaturated compound, more preferably a (meth) acrylate compound. The (meth) acrylate compound is also preferably a urethane (meth) acrylate compound.
From the viewpoint of the strength of the layer a, the polymerizable compound preferably contains a polymerizable compound having 2 or more functions, more preferably contains a polymerizable compound having 3 to 10 functions, and still more preferably contains a polymerizable compound having 4 to 8 functions.
Further, from the viewpoint of the strength of the layer a, the polymerizable compound preferably contains an ethylenically unsaturated compound having 2 or more functions, and more preferably contains a (meth) acrylate compound having 2 or more functions.
As the polymerizable compound, commercially available ones can be used.
Examples of the commercially available polymerizable compounds include ARONIX (registered trademark) M-350 and ARONIX (registered trademark) M-1960 manufactured by TOAGOSEI CO., LTD.
As the polymerizable compound, a polymerizable compound used for a photosensitive resin layer described later can be suitably used.
When the electroconductive ink contains a polymerizable compound, the electroconductive ink may contain only 1 polymerizable compound, or may contain 2 or more polymerizable compounds.
When the conductive ink contains a polymerizable compound, the content of the polymerizable compound in the conductive ink is preferably 0.1 to 60% by mass, more preferably 0.3 to 50% by mass, and even more preferably 0.5 to 40% by mass, relative to the total solid content in the conductive ink, from the viewpoint of the strength of the layer a.
The polymerization initiator is not particularly limited, and a photopolymerization initiator is preferable.
The photopolymerization initiator is preferably a photo radical polymerization initiator.
The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.
Examples of the photopolymerization initiator include a photopolymerization initiator having an oxime ester structure (hereinafter, also referred to as an "oxime-based photopolymerization initiator"), a photopolymerization initiator having an α -aminoalkyl benzophenone structure (hereinafter, also referred to as an "α -aminoalkyl benzophenone-based photopolymerization initiator"), a photopolymerization initiator having an α -hydroxyalkyl benzophenone structure (hereinafter, also referred to as an "α -hydroxyalkyl benzophenone-based polymerization initiator"), a photopolymerization initiator having an acylphosphine oxide structure (hereinafter, also referred to as an "acylphosphine oxide-based photopolymerization initiator"), and a photopolymerization initiator having an N-phenylglycine structure (hereinafter, also referred to as an "N-phenylglycine-based photopolymerization initiator").
Among these, preferable as the photopolymerization initiator is an α -hydroxyalkyl benzophenone-based polymerization initiator [ e.g., omnirad (registered trademark) 184 manufactured by IGM Resins b.v. ].
As the polymerization initiator, a polymerization initiator used for a photosensitive resin layer described later can also be suitably used.
When the electroconductive ink contains a polymerization initiator, it may contain only 1 kind of polymerization initiator or 2 or more kinds of polymerization initiator.
When the electroconductive ink contains a polymerization initiator, the content of the polymerization initiator in the electroconductive ink is preferably 0.01 to 20% by mass, more preferably 0.03 to 15% by mass, and even more preferably 0.05 to 10% by mass, relative to the total solid content in the electroconductive ink, from the viewpoint of the strength of the layer a.
The conductive ink also preferably contains a metal nanoparticle and a thermally crosslinkable compound.
The thermally crosslinkable compound is preferably a blocked isocyanate compound, for example.
As the thermally crosslinkable compound in the conductive ink, a thermally crosslinkable compound used in a photosensitive resin layer described later can be suitably used.
When the conductive ink contains a thermally crosslinkable compound, the conductive ink may contain only 1 thermally crosslinkable compound or may contain 2 or more thermally crosslinkable compounds.
When the conductive ink contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound in the conductive ink is preferably 0.1 to 20% by mass, more preferably 0.3 to 15% by mass, and even more preferably 0.5 to 10% by mass, relative to the total solid content in the conductive ink, from the viewpoint of the strength of the layer a.
The conductive ink may contain various additives.
The additive may be a known additive such as a dispersant.
Examples of the dispersant include DisperBYK-111 (BYK co., LTD).
The conductive ink may contain a solvent.
The solvent contained in the conductive ink may be water, an organic solvent, or a mixture of these.
The organic solvent is preferably a hydrocarbon such as toluene, dodecane, tetradecane, cyclododecene, n-heptane, or n-undecane, or an alcohol such as ethanol or isopropanol.
Layer a is preferably formed to be larger than the desired conductive portion size.
< procedure 1-2>
Step 1-2 is a step of forming a resist on the layer a prepared in step 1-1.
The method for forming the resist on the layer a is not particularly limited, and a known resist forming method can be used.
The step 1-2 is preferably a step of forming a resist by transferring the photosensitive transfer material onto the layer a in contact therewith, and more preferably a step of forming a resist by transferring the photosensitive transfer material formed in advance on the temporary support onto the layer a in contact therewith.
As a method for transferring a resist onto the layer a using a photosensitive transfer material, a method of bringing a photosensitive resin layer (corresponding to a resist) in the photosensitive transfer material into contact with the layer a and pressing the photosensitive transfer material and the layer a is preferable. According to this method, the adhesion between the photosensitive resin layer in the photosensitive transfer material and the layer a is improved, and therefore the photosensitive resin layer can be used more suitably as a resist for etching the conductive layer.
The photosensitive transfer material used in the method for producing a laminate according to the present invention is preferably a photosensitive transfer material.
The resist may be either positive or negative.
The resist may contain a polymerizable compound, a photopolymerization initiator, and an alkali-soluble resin, or may contain a resin having polarity changed by the action of an acid [ preferably an acid-decomposable resin (i.e., a polymer including a structural unit having an acid group protected by an acid-decomposable group) ] and a photoacid generator, or may contain a resin including a structural unit having a phenolic hydroxyl group, and a quinone diazide compound.
Among these, the resist preferably contains a polymerizable compound, a photopolymerization initiator, and an alkali-soluble resin.
The method of the pressure-sensitive adhesive layer a and the photosensitive transfer material is not particularly limited, and a known transfer method and lamination method can be used.
The photosensitive transfer material is preferably bonded to the layer a by overlapping an outermost layer of the photosensitive transfer material on the side having the photosensitive resin layer with respect to the temporary support with the layer a and applying pressure and heat using a mechanism such as a roller.
For example, a known laminator such as a laminator or a vacuum laminator can be used for lamination. In addition, for example, an automatic cutting laminator that can further improve productivity can be used for lamination.
The lamination temperature is not particularly limited, but is preferably, for example, 70℃to 130 ℃.
When the photosensitive transfer material has a protective film, a step of peeling the protective film is preferably included before the steps 1 to 2.
The method of peeling the protective film is not particularly limited, and a known method can be applied.
When a photosensitive transfer material is used, a peeling step of peeling off the temporary support is preferably included between the steps 1-2 and 1-3 or between the exposure and development processes in the steps 1-3.
The method of peeling off the temporary support is not particularly limited, and the same method as the method of peeling off the cover film described in paragraphs [0161] to [0162] of JP-A2010-072589 can be applied.
< procedure 1-3>
The step 1-3 is a step of patterning the resist formed in the step 1-2.
The steps 1 to 3 are preferably steps of obtaining a patterned resist by pattern-exposing and developing the resist.
The pattern exposure is a pattern-like exposure process, i.e., an exposure process in which there are exposed portions and non-exposed portions.
The positional relationship between the exposed area and the unexposed area in the pattern exposure is not particularly limited, and can be appropriately adjusted.
The detailed arrangement and specific size of the pattern in the pattern exposure are not particularly limited.
For example, from the viewpoint of improving the display quality of a display device (for example, a touch panel) including an input device having circuit wiring manufactured by an etching method and reducing the area occupied by the extracted wiring, at least a part of the pattern (preferably, an electrode pattern of the touch panel and/or a part of the extracted wiring) preferably includes a thin line having a width of 20 μm or less, and more preferably includes a thin line having a width of 10 μm or less.
The line width of the patterned resist that can be obtained in the steps 1 to 3 is preferably 1 μm to 20. Mu.m, more preferably 5 μm to 20. Mu.m, still more preferably 10 μm to 20. Mu.m, and particularly preferably 10 μm to 15. Mu.m.
Further, from the viewpoint of further exhibiting the effects of the present invention, the distance between patterns of the patterned resist obtainable in steps 1 to 3 is preferably 1 μm to 20 μm, the distance between patterns is more preferably 5 μm to 20 μm, the distance between patterns is more preferably 10 μm to 20 μm, and the distance between patterns is particularly preferably 10 μm to 15 μm.
The light source used for exposure may be appropriately selected and used as long as it is a light source that irradiates light (e.g., 365nm, 405nm, or 436 nm) of a wavelength capable of exposing the resist formed in steps 1 to 2.
Specific examples of the light source used for exposure include an ultra-high pressure mercury lamp, a metal halide lamp, and an LED (Light Emitting Diode ).
The exposure is preferably 5mJ/cm 2 ～200mJ/cm 2 More preferably 10mJ/cm 2 ～100mJ/cm 2 。
Preferred embodiments of the light source, the exposure amount, and the exposure method used in the exposure in the method for producing a laminate according to the present invention include, for example, those described in paragraphs [0146] to [0147] of International publication No. 2018/155193, and these descriptions are incorporated herein by reference.
In the case of using the photosensitive transfer material, in the step 1-3, the pattern exposure may be performed after the temporary support is peeled off from the transfer layer (for example, the photosensitive resin layer), or the pattern exposure may be performed via the temporary support before the temporary support is peeled off, and then the temporary support may be peeled off.
In the case where the temporary support is peeled off before exposure, exposure may be performed in contact with the transfer layer, or exposure may be performed in the vicinity of the transfer layer without contact. In the case of exposing without peeling the temporary support, the mask may be exposed in contact with the temporary support, or may be exposed in the vicinity of the temporary support without contact. In view of preventing contamination of the mask due to contact between the transfer layer and the mask and avoiding influence on exposure due to foreign matter adhering to the mask, it is preferable to perform pattern exposure without peeling off the temporary support.
In the exposure method, for example, in the case of contact exposure, a contact exposure method can be selected, whereas in the case of non-contact exposure, a proximity exposure method, a lens system or mirror system projection exposure (so-called Projection exposure) method, and a direct exposure (so-called direct drawing exposure) method using an exposure laser or the like can be appropriately selected. In the case of projection exposure by a lens system or a mirror system, an exposure machine having an appropriate lens aperture Number (NA) can be used depending on the required resolving power, focal depth, and the like. In the case of the direct exposure method, the drawing may be performed directly on the resist, or the reduction projection exposure may be performed on the resist through a lens. The exposure may be performed not only under the atmosphere but also under reduced pressure or vacuum, or may be performed by interposing a liquid such as water between the light source and the transfer layer.
In order to reduce diffraction of light and scattering of light and to improve resolution, exposure in steps 1 to 3 is preferably performed by contact exposure in which the transfer layer is brought into contact with the mask after the temporary support is peeled off from the transfer layer. The exposure in steps 1 to 3 is preferably performed by direct drawing exposure or projection exposure from the viewpoint of reducing the influence on the mask and resist.
The development treatment in steps 1 to 3 is preferably performed using a developer.
The developer is not particularly limited as long as it can remove a non-image portion (so-called unnecessary portion) of the resist (photosensitive resin layer). As the developer, for example, a known developer such as the developer described in japanese patent application laid-open No. 5-72724 can be used.
The developer is preferably an aqueous alkali developer containing a compound having pka=7 to 13 at a concentration of 0.05mol/L to 5mol/L (liter).
The developer may contain a water-soluble organic solvent and/or a surfactant.
Examples of the basic compound that can be contained in the basic aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).
The developer described in paragraph [0194] of International publication No. 2015/093271 is also preferably used. This description is incorporated by reference into this specification.
The development method preferably used is, for example, the development method described in paragraph [0195] of International publication No. 2015/093271. This description is incorporated by reference into this specification.
The development method is not particularly limited, and may be, for example, spin-coating immersion development, shower and spin development, or immersion development.
The shower development is a development process in which a developer is sprayed onto an exposed resist (photosensitive resin layer) to remove a non-image portion.
Preferably, after the development step, the development residues are removed by spraying and blowing a cleaning agent.
The liquid temperature of the developer is not particularly limited, but is preferably 20 to 40 ℃.
< procedure 1-4>
The steps 1 to 4 are as follows: at least a part of the resin contained in layer a is left and layer a is etched using the resist patterned in steps 1 to 3 (hereinafter, also referred to as "resist pattern") as a mask.
As the etching treatment method, a known method can be applied.
The etching treatment method is preferably a wet etching method using an etching liquid.
The etching liquid used in the wet etching method may be an acidic or alkaline etching liquid appropriately selected according to the etching target.
Examples of the acidic etching solution include an aqueous solution of an acidic component selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid and phosphoric acid, and a mixed aqueous solution of an acidic component and a salt selected from iron (II) chloride, iron (III) chloride, iron (II) nitrate, iron (III) nitrate, iron (II) sulfate, iron (III) sulfate, ammonium fluoride and potassium permanganate. The acidic component may be a component obtained by combining a plurality of acidic components.
Examples of the alkaline etching liquid include an aqueous solution containing only an alkaline component selected from sodium hydroxide, potassium hydroxide, ammonia, an organic amine and a salt of an organic amine (for example, tetramethylammonium hydroxide), and a mixed aqueous solution of an alkaline component and a salt (for example, potassium permanganate). The alkaline component may be a component obtained by combining a plurality of alkaline components.
The etching liquid preferably contains at least 1 selected from the group consisting of ferric nitrate and ferric sulfate. In order to control the etching rate and the shape of the material to be etched, it is preferable to use the material in combination with other acids, organic solvents, surfactants, amines, inorganic salts, and the like.
The etching treatment can be performed by bringing the etching liquid into contact with the layer a by a known method such as a spraying method, or a dipping method.
From the viewpoint of controlling the residual amount of the resin contained in the layer a at the portion not masked by the resist pattern, it is preferable to perform the etching treatment by spraying an etching liquid to the layer a.
The liquid temperature of the etching liquid is not particularly limited, but is preferably, for example, 30 to 60 ℃.
The etching treatment time is not particularly limited, and may be appropriately set according to the desired residual amount of the resin, for example. The etching treatment time may be, for example, 30 seconds to 90 seconds.
In steps 1 to 4, at least a part of the resin contained in layer a is left.
Since the etching solution is a liquid having a function of dissolving metal, when the layer a is subjected to etching treatment using the etching solution, the metal component of the metal nano-body contained in the layer a at the portion not masked by the resist pattern can be dissolved. For example, the metal component of the metal nano-body contained in the layer A can be completely removed by controlling the composition of the etching solution (for example, the kind of the acidic component or the alkali component contained in the etching solution, the concentration of the acid or the alkali, the kind of the additive, etc.), the liquid temperature of the etching solution, the etching treatment time, etc. In addition to the above control, for example, the shower pressure, the etching treatment time, and the like are controlled, and the removal of the resin contained in the layer a of the portion not masked by the resist pattern is adjusted, whereby at least a part of the resin can be left.
< procedure 1-5>
The steps 1 to 5 are steps for forming a conductive portion by removing the resist (i.e., the resist pattern) patterned in the steps 1 to 3.
The method for removing the remaining resist pattern is not particularly limited, and examples thereof include a method for removing the resist pattern by chemical treatment, and a method for removing the resist pattern by using a removing liquid is preferable.
As a method for removing the resist pattern, a method in which the remaining resist pattern is immersed in a removing liquid under stirring is given.
The liquid temperature of the removing liquid is preferably 30 to 80 ℃, more preferably 40 to 80 ℃. The immersion time is not particularly limited, and examples thereof include 1 minute to 30 minutes.
Examples of the removing liquid include a removing liquid obtained by dissolving an inorganic basic component or an organic basic component in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution of these.
Examples of the inorganic alkaline component include sodium hydroxide and potassium hydroxide. Examples of the organic base component include a primary amine compound, a secondary amine compound, a tertiary amine compound, and a quaternary ammonium salt compound.
The residual resist pattern can be removed by a known method such as a spray method, a shower method, or a spin-coating immersion method using a removing liquid.
[ method for manufacturing according to embodiment 2 ]
The manufacturing method according to embodiment 2 includes, in order: a step of preparing a substrate having a metal-containing layer B (hereinafter, also referred to as "step 2-1"); a step of forming a resist on the layer B (hereinafter, also referred to as "step 2-2"); a step of patterning the resist (hereinafter, also referred to as "step 2-3"); a step of etching the layer B using the patterned resist as a mask (hereinafter, also referred to as "step 2-4"); a step of removing the patterned resist to form a conductive portion (hereinafter, also referred to as "step 2-5"); a step of forming a negative photosensitive resin layer between adjacent conductive portions (hereinafter, also referred to as "steps 2 to 6"); and a step of exposing the negative photosensitive resin layer (hereinafter, also referred to as "step 2-7").
The manufacturing method according to embodiment 2 is preferably the following manufacturing method: the step of forming a negative photosensitive resin layer between the conductive portions (i.e., steps 2 to 6) is a step of forming a negative photosensitive resin layer between the conductive portions on the side opposite to the base material and the adjacent conductive portions, and the step of exposing the negative photosensitive resin layer (i.e., steps 2 to 7) is a step of exposing the conductive portions on the side opposite to the side having the conductive portions of the base material as a mask, and further removing the unexposed negative photosensitive resin layer (hereinafter, also referred to as "steps 2 to 8").
The steps of the above steps will be described in detail below.
< procedure 2-1>
Step 2-1 is a step of preparing a substrate having a layer B containing metal.
As the base material, the above-described base material can be suitably used.
The metal in the layer B is preferably a metal in the conductive portion described above.
Layer B may contain 1 metal or 2 or more metals.
The metal content in the layer B is preferably 50 to 100 mass%, more preferably 70 to 100 mass%, even more preferably 90 to 100 mass%, and particularly preferably 100 mass%, based on the total mass of the layer B, that is, the layer B is formed of a metal.
Layer B may contain a resin in addition to a metal.
The resin in the layer B is preferably a resin in the conductive portion described above.
When the layer B contains a resin, 1 resin may be contained, or 2 or more resins may be contained.
The layer B preferably contains no resin or a content of the resin exceeding 0 mass% and 50 mass% or less relative to the total mass of the layer B, more preferably contains no resin or a content of the resin exceeding 0 mass% and 30 mass% or less relative to the total mass of the layer B, still more preferably contains no resin or a content of the resin exceeding 0 mass% and 10 mass% or less relative to the total mass of the layer B, and particularly preferably contains no resin.
Layer B may further comprise various additives.
Examples of the various additives in the layer B include the various additives in the conductive portion described above.
The thickness M of the layer B is not particularly limited, but is preferably 0.01 μm to 10.0 μm, more preferably 0.05 μm to 5.0 μm, still more preferably 0.08 μm to 3.0 μm, and particularly preferably 0.1 μm to 2.0 μm, from the viewpoints of conductivity and film formability, for example.
The thickness of the layer B is an average value (i.e., average thickness) of the thicknesses of 10 sites measured by observing a cross section in a direction perpendicular to the in-plane direction using a Scanning Electron Microscope (SEM).
The method for forming the layer B is not particularly limited, and for example, sputtering, vapor deposition, and the like are preferable.
In the case of sputtering, an inert gas (mainly, argon) is introduced in vacuum, and a negative voltage is applied to a target (for example, a plate-shaped film-forming material). The applied voltage treatment produces a glow discharge that ionizes the inert gas atoms. The gas ions are caused to collide with the surface of the target at a high speed and vigorously, particles (e.g., atoms and/or molecules) of the film-forming material constituting the target are ejected, and the particles are caused to adhere or stack vigorously to the surface of the base material or substrate, thereby forming a thin film.
Examples of the vapor deposition method include an induction heating vapor deposition method, a resistance heating vapor deposition method, a laser beam vapor deposition method, and an electron beam vapor deposition method. Although any vapor deposition method may be used, from the viewpoint of having a high film formation speed, an electron beam vapor deposition method may be suitably used. In the vapor deposition, the vapor deposition may be performed while cooling the film so as not to increase the temperature of the substrate.
The method of forming the layer B may be a method of dispersing conductive ink, which is a material containing a conductive material of a metal nano-body, in a liquid by coating. After the application, drying, calcination, and the like may be performed as needed.
The details of the conductive ink and the method of applying the conductive ink are the same as those described in step 1-1 of the manufacturing method according to embodiment 1, and therefore, the description thereof is omitted here.
Layer B is preferably formed to be larger than the desired conductive portion size.
< procedure 2-2>
Step 2-2 is a step of forming a resist on the layer B prepared in step 2-1.
The details of step 2-2 are the same as those described in step 1-2 of the manufacturing method according to embodiment 1 except that layer a is layer B, and therefore, the description thereof is omitted here.
< procedure 2-3>
Step 2-3 is a step of patterning the resist formed in step 2-2.
The details of steps 2 to 3 are the same as those described in steps 1 to 3 of the production method according to embodiment 1, and therefore, the description thereof is omitted here.
< procedure 2-4>
Step 2-4 is a step of etching the layer B using the resist (i.e., the resist pattern) patterned in step 2-3 as a mask.
The details of the etching treatment method are the same as those described in steps 1 to 4 of the manufacturing method according to embodiment 1, except for the following points.
In step 2-4, the metal contained in the layer B is removed at the portion not masked by the resist pattern by etching the layer B using the resist pattern as a mask. The metal is preferably completely removed.
For example, the metal contained in the layer B can be completely removed by controlling the composition of the etching solution (for example, the kind of the acidic component or the alkali component contained in the etching solution, the concentration of the acid or the alkali, the kind of the additive, etc.), the liquid temperature of the etching solution, the etching treatment time, etc.
In addition, since the etching solution has a function of dissolving the metal, when the resin is contained in the layer B, the resin contained in the layer B may remain in a portion not masked by the resist pattern. A part of the resin contained in the layer B may not be removed, but is preferably completely removed.
For example, the resin contained in the layer B can be completely removed by controlling the shower pressure, etching treatment time, and the like.
< procedure 2-5>
Step 2-5 is a step of removing the resist (i.e., the resist pattern) patterned in step 2-3 to form a conductive portion.
The details of steps 2 to 5 are the same as those described in steps 1 to 5 of the production method according to embodiment 1, and therefore, the description thereof is omitted here.
< procedure 2-6>
The step 2-6 is a step of forming a negative photosensitive resin layer between the adjacent conductive portions formed in the step 2-5, and preferably includes the following steps: a negative photosensitive resin layer is formed between the surface of the conductive portion formed in step 2-5 opposite to the base material and the adjacent conductive portion (i.e., the uneven surface formed by the conductive portion and the base material formed in step 2-5).
The method for forming the negative photosensitive resin layer between the conductive portions is not particularly limited, and a known resist forming method can be used.
The steps 2 to 6 are preferably steps of forming a negative photosensitive resin layer by transferring a photosensitive transfer material in contact between the surface of the conductive portion opposite to the base material and the adjacent conductive portion (i.e., the concave-convex surface formed by the conductive portion and the base material formed in the steps 2 to 5), and more preferably steps of forming a negative photosensitive resin layer by transferring a photosensitive transfer material formed in advance on a temporary support in contact with the concave-convex surface formed by the conductive portion and the base material formed in the steps 2 to 5.
As a method for transferring the negative photosensitive resin layer to the uneven surface using the photosensitive transfer material, a method of bringing the negative photosensitive resin layer in the photosensitive transfer material into contact with the uneven surface to press-contact the photosensitive transfer material and the uneven surface is preferable. According to this method, the adhesion between the negative photosensitive resin layer in the photosensitive transfer material and the uneven surface can be improved.
The negative photosensitive resin layer preferably contains a polymerizable compound, a photopolymerization initiator, and an alkali-soluble resin.
The method for pressing the photosensitive transfer material and the uneven surface is not particularly limited, and a known transfer method and lamination method can be used.
The photosensitive transfer material is preferably bonded to the uneven surface by overlapping an outermost layer of the photosensitive transfer material on the side having the photosensitive resin layer with respect to the temporary support with the uneven surface, and applying pressure and heat using a mechanism such as a roller.
For example, a known laminator such as a laminator or a vacuum laminator can be used for lamination. In addition, for example, an automatic cutting laminator that can further improve productivity can be used for lamination.
The lamination temperature is not particularly limited, but is preferably, for example, 70℃to 130 ℃.
When the photosensitive transfer material has a protective film, a step of peeling the protective film is preferably included before steps 2 to 6.
The method of peeling the protective film is not particularly limited, and a known method can be applied.
When a photosensitive transfer material is used, a temporary support peeling step of peeling off the temporary support is preferably included between steps 2 to 6 and 2 to 7 or between steps 2 to 7 and 2 to 8.
The method of peeling the temporary support is as described above.
< procedure 2-7>
The steps 2 to 7 are steps of exposing the negative photosensitive resin layer formed in the steps 2 to 6. In the steps 2 to 7, the negative photosensitive resin layer is preferably exposed from the side of the substrate opposite to the side having the conductive portion using the conductive portion as a mask, from the viewpoint of a simpler method.
The light source used for exposure may be appropriately selected and used as long as it is a light source that irradiates light (for example, 365nm, 405nm, or 436 nm) of a wavelength capable of exposing the negative photosensitive resin layer formed in steps 2 to 6.
Specific examples of the light source used for exposure include an ultra-high pressure mercury lamp, a metal halide lamp, and an LED (Light Emitting Diode ).
The exposure is preferably 5mJ/cm 2 ～200mJ/cm 2 More preferably 10mJ/cm 2 ～100mJ/cm 2 。
In the case of using the photosensitive transfer material, in steps 2 to 7, the pattern exposure may be performed after the temporary support is peeled off from the transfer layer (for example, photosensitive resin layer), or the pattern exposure may be performed via the temporary support before the temporary support is peeled off, and then the temporary support may be peeled off.
The details of the exposure method are the same as those described in steps 1 to 3 of the manufacturing method according to embodiment 1, and therefore, the description thereof will be omitted here.
< procedure 2-8>
The production method according to embodiment 2 preferably further includes a step of removing the unexposed negative photosensitive resin layer (i.e., steps 2 to 8) in addition to the above-described steps.
The method for removing the unexposed negative-type photosensitive resin layer is not particularly limited, and examples thereof include a method for removing the negative-type photosensitive resin layer by chemical treatment, and a method for removing the negative-type photosensitive resin layer by using a removing liquid is preferable.
As a method for removing the unexposed negative photosensitive resin layer, a method of immersing the unexposed negative photosensitive resin layer in a removing liquid under stirring is given.
The liquid temperature of the removing liquid is preferably 30 to 80 ℃, more preferably 40 to 80 ℃. The immersion time is not particularly limited, and examples thereof include 1 minute to 30 minutes.
Examples of the removing liquid include a removing liquid obtained by dissolving an inorganic basic component or an organic basic component in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution of these.
Examples of the inorganic alkaline component include sodium hydroxide and potassium hydroxide. Examples of the organic base component include a primary amine compound, a secondary amine compound, a tertiary amine compound, and a quaternary ammonium salt compound.
The unexposed negative photosensitive resin layer can be removed by a known method such as a spray method, a shower method, or a spin-coating immersion method using a removing liquid.
< other procedure >
The method for producing a laminate according to the present invention may include any step (other step) other than the above steps. The other steps include, for example, the following steps, but are not limited to these steps.
The exposure step, the development step, and other steps that can be applied to the method for producing a laminate according to the present invention include the steps described in paragraphs [0035] to [0051] of JP 2006-23696A. These disclosures are incorporated into the present specification by reference thereto.
Examples of the other steps include a step of reducing the reflectance of visible light as described in paragraph [0172] of international publication No. 2019/022089, a step of forming a new conductive layer on an insulating film as described in paragraph [0172] of international publication No. 2019/022089, and the like, but the present invention is not limited to these steps.
Procedure for reducing the reflectivity of visible light
The method for manufacturing a laminate according to the present invention may include a step of performing a treatment for reducing the visible ray reflectance of a part or all of the conductive portion.
As the treatment for reducing the reflectance of visible light, an oxidation treatment is given.
For example, in the case where the conductive portion includes copper, the conductive portion is oxidized to be copper oxide, and the conductive portion is blackened, whereby the visible ray reflectance of the conductive portion can be reduced.
The treatment for reducing the reflectance of visible light is described in paragraphs [0017] to [0025] of Japanese patent application laid-open No. 2014-150118 and paragraphs [0041], paragraph [0042], paragraph [0048] and paragraph [0058] of Japanese patent application laid-open No. 2013-206315, and these descriptions are incorporated herein by reference.
A step of forming an insulating film and a step of forming a new conductive layer on the surface of the insulating film
The method for producing a laminate according to the present invention preferably includes a step of forming an insulating film on the surface of the conductive portion and a step of forming a new conductive portion on the surface of the insulating film.
By performing the above steps, a second electrode pattern insulated from the first electrode pattern can be formed.
The step of forming the insulating film is not particularly limited, and a known method of forming a permanent film is exemplified. Further, an insulating film having a desired pattern can be formed by photolithography using an insulating photosensitive material.
The step of forming a new conductive portion on the surface of the insulating film is not particularly limited, and for example, a photosensitive material having conductivity may be used to form a new conductive portion having a desired pattern by photolithography.
In the method for producing a laminate according to the present invention, it is also preferable to use a substrate having a plurality of layers a and B on both surfaces thereof, and to form conductive portions sequentially or simultaneously on the layers a and B formed on both surfaces of the substrate. In this way, a circuit wiring for a touch panel in which the first conductive pattern is formed on one surface of the base material and the second conductive pattern is formed on the other surface can be manufactured. It is also preferred that such manufacture is performed in a roll-to-roll fashion.
[ photosensitive transfer Material ]
The photosensitive transfer material used in the method for producing a laminate according to the present invention preferably includes a temporary support and a transfer layer including a photosensitive resin layer, and more preferably includes a temporary support, a transfer layer including a photosensitive resin layer, and a protective film in this order.
The photosensitive transfer material used in the present invention may have other layers between the temporary support and the photosensitive resin layer, between the photosensitive resin layer and the protective film, and the like.
Examples of the other layer include a thermoplastic resin layer and a water-soluble resin layer.
The photosensitive resin layer, the protective film, and the other layers may be single layers or may be a plurality of layers of 2 or more layers.
The photosensitive transfer material used in the present invention is preferably structured as a temporary support, a photosensitive resin layer, and a protective film.
The photosensitive transfer material used in the present invention may be a roll-shaped photosensitive transfer material.
The following describes the respective elements constituting the photosensitive transfer material.
[ temporary support ]
The photosensitive transfer material used in the present invention preferably has a temporary support.
The temporary support is a support that supports a photosensitive resin layer or a transfer layer of the photosensitive resin layer and is peelable.
The temporary support may be a single layer or a plurality of layers of 2 or more layers.
The temporary support preferably has light transmittance from the viewpoint that the photosensitive resin layer can be exposed via the temporary support when the photosensitive resin layer is subjected to pattern exposure.
In the present invention, "light-transmitting" means that the transmittance of light of a wavelength used for pattern exposure is 50% or more.
The temporary support preferably has a transmittance of 60% or more, more preferably 70% or more, of light of a wavelength (more preferably 365 nm) used for pattern exposure, from the viewpoint of improving the exposure sensitivity of the photosensitive resin layer.
The transmittance of the layer included in the photosensitive transfer material is a ratio of the intensity of the outgoing light emitted through the layer with respect to the intensity of the incoming light when the light is incident in a direction (thickness direction) perpendicular to the main surface of the layer, and can be measured using a multifunctional spectrometer (for example, otsuka Electronics co., ltd. Manufactured MCPD Series).
Examples of the material constituting the temporary support include a glass substrate, a resin film, and paper, and from the viewpoints of strength, flexibility, and light transmittance, the resin film is preferable.
Examples of the resin film include polyethylene terephthalate (PET) film, cellulose triacetate film, polystyrene film, and polycarbonate film.
Among these, the resin film is preferably a PET film, and more preferably a biaxially stretched PET film.
The thickness of the temporary support is not particularly limited, and may be selected according to the material from the viewpoints of, for example, strength as a support, flexibility required for adhesion, and light transmittance.
The thickness of the temporary support is preferably 5 μm to 100 μm.
For example, the thickness of the temporary support is more preferably 10 μm to 50 μm, still more preferably 10 μm to 20 μm, and particularly preferably 10 μm to 16 μm from the viewpoint of handleability and versatility.
Further, the thickness of the temporary support is preferably 50 μm or less, more preferably 25 μm or less, further preferably 20 μm or less, and particularly preferably 16 μm or less, from the viewpoints of defect suppression, resolution, and linearity of the resin pattern, for example.
The thickness of the temporary support was calculated as an average value of arbitrary 5 points measured by cross-sectional observation using a scanning electron microscope (SEM: scanning Flectron Microscope).
Further, the film used as the temporary support is preferably free from deformation such as wrinkles and the like, damage, and the like.
The number of particles, foreign matters, and defects contained in the temporary support is preferably small from the viewpoints of the pattern formability at the time of pattern exposure via the temporary support and the transparency of the temporary support.
Enclosed in temporary supportThe total amount of particles, foreign matters and defects contained in the composition is preferably 50 particles/10 mm 2 Hereinafter, more preferably 10 pieces/10 mm 2 Hereinafter, it is more preferable that the number is 3/10 mm 2 Particularly preferably 0/1 Omm 2 。
From the viewpoints of pattern formability at the time of pattern exposure via the temporary support and transparency of the temporary support, it is preferable that the temporary support has a small haze. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 1.0% or less, further preferably 0.5% or less, and particularly preferably 0.1% or less.
For the haze value in the present invention, a haze meter [ for example NIPPON DENSHOKU INDUSTRIES co., NDH-2000 (model) ] manufactured by ltd. Was used by following JIS K7105: 1981.
In order to impart handleability, a layer containing fine particles (also referred to as a "lubricant layer") may be provided on the surface of the temporary support.
The lubricant layer may be provided on one surface of the temporary support or on both surfaces.
The diameter of the particles contained in the lubricant layer can be, for example, 0.05 μm to 0.8 μm. The film thickness of the lubricant layer can be, for example, 0.05 μm to 1.0 μm.
From the viewpoints of conveyability, defect suppression of the resin pattern, and resolution, the arithmetic average roughness Ra of the surface of the temporary support on the side opposite to the photosensitive resin layer side is preferably equal to or greater than the arithmetic average roughness Ra of the surface of the temporary support on the photosensitive resin layer side.
The arithmetic average roughness Ra of the surface of the temporary support opposite to the photosensitive resin layer side is preferably 100nm or less, more preferably 50nm or less, further preferably 20nm or less, particularly preferably 10nm or less, from the viewpoints of conveyability, defect suppression of the resin pattern, and resolution.
The arithmetic average roughness Ra of the photosensitive resin layer side surface in the temporary support is preferably 100nm or less, more preferably 50nm or less, further preferably 20nm or less, particularly preferably 10nm or less, from the viewpoints of releasability of the temporary support, defect suppression of the resin pattern, and resolution.
The value of the "arithmetic average roughness Ra of the side surface of the temporary support opposite to the photosensitive resin layer side" - "of the temporary support is preferably Onm to 10nm, more preferably Onm to 5nm, from the viewpoints of conveyability, defect suppression of the resin pattern, and resolution.
The arithmetic average roughness Ra of the surface of the temporary support or protective film in the present invention is measured by the following method.
The temporary support or protective film surface was measured using a three-dimensional optical profiler (New View7300, manufactured by Zygo Corporation) under the following conditions, thereby obtaining a surface profile.
As the measurement/analysis software, microscope Application of MetroPro ver8.3.2 was used. Next, the Surface Map screen is displayed using the measurement/analysis software, and histogram data is obtained on the Surface Map screen. From the obtained histogram data, an arithmetic average roughness is calculated, and an Ra value of the surface of the temporary support or protective film is obtained.
When the temporary support or the protective film is bonded to the photosensitive resin layer or the like, the temporary support or the protective film is peeled from the photosensitive resin layer, and the Ra value of the surface on the peeled side is measured.
In order to suppress peeling of the temporary support due to adhesion between the stacked laminate and the laminate stacked up and down, when the wound laminate is conveyed again by the roll-to-roll method, the peeling force of the temporary support, specifically, the peeling force between the temporary support and the photosensitive resin layer is preferably 0.5mN/mm or more, more preferably 0.5mN/mm to 2.0mN/mm.
The peel force of the temporary support in the present invention is measured in the following manner.
A copper layer having a thickness of 200nm was formed on a polyethylene terephthalate (PET) film having a thickness of 100 μm by a sputtering method, thereby producing a PET substrate with a copper layer.
The protective film was peeled off from the photosensitive transfer material thus produced, and laminated on the copper-layer-equipped PET substrate under lamination conditions of a lamination roller temperature of 100℃and a line pressure of 0.6MPa and a line speed (i.e., lamination speed) of 1.0 m/min. Next, after an adhesive tape (PRINTACK manufactured by NITTO DENKO corporation) was attached to the surface of the temporary support, a laminate having at least the temporary support and the photosensitive resin layer on the PET substrate with a copper layer was cut into 70mm×10mm to prepare a sample. The PET substrate side of the sample was fixed to a sample stage.
Tensile compression tester (model number: SV-55, manufactured by IMADA-SS Corporation), the tape was stretched at 5.5 mm/sec in a direction of 180 degrees, thereby peeling was performed between the photosensitive resin layer and the temporary support, and the force (peeling force) required for peeling was measured.
Preferred embodiments of the temporary support are described in, for example, paragraphs [0017] and [0018] of Japanese patent application laid-open No. 2014-85643, paragraphs [0019] to [0026] of Japanese patent application laid-open No. 2016-27363, paragraphs [0041] to [0057] of International publication No. 2012/081680, paragraphs [0029] to [0040] of International publication No. 2018/179370, and paragraphs [0012] to [0032] of Japanese patent application laid-open No. 2019-101405, and these descriptions are incorporated by reference into the present specification.
[ photosensitive resin layer ]
The photosensitive transfer material used in the present invention preferably has a photosensitive resin layer.
In the photosensitive transfer material used in the production method according to embodiment 1, the photosensitive resin layer may be a positive photosensitive resin layer or a negative photosensitive resin layer, and is preferably a negative photosensitive resin layer.
In the photosensitive transfer material used in the production method according to embodiment 2, the photosensitive resin layer is a negative photosensitive resin layer.
The negative photosensitive resin layer preferably contains a polymerizable compound, a photopolymerization initiator, and an alkali-soluble resin, and more preferably contains an ethylenically unsaturated compound (5 to 70 mass%), a photopolymerization initiator (0.01 to 20 mass%), and an alkali-soluble resin (10 to 90 mass%) based on the total mass of the photosensitive resin layer.
The positive photosensitive resin layer is not limited, and a known positive photosensitive resin layer can be used.
The positive photosensitive resin layer preferably contains an acid-decomposable resin, that is, a polymer having a structural unit having an acid group protected by an acid-decomposable group, and a photoacid generator. The positive photosensitive resin layer preferably contains a resin having a structural unit having a phenolic hydroxyl group, and a quinone diazide compound. The positive photosensitive resin layer is more preferably a chemically amplified positive photosensitive resin layer containing a polymer having a structural unit having an acid group protected by an acid-decomposable group and a photoacid generator.
The respective components will be described in order below. In the following description, the term "photosensitive resin layer" refers to both a positive photosensitive resin layer and a negative photosensitive resin layer.
< polymerizable Compound >
The negative photosensitive resin layer preferably contains a polymerizable compound.
In the present invention, the "polymerizable compound" is a compound that is polymerized by the action of a photopolymerization initiator described later, and refers to a compound different from an alkali-soluble resin described later.
The polymerizable group of the polymerizable compound is not particularly limited as long as it is a group involved in polymerization reaction, and examples thereof include a group having an ethylenically unsaturated group such as a vinyl group, an acryl group, a methacryl group, a styryl group, and a maleimido group; and a group having a cationically polymerizable group such as an epoxy group or an oxetanyl group.
The polymerizable group is preferably a group having an ethylenically unsaturated group, and more preferably an acryl group or a methacryl group.
The polymerizable compound preferably contains an ethylenically unsaturated compound, and more preferably contains a (meth) acrylate compound.
From the viewpoints of resolution and pattern formation, the negative photosensitive resin layer preferably contains a polymerizable compound having 2 or more functions (so-called polyfunctional polymerizable compound), and more preferably contains a polymerizable compound having 3 or more functions. Here, the polymerizable compound having 2 or more functions means a compound having 2 or more polymerizable groups in one molecule.
Further, from the viewpoint of excellent resolution and releasability, the number of polymerizable groups in one molecule of the polymerizable compound is preferably 6 or less.
From the viewpoint of more excellent balance of photosensitivity, resolution and releasability, the negative photosensitive resin layer preferably contains a 2-functional or 3-functional ethylenically unsaturated compound, more preferably contains a 2-functional ethylenically unsaturated compound.
From the viewpoint of excellent releasability, the ratio of the content of the 2-functional or 3-functional ethylenically unsaturated compound relative to the total content of the ethylenically unsaturated compounds in the negative photosensitive resin layer is preferably 60 mass% or more, more preferably 70 mass% or more, and still more preferably 90 mass% or more. The upper limit is not particularly limited and may be 100 mass%. That is, all of the ethylenically unsaturated compounds contained in the negative photosensitive resin layer may be 2-functional ethylenically unsaturated compounds.
From the viewpoints of resolution and pattern formability, the negative photosensitive resin layer preferably contains a polymerizable compound having a polyalkylene oxide structure, and more preferably contains a polymerizable compound having a polyethylene oxide structure.
As the polymerizable compound having a polyalkylene oxide structure, for example, polyalkylene glycol di (meth) acrylate described later is preferable.
Olefinically unsaturated compounds B1-
The negative photosensitive resin layer preferably contains an ethylenically unsaturated compound B1 having an aromatic ring and 2 ethylenically unsaturated groups. The ethylenically unsaturated compound B1 is a 2-functional ethylenically unsaturated compound having 1 or more aromatic rings in one molecule among the ethylenically unsaturated compounds.
From the viewpoint of more excellent resolution, the ratio of the mass of the ethylenically unsaturated compound B1 to the mass of the ethylenically unsaturated compound in the negative photosensitive resin layer is preferably 40 mass% or more, more preferably 50 mass% or more, still more preferably 55 mass% or more, and particularly preferably 60 mass% or more. The upper limit is not particularly limited, but is preferably 99 mass% or less, more preferably 95 mass% or less, further preferably 90 mass% or less, particularly preferably 85 mass% or less, from the viewpoint of releasability.
Examples of the aromatic ring of the ethylenically unsaturated compound B1 include aromatic hydrocarbon rings such as benzene ring, naphthalene ring, and anthracene ring, aromatic heterocyclic rings such as thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring, and pyridine ring, and condensed rings thereof.
Among these, the aromatic ring of the ethylenically unsaturated compound B1 is preferably an aromatic hydrocarbon ring, and more preferably a benzene ring.
The aromatic ring of the ethylenically unsaturated compound B1 may have a substituent.
The ethylenically unsaturated compound B1 may have only 1 aromatic ring or may have 2 or more aromatic rings.
In order to improve the resolution by suppressing swelling of the negative photosensitive resin layer by the developer, the ethylenically unsaturated compound B1 preferably has a bisphenol structure.
Examples of the bisphenol structure include bisphenol a structure derived from bisphenol a (2, 2-bis (4-hydroxyphenyl) propane), bisphenol F structure derived from bisphenol F (2, 2-bis (4-hydroxyphenyl) methane), and bisphenol B structure derived from bisphenol B (2, 2-bis (4-hydroxyphenyl) butane).
Among these, bisphenol a is preferable as the bisphenol structure.
Examples of the ethylenically unsaturated compound B1 having a bisphenol structure include compounds having a bisphenol structure and 2 ethylenically unsaturated groups (preferably, (meth) acryloyl groups) bonded to both ends of the bisphenol structure.
The bisphenol structure may be directly bonded to 2 ethylenically unsaturated groups at both ends, or may be bonded to the bisphenol structure via 1 or more alkyleneoxy groups.
The alkyleneoxy group added to both ends of the bisphenol structure is preferably ethyleneoxy group or propyleneoxy group, and more preferably ethyleneoxy group.
The number of alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16, more preferably 6 to 14, per 1 molecule.
The olefinically unsaturated compounds B1 having a bisphenol structure are described in paragraphs [0072] to [0080] of Japanese patent application laid-open No. 2016-224162, and these descriptions are incorporated into the present specification by reference.
The ethylenically unsaturated compound B1 is preferably a 2-functional ethylenically unsaturated compound having a bisphenol a structure, and more preferably 2, 2-bis (4- ((meth) acryloxypolyalkoxy) phenyl) propane.
Examples of the 2, 2-bis (4- ((meth) acryloxypolyalkoxy) phenyl) propane include 2, 2-bis (4- (methacryloxydiethoxy) phenyl) propane [ Hitachi Chemical Co., ltd. ], 2-bis (4- (methacryloxyethoxypropoxy) phenyl) propane [ Shin-Nakamura Chemical Co., ltd. ], 2-bis (4- (methacryloxytriethoxy tetrapropoxy) phenyl) propane [ Hitachi Chemical Co. ], ltd. manufactured "FA-3200MY", 2-bis (4- (methacryloyloxy pentadecyloxy) phenyl) propane [ Shin-Nakamura Chemical co., ltd. Manufactured "BPE-1300", 2-bis (4- (methacryloyloxy diethoxy) phenyl) propane [ Shin-Nakamura Chemical co., ltd. Manufactured "BPE-200", ethoxylated (10) bisphenol a diacrylate [ Shin-Nakamura Chemical co., ltd. Manufactured "NK Ester a-BPE-10").
As the ethylenically unsaturated compound B1, a compound represented by the following formula (Bis) can be used.
[ chemical formula 1]
The [ (x) ray ]Bis), R is 1 R is R 2 Each independently represents a hydrogen atom or a methyl group, A is C 2 H 4 B is C 3 H 6 ，n 1 N is as follows 3 Each independently represents an integer of 1 to 39, and n 1 +n 3 Is an integer of 2 to 40, n 2 N is as follows 4 Each independently represents an integer of 0 to 29, and n 2 +n 4 The sequence of the repeating units of- (A-O) -and- (B-O) -may be random, with an integer of 0 to 30, or may be block-wise. In the case of blocks, - (A-O) -and- (B-O) -can both be bisphenol structural sides.
In one aspect, n 1 +n 2 +n 3 +n 4 Preferably an integer of 2 to 20, more preferably an integer of 2 to 16, and even more preferably an integer of 4 to 12. And n is 2 +n 4 Preferably an integer of 0 to 10, more preferably an integer of 0 to 4, still more preferably an integer of 0 to 2, and particularly preferably 0.
The ethylenically unsaturated compound B1 may be used singly or in combination of 2 or more.
From the viewpoint of more excellent resolution, the content of the ethylenically unsaturated compound B1 in the negative photosensitive resin layer is preferably 10 mass% or more, more preferably 20 mass% or more, relative to the total mass of the negative photosensitive resin layer. The upper limit is not particularly limited, but is preferably 70 mass% or less, more preferably 60 mass% or less, from the viewpoints of transferability and edge fusion (i.e., a phenomenon in which components in the negative photosensitive resin layer bleed out from the end portion of the photosensitive transfer material).
The negative photosensitive resin layer may contain an ethylenically unsaturated compound other than the ethylenically unsaturated compound B1.
The ethylenically unsaturated compounds other than the ethylenically unsaturated compound B1 are not particularly limited, and may be appropriately selected from known compounds. Examples thereof include compounds having 1 ethylenically unsaturated group in one molecule (so-called monofunctional ethylenically unsaturated compounds), 2-functional ethylenically unsaturated compounds having no aromatic ring, and ethylenically unsaturated compounds having 3 or more functions.
Examples of the monofunctional ethylenically unsaturated compound include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxy ethyl (meth) acrylate.
Examples of the 2-functional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, urethane di (meth) acrylate, and trimethylolpropane diacrylate.
Examples of alkylene glycol di (meth) acrylates include tricyclodecane dimethanol diacrylate [ Shin-Nakamura Chemical co., ltd. Manufactured "a-DCP", "tricyclodecane dimethanol dimethacrylate [ Shin-Nakamura Chemical co., ltd. Manufactured" DCP "," 1, 9-nonanediol diacrylate [ Shin-Nakamura Chemical co., ltd. Manufactured "a-NOD-N", "1, 6-hexanediol diacrylate [ Shin-Nakamura Chemical co., ltd. Manufactured" and "a-HD-N", ethylene glycol dimethacrylate, 1, 10-decane diol diacrylate and quaternary pentanediol di (meth) acrylate).
Examples of the polyalkylene glycol di (meth) acrylate include polyethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di (meth) acrylate.
Examples of the urethane di (meth) acrylate include propylene oxide-modified urethane di (meth) acrylate and ethylene oxide-and propylene oxide-modified urethane di (meth) acrylate. Examples of the commercial products of urethane di (meth) acrylate include "8UX-015A" manufactured by LTD. And "UA-32P" manufactured by Shin-Nakamura Chemical Co., ltd. And "UA-Nakamura Chemical Co., ltd. And" UA-1100H "manufactured by Ltd.
Examples of the ethylenically unsaturated compound having 3 or more functions include dipentaerythritol (tri/tetra/penta/hexa) (meth) acrylate, pentaerythritol (tri/tetra) (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, trimethylolethane tri (meth) acrylate, isocyanuric acid tri (meth) acrylate, glycerol tri (meth) acrylate, and alkylene oxide modified products of these.
Here, "tri/tetra/penta/hexa) (meth) acrylate" is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate, and "(tri/tetra) (meth) acrylate" is a concept including tri (meth) acrylate and tetra (meth) acrylate.
In one embodiment, the negative photosensitive resin layer preferably contains the above-mentioned ethylenically unsaturated compounds B1 and 3 or more functional ethylenically unsaturated compounds, more preferably contains the above-mentioned ethylenically unsaturated compounds B1 and 2 or more ethylenically unsaturated compounds 3 or more functional ethylenically unsaturated compounds. In this case, the ratio of the total content mass of the ethylenically unsaturated compounds B1 to the total content mass of the ethylenically unsaturated compounds having 3 or more functions is preferably (total content mass of the ethylenically unsaturated compounds B1): (total content mass of ethylenically unsaturated compounds of 3 functions or more) =1: 1 to 5:1, more preferably 1.2:1 to 4:1, further preferably 1.5:1 to 3:1.
examples of the alkylene oxide-modified product of the ethylenically unsaturated compound having 3 or more functions include caprolactone-modified (meth) acrylate compound [ KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku co., ltd., shin-Nakamura Chemical co., ltd., manufactured by a-9300-1CL, etc. ], alkylene oxide-modified (meth) acrylate compound [ Nippon Kayaku co., ltd., manufactured by KAYARAD (registered trademark) RP-1040, shin-Nakamura Chemical co.), ltd, manufactured "ATM-35E", manufactured "a-9300", DAICEL-all ndex ltd, manufactured "EBECRYL (registered trademark) 135", etc. ", ethoxylated triglyceride (Shin-Nakamura Chemical co., ltd, manufactured" a-GLY-9E ", etc."), ARONIX (registered trademark) TO-2349 [ TOAGOSEI co., ltd, manufactured ], ARONIX M-520 [ TOAGOSEI co., ltd, manufactured ], and ARONIX M-510 [ TOAGOSEI co., ltd, manufactured ].
As the ethylenically unsaturated compound other than the ethylenically unsaturated compound B1, those having an acid group described in paragraphs [0025] to [0030] of JP-A-2004-239942 can be used.
From the viewpoints of resolution and linearity, the ratio Mm/Mb of the content Mm of the ethylenically unsaturated compound in the negative photosensitive resin layer to the content Mb of the alkali-soluble resin is preferably 1.0 or less, more preferably 0.9 or less, and still more preferably 0.5 to 0.9.
Further, from the viewpoint of curability and resolution, the ethylenically unsaturated compound in the negative photosensitive resin layer preferably contains a (meth) acrylic compound.
Further, from the viewpoints of curability, resolution, and linearity, the ethylenically unsaturated compound in the negative photosensitive resin layer more preferably contains a (meth) acrylic compound, and the content of the acrylic compound relative to the content of the (meth) acrylic compound contained in the negative photosensitive resin layer is 60 mass% or less.
The molecular weight of the ethylenically unsaturated compound containing the ethylenically unsaturated compound B1 [ in the case of having a molecular weight distribution, the weight average molecular weight (Mw) ] is preferably 200 to 3,000, more preferably 280 to 2,200, and further preferably 300 to 2,200.
When the negative photosensitive resin layer contains a polymerizable compound, the negative photosensitive resin layer may contain only 1 polymerizable compound or may contain 2 or more polymerizable compounds.
When the negative photosensitive resin layer contains a polymerizable compound, the content of the polymerizable compound in the negative photosensitive resin layer is preferably 10 to 70 mass%, more preferably 20 to 60 mass%, and even more preferably 20 to 50 mass% relative to the total mass of the negative photosensitive resin layer.
< photopolymerization initiator >
The negative photosensitive resin layer preferably contains a photopolymerization initiator.
The photopolymerization initiator is a compound that starts polymerization of an ethylenically unsaturated compound upon receiving activation light such as ultraviolet light, visible light, or X-ray. The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.
Examples of the photopolymerization initiator include a photo radical polymerization initiator and a photo cation polymerization initiator.
Among these, a photo radical polymerization initiator is preferable from the viewpoints of resolution and patterning.
Examples of the photo-radical polymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α -aminoalkylbenzophenone structure, a photopolymerization initiator having an α -hydroxyalkylbenzophenone structure, a photopolymerization initiator having an acylphosphine oxide structure, a photopolymerization initiator having an N-phenylglycine structure, and a bisimidazole compound.
As the photo radical polymerization initiator, for example, those described in paragraphs [0031] to [0042] of JP 2011-95716 and in paragraphs [0064] to [0081] of JP 2015-14783 can be used.
Examples of the photo radical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, methoxyphenyl (p, p ' -dimethoxybenzyl), TAZ-110 [ product name, midori Kagaku Co., ltd., manufacture ], benzophenone, TAZ-111 [ product name, midori Kagaku Co., ltd., manufacture ], irgacure (registered trademark) OXE01, OXE02, OXE03 and OXE04 [ all product names, manufactured by BASF corporation ], omnirad (registered trademark) 651 and 369 [ all product names, manufactured by IGM Resins B.V. manufacture ], and 2,2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenyl-1, 2' -bis imidazole [ Tokyo Chemical Industry Co., manufacture ], and Ltd.
Examples of the commercially available photo radical polymerization initiator include 1- [4- (phenylthio) phenyl ] -1, 2-octanedione-2- (o-benzoyloxy) [ product name: IRGACURE (registered trademark) OXE01, manufactured by BASF corporation ], 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone-1- (ortho-acetyl oxime) [ product name: IRGACURE (registered trademark) OXE02 manufactured by BASF corporation), IRGACURE (registered trademark) OXE03 (manufactured by BASF corporation), 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] -1-butanone (product name: omnirad 379EG,IGM Resins B.V manufactured), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (product name: omnirad 907,IGM Resins B.V manufactured), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropanoyl) benzyl ] phenyl } -2-methylpropan-1-one (product name: omnirad 127,IGM Resins B.V manufactured), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 (product name: omni6898 manufactured), 2-hydroxy-2-methyl-1-phenylpropane-1-one (product name: omnirad 1173,IGM Resins B.V manufactured), 2-hydroxy-phenyl-2-cyclohexyl-1-ketone (product name: omnirad 907,IGM Resins B.V manufactured), 2-hydroxy-phenyl-2-methylpropano-1-one (product name: omnirad 127,IGM Resins B.V manufactured), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone (product name: omnirad 369,IGM Resins B.V manufactured), 2-hydroxy-2-phenyl-1-ketone (product name: omnirad 3, 2-hydroxy-2-phenylphosphine) 2-hydroxy-phenyl-2-hydroxy-phenyl) 2-hydroxy-1-ketone (product name: omnih, IGM Resins b.v. manufactured ], bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide [ product name: omnirad 819,IGM Resins B.V, product), photopolymerization initiator of oxime ester series [ product name: lunar 6,DKSH Management Ltd, manufactured ], 2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenylbisimidazole (2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer) [ product name: B-CIM manufactured by Hampford Co., ltd. ] and 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer [ product name: BCTB, tokyo Chemical Industry co., ltd.
Photo-cationic polymerization initiators (so-called photoacid generators) are compounds that receive activating light to generate an acid. The photo cation polymerization initiator is preferably a compound which generates an acid by sensing an activating light having a wavelength of 300nm or more, preferably 300 to 450nm, but the chemical structure thereof is not particularly limited. The photo-cation polymerization initiator that does not directly induce an activating light having a wavelength of 300nm or more can be preferably used in combination with a sensitizer if it is a compound that generates an acid by inducing an activating light having a wavelength of 300nm or more with a sensitizer.
The photo-cation polymerization initiator is preferably a photo-cation polymerization initiator that generates an acid having a pKa of 4 or less, more preferably a photo-cation polymerization initiator that generates an acid having a pKa of 3 or less, and particularly preferably a photo-cation polymerization initiator that generates an acid having a pKa of 2 or less. The lower limit of pKa is not particularly limited, but is preferably-10.0 or more, for example.
Examples of the photo-cationic polymerization initiator include an ionic photo-cationic polymerization initiator and a nonionic photo-cationic polymerization initiator.
Examples of the ionic photo-cationic polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary amine salts.
As the ionic photo-cation polymerization initiator, the ionic photo-cation polymerization initiators described in paragraphs [0114] to [0133] of JP-A2014-85643 can be used.
Examples of the nonionic photo-cationic polymerization initiator include trichloromethyl-symmetrical triazines, diazomethane compounds, imide sulfonate compounds and oxime sulfonate compounds. As the trichloromethyl-symmetrical triazines, diazomethane compounds and imide sulfonate compounds, those described in paragraphs [0083] to [0088] of Japanese patent application laid-open No. 2011-221494 can be used. As the oxime sulfonate compound, those described in paragraphs [0084] to [0088] of International publication No. 2018/179640 can be used.
When the negative photosensitive resin layer contains a photopolymerization initiator, it may contain only 1 kind of photopolymerization initiator or 2 or more kinds of photopolymerization initiators.
When the negative photosensitive resin layer contains a photopolymerization initiator, the content of the photopolymerization initiator in the negative photosensitive resin layer is not particularly limited, but is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and further preferably 1.0 mass% or more, relative to the total mass of the photosensitive resin layer. The upper limit is not particularly limited, but is preferably 10 mass% or less, more preferably 5 mass% or less, relative to the total mass of the negative photosensitive resin layer.
< alkali-soluble resin (negative) >)
The negative photosensitive resin layer preferably contains an alkali-soluble resin.
In the present invention, the term "alkali-soluble" means that the solubility of 100g of a 1% by mass aqueous sodium carbonate solution having a liquid temperature of 22 ℃ is 0.1g or more.
The alkali-soluble resin is not particularly limited, and for example, a known alkali-soluble resin used for resists can be suitably used.
And, the alkali-soluble resin is preferably a binder polymer.
The alkali-soluble resin is preferably an alkali-soluble resin having an acid group.
As the alkali-soluble resin, a polymer a described later is preferable.
Polymer A-
As the alkali-soluble resin, polymer a is preferably contained.
The acid value of the polymer a is preferably 220mgKOH/g or less, more preferably less than 200mgKOH/g, and even more preferably less than 190mgKOH/g, from the viewpoint of further improvement in resolution due to suppression of swelling of the negative photosensitive resin layer by the developer. The lower limit is not particularly limited, but from the viewpoint of further improving the developability, it is preferably 60mgKOH/g or more, more preferably 120mgKOH/g or more, still more preferably 150mgKOH/g or more, particularly preferably 170mgKOH/g or more.
The acid value was the mass [ mg ] of potassium hydroxide required for neutralizing 1g of the sample, and in the present invention, the unit was expressed as mgKOH/g. The acid value can be calculated, for example, from the average content of acid groups in the compound.
The acid value of the polymer a can be adjusted according to the type of the structural unit constituting the polymer a and the content of the structural unit containing an acid group.
The weight average molecular weight of polymer a is preferably 5,000 ～ 500,000.
When the weight average molecular weight of the polymer a is 500,000 or less, resolution and developability can be further improved.
The weight average molecular weight of the polymer a is more preferably 100,000 or less, still more preferably 60,000 or less, particularly preferably 50,000 or less.
When the weight average molecular weight of the polymer a is 5,000 or more, the properties of the developed aggregate and the properties of the edge-meltability and chipping-property unexposed film can be more easily controlled.
The weight average molecular weight of the polymer a is more preferably 10,000 or more, still more preferably 20,000 or more, and particularly preferably 30,000 or more.
The edge meltability means a degree of the photosensitive resin layer easily overflows from the end surface of the roller when the photosensitive transfer material is wound into a roll shape.
Chipping refers to the degree of easy flying of a wafer when an unexposed film is cut by a cutter. If chips adhere to the upper surface of the photosensitive resin layer or the like, the chips are transferred to the mask by a subsequent exposure step or the like, and cause defective products.
The dispersity of the polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, still more preferably 1.0 to 4.0, still more preferably 1.0 to 3.0.
In the present invention, the weight average molecular weight and the like are values measured using gel permeation chromatography. And the dispersity is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight/number average molecular weight).
From the viewpoint of suppressing the line width from becoming thicker and the resolution from deteriorating when the focus position is shifted during exposure, the negative photosensitive resin layer preferably contains a monomer component having an aromatic hydrocarbon as the polymer a. Examples of such aromatic hydrocarbons include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group.
The content of the monomer component having an aromatic hydrocarbon in the polymer a is preferably 20 mass% or more, more preferably 30 mass% or more, still more preferably 40 mass% or more, particularly preferably 45 mass% or more, and most preferably 50 mass% or more, based on the total mass of all the monomer components. The upper limit is not particularly limited, but is preferably 95 mass% or less, more preferably 85 mass% or less. The content of the monomer component having aromatic hydrocarbon in the case of containing a plurality of polymers a was determined as a weight average value.
Examples of the monomer having an aromatic hydrocarbon include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methyl styrene, vinyl toluene, t-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, and the like).
Among these, monomers having an aromatic hydrocarbon are preferably monomers having an aralkyl group or styrene.
In one embodiment, when the monomer component having an aromatic hydrocarbon in the polymer a is styrene, the content of the styrene monomer component is preferably 20 to 50% by mass, more preferably 25 to 45% by mass, still more preferably 30 to 40% by mass, and particularly preferably 30 to 35% by mass, based on the total mass of all the monomer components.
Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (a removed benzyl group) and a substituted or unsubstituted benzyl group.
Among these, a substituted or unsubstituted benzyl group is preferable as the aralkyl group.
Examples of the monomer having a phenylalkyl group include phenethyl (meth) acrylate.
Examples of the monomer having a benzyl group include (meth) acrylic acid esters having a benzyl group (e.g., benzyl (meth) acrylate, chlorobenzyl (meth) acrylate, etc.) and vinyl monomers having a benzyl group (e.g., vinylbenzyl chloride, benzyl alcohol, etc.).
Among these, benzyl (meth) acrylate is preferable as the monomer having a benzyl group.
In one embodiment, when the monomer component having an aromatic hydrocarbon in the polymer a is benzyl (meth) acrylate, the content of the benzyl (meth) acrylate monomer component is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, still more preferably 70 to 90% by mass, and particularly preferably 75 to 90% by mass, based on the total mass of all the monomer components.
The polymer a containing a monomer component having an aromatic hydrocarbon is preferably obtained by polymerizing a monomer having an aromatic hydrocarbon with at least 1 of the first monomers described later and/or at least 1 of the second monomers described later.
The polymer a not containing a monomer component having an aromatic hydrocarbon is preferably obtained by polymerizing at least 1 kind of a first monomer described later, more preferably by copolymerizing at least 1 kind of the first monomer with at least 1 kind of a second monomer described later.
The first monomer is a monomer having a carboxyl group in the molecule.
Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester.
Among these, as the first monomer, (meth) acrylic acid is preferable.
The content of the first monomer in the polymer a is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 15 to 30% by mass, based on the total mass of all the monomer components.
The copolymerization ratio of the first monomer is preferably 10 to 50% by mass based on the total mass of all the monomer components.
The copolymerization ratio of the first monomer is preferably 10 mass% or more, more preferably 15 mass% or more, and still more preferably 20 mass% or more from the viewpoint of exhibiting good developability, controlling edge meltability, and the like.
The copolymerization ratio of the first monomer is preferably 50 mass% or less from the viewpoint of high resolution and the skirt shape of the resist pattern and the viewpoint of chemical resistance of the resist pattern, more preferably 35 mass% or less, still more preferably 30 mass% or less, particularly preferably 27 mass% or less from these viewpoints.
The second monomer is non-acidic and is a monomer having at least 1 polymerizable unsaturated group in the molecule.
Examples of the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and esters of vinyl alcohol such as vinyl acetate and (meth) acrylonitrile.
Among these, the second monomer is preferably at least 1 selected from the group consisting of methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and n-butyl (meth) acrylate, and more preferably methyl (meth) acrylate.
The content of the second monomer in the polymer a is preferably 5 to 60% by mass, more preferably 15 to 50% by mass, and even more preferably 20 to 45% by mass, based on the total mass of all the monomer components.
From the viewpoint of suppressing the line width from becoming thicker and the resolution from deteriorating when the focus position is shifted at the time of exposure, the polymer a preferably contains a monomer having an aralkyl group and/or styrene as a monomer.
The polymer a is preferably a copolymer containing methacrylic acid, benzyl methacrylate and styrene, a copolymer containing methacrylic acid, methyl methacrylate, benzyl methacrylate and styrene, or the like, for example.
In one embodiment, the polymer a preferably contains 25 to 40% by mass of a monomer component having an aromatic hydrocarbon, 20 to 35% by mass of a first monomer component, and 30 to 45% by mass of a second monomer component. In another embodiment, the polymer preferably contains 70 to 90 mass% of the monomer component having an aromatic hydrocarbon and 10 to 25 mass% of the first monomer component.
The polymer a may have any one of a linear structure, a branched structure, or an alicyclic structure in a side chain. The branched structure or alicyclic structure can be introduced into the side chain of the polymer a by using a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain. The group having an alicyclic structure may be monocyclic or polycyclic.
Specific examples of the monomer having a group with a branched structure in the side chain include isopropyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isopentyl (meth) acrylate, tert-amyl (meth) acrylate, isoamyl (meth) acrylate, 2-octyl (meth) acrylate, 3-octyl (meth) acrylate and tert-octyl (meth) acrylate.
Among these, the monomer having a group having a branched structure in a side chain is preferably at least 1 selected from isopropyl (meth) acrylate, isobutyl (meth) acrylate and t-butyl methacrylate, and more preferably at least 1 selected from isopropyl methacrylate and t-butyl methacrylate.
Examples of the monomer having a group having an alicyclic structure in a side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group. Further, as the monomer containing a group having an alicyclic structure in a side chain, there is exemplified a (meth) acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms (the number of carbon atoms).
More specific examples of the monomer having an alicyclic structure in the side chain include (meth) acrylic acid (bicyclo [2.2.1] heptyl-2), (meth) acrylic acid-1-adamantyl ester, (meth) acrylic acid-2-adamantyl ester, (meth) acrylic acid-3-methyl-1-adamantyl ester, (meth) acrylic acid-3, 5-dimethyl-1-adamantyl ester, (meth) acrylic acid-3-ethyladamantyl ester, (meth) acrylic acid-3-methyl-5-ethyl-1-adamantyl ester, (meth) acrylic acid-3, 5, 8-triethyl-1-adamantyl ester, (meth) acrylic acid-3, 5-dimethyl-8-ethyl-1-adamantyl ester, (meth) acrylic acid-2-methyl-2-adamantyl ester, (meth) acrylic acid-2-ethyl-2-adamantyl ester, (meth) acrylic acid-3-hydroxy-1-adamantyl ester, (meth) acrylic acid octahydro-4, 7-linolene (5-methyl) -5-ethyl-1-adamantyl ester, (meth) acrylic acid-1-octahydro-menthol, (meth) acrylic acid-1-menthyl ester Tricyclodecane (meth) acrylate, 3-hydroxy-2, 6-trimethyl-bicyclo [3.1.1] heptyl (meth) acrylate, 3, 7-trimethyl-4-hydroxy-bicyclo [4.1.0] heptyl (meth) acrylate, camphene (meth) acrylate, isobornyl (meth) acrylate, fenchyl (meth) acrylate, 2, 5-trimethylcyclohexyl (meth) acrylate and cyclohexyl (meth) acrylate.
Among these, the monomer having a group having an alicyclic structure in a side chain is preferably at least 1 selected from cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, fenchyl (meth) acrylate, 1-menthyl (meth) acrylate, and tricyclodecane (meth) acrylate, and more preferably at least 1 selected from cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, 2-adamantyl (meth) acrylate, and tricyclodecane (meth) acrylate.
The polymer A may be used alone in an amount of 1 or 2 or more.
In the case of using 2 or more kinds of polymers a, it is preferable to use 2 kinds of polymers a containing a monomer component having an aromatic hydrocarbon or to use a polymer a containing a monomer component having an aromatic hydrocarbon and a polymer a not containing a monomer component having an aromatic hydrocarbon. In the latter case, the proportion of the polymer a containing the monomer component having an aromatic hydrocarbon to be used is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more, relative to the total amount of the polymer a.
The synthesis of the polymer a is preferably carried out by adding a proper amount of a radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile to a solution obtained by diluting the above-described single or multiple monomers with a solvent such as acetone, methyl ethyl ketone, isopropyl alcohol, etc., and heating and stirring the mixture. In some cases, synthesis is performed while dropping a part of the mixture into the reaction solution. After the completion of the reaction, a solvent may be further added to adjust the concentration to a desired level. As the synthesis method, in addition to the solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may be used.
The glass transition temperature (Tg) of the polymer A is preferably from 30℃to 135 ℃.
When the polymer a having a Tg of 135 ℃ or less is used in the negative photosensitive resin layer, the thickness of the line becomes large and the resolution is prevented from deteriorating when the focus position is shifted during exposure. From this viewpoint, the Tg of the polymer A is more preferably 130℃or lower, still more preferably 120℃or lower, particularly preferably 110℃or lower. In addition, when the polymer a having a Tg of 30 ℃ or higher is used in the negative photosensitive resin layer, edge melting resistance can be improved. From this viewpoint, the Tg of the polymer A is more preferably 40℃or higher, still more preferably 50℃or higher, particularly preferably 60℃or higher, and most preferably 70℃or higher.
The negative photosensitive resin layer may contain a resin other than the alkali-soluble resin.
Examples of the resin other than the alkali-soluble resin include an acrylic resin, a styrene-acrylic copolymer (a copolymer having a styrene content of 40 mass% or less), a polyurethane resin, a polyvinyl alcohol, a polyvinyl formaldehyde, a polyamide resin, a polyester resin, an epoxy resin, a polyacetal resin, a polyhydroxystyrene resin, a polyimide resin, a polybenzoxazole resin, a silicone resin, a polyethylenimine, a polyallylamine, and a polyalkylene glycol.
When the negative photosensitive resin layer contains an alkali-soluble resin, the negative photosensitive resin layer may contain only 1 alkali-soluble resin or 2 or more alkali-soluble resins.
When the negative photosensitive resin layer contains an alkali-soluble resin, the content of the alkali-soluble resin in the negative photosensitive resin layer is preferably 10 to 90 mass%, more preferably 30 to 70 mass%, and even more preferably 40 to 60 mass% relative to the total mass of the negative photosensitive resin layer.
When the content of the alkali-soluble resin in the negative photosensitive resin layer is 10 mass% or more relative to the total mass of the negative photosensitive resin layer, the edge melting resistance can be further improved.
When the content of the alkali-soluble resin in the negative photosensitive resin layer is 90 mass% or less relative to the total mass of the negative photosensitive resin layer, the development time can be further controlled.
< polymerization inhibitor >
The negative photosensitive resin layer may contain a polymerization inhibitor.
As the polymerization inhibitor, a radical polymerization inhibitor is preferable.
Examples of the polymerization inhibitor include thermal polymerization inhibitors described in Japanese patent publication No. 4502784 [0018 ].
As the thermal polymerization inhibitor, phenothiazine, phenoxazine or 4-methoxyphenol is preferable. Examples of the other polymerization inhibitor include naphthylamine, cuprous chloride, nitrosophenyl hydroxylamine aluminum salt and diphenyl nitrosoamine.
When the negative photosensitive resin layer contains a polymerization inhibitor, it may contain only 1 kind of polymerization inhibitor or may contain 2 or more kinds of polymerization inhibitor.
When the negative photosensitive resin layer contains a polymerization inhibitor, the content of the polymerization inhibitor in the negative photosensitive resin layer is preferably 0.01 to 3 mass%, more preferably 0.05 to 1 mass%, relative to the total mass of the negative photosensitive resin layer.
When the content of the polymerization inhibitor in the negative photosensitive resin layer is 0.01 mass% or more relative to the total mass of the negative photosensitive resin layer, storage stability can be imparted to the negative photosensitive resin layer.
When the content of the polymerization inhibitor in the negative photosensitive resin layer is 3 mass% or less relative to the total mass of the negative photosensitive resin layer, the sensitivity can be maintained more satisfactorily.
< Compound having unshared Electron pair >
From the viewpoint of adhesion between the layer a containing the metal nano-body and the resin and the layer B containing the metal, the photosensitive resin layer preferably contains a compound having an unshared electron pair.
The compound having an unshared electron pair is preferably a compound containing at least a nitrogen atom, an oxygen atom or a sulfur atom, more preferably a heterocyclic compound, a thiol compound or a disulfide compound, and even more preferably a heterocyclic compound, from the viewpoint of adhesion between the layer a containing a metal nanoparticle and a resin and the layer B containing a metal.
The heterocycle of the heterocyclic compound may be a single ring or a multi-ring.
Examples of the hetero atom of the heterocyclic compound include a nitrogen atom, an oxygen atom and a sulfur atom.
The heterocyclic compound preferably contains at least 1 atom selected from a nitrogen atom, an oxygen atom and a sulfur atom, more preferably contains a nitrogen atom.
The heterocyclic compound containing a nitrogen atom (i.e., a nitrogen-containing heterocyclic compound) preferably has a heterocyclic ring containing 2 or more nitrogen atoms, more preferably has a heterocyclic ring containing 3 or more nitrogen atoms, and still more preferably has a heterocyclic ring containing 3 or 4 nitrogen atoms.
Examples of the heterocyclic compound include triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodamine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, benzoxazole compounds, and pyrimidine compounds.
Among these, the heterocyclic compound is preferably at least 1 compound selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodanine compound, a benzothiazole compound, a thiazole compound, a benzimidazole compound, and a benzoxazole compound, more preferably at least 1 compound selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a thiazole compound, a benzothiazole compound, a benzimidazole compound, and a benzoxazole compound, still more preferably at least 1 compound selected from the group consisting of a triazole compound and a tetrazole compound, and particularly preferably a triazole compound.
Preferred specific examples of the heterocyclic compound are shown below.
Examples of the triazole compound and benzotriazole compound include the following compounds.
[ chemical formula 2]
[ chemical formula 3]
As tetrazolium compounds, the following compounds can be exemplified.
[ chemical formula 4]
[ chemical formula 5]
The thiadiazole compounds can be exemplified by the following compounds.
[ chemical formula 6]
As the triazine compound, the following compounds can be exemplified.
[ chemical formula 7]
As the rhodanine compound, the following compounds can be exemplified.
[ chemical formula 8]
As the thiazole compounds, the following compounds can be exemplified.
[ chemical formula 9]
As benzothiazole compounds, the following compounds can be exemplified.
[ chemical formula 10]
As benzimidazole compounds, the following compounds can be exemplified.
[ chemical formula 11]
[ chemical formula 12]
As the benzoxazole compound, the following compounds can be exemplified.
[ chemical formula 13]
Examples of the sulfur-containing compound include a thiol compound and a disulfide compound.
Examples of the thiol compound include aliphatic thiol compounds.
Examples of the aliphatic thiol compound include monofunctional aliphatic thiol compounds and polyfunctional aliphatic thiol compounds (i.e., aliphatic thiol compounds having 2 or more functions).
Examples of the monofunctional aliphatic thiol compound include 1-octanethiol, 1-dodecanethiol, β -mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and octadecyl-3-mercaptopropionate.
Examples of the polyfunctional aliphatic thiol compound include trimethylolpropane tris (3-mercaptobutyrate), 1, 4-bis (3-mercaptobutanoyloxy) butane, pentaerythritol tetrakis (3-mercaptobutanoate), 1,3, 5-tris (3-mercaptobutanoyloxy) ethyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, trimethylolethane tris (3-mercaptobutanoate), tris [ (3-mercaptopropionyloxy) ethyl ] isocyanurate, trimethylolpropane tris (3-mercaptopropanoate), pentaerythritol tetrakis (3-mercaptopropanoate), tetraethyleneglycol bis (3-mercaptopropanoate), dipentaerythritol hexa (3-mercaptopropanoate), ethylene glycol dithiopropanoate, 1, 4-bis (3-mercaptobutanoyloxy) butane, 1, 2-ethane dithiol, 1, 3-propane dithiol, 1, 6-hexamethylenedithiol, 2' - (ethylene dithiol), and meso-dimercaptoethyl succinate.
Examples of the disulfide compound include 2- (4 '-morpholinodithio) benzothiazole, 2' -benzothiazole disulfide, bis (2-benzoylaminophenyl) disulfide, 1-thiobis (2-naphthol), bis (2, 4, 5-trichlorophenyl) disulfide, 4 '-dithiomorpholine, tetraethylthiuram disulfide, dibenzyl disulfide, bis (2, 4-dinitrophenyl) disulfide, 4' -diaminodiphenyl disulfide, diallyl disulfide, di-t-butyl disulfide, bis (6-hydroxy-2-naphthyl) disulfide, dicyclohexyldisulfide, thioamine isobutyrate disulfide and diphenyl disulfide.
From the viewpoint of adhesion between the metal nanoparticle and resin containing layer a and the metal containing layer B, the molecular weight of the compound having an unshared electron pair is preferably less than 1,000, more preferably 50 to 500, still more preferably 50 to 200, and particularly preferably 50 to 150.
In the case where the photosensitive resin layer contains a compound having an unshared electron pair, the photosensitive resin layer may contain only 1 compound having an unshared electron pair, or may contain 2 or more compounds.
In the case where the photosensitive resin layer contains a compound having an unshared electron pair, the content of the compound having an unshared electron pair in the photosensitive resin layer is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, even more preferably 0.3 to 8% by mass, and particularly preferably 0.5 to 5% by mass, relative to the total mass of the photosensitive resin layer, from the viewpoint of adhesion between the layer a containing the metal nanoparticle and the resin and the layer B containing the metal.
< pigment >
The photosensitive resin layer preferably contains a dye, and more preferably contains a dye (hereinafter, also referred to as "dye N") having a maximum absorption wavelength of 450nm or more in a wavelength range of 400nm to 780nm at the time of color development and having a maximum absorption wavelength changed by an acid, a base or a radical, from the viewpoints of visibility of an exposed portion and a non-exposed portion, pattern visibility after development, and resolution.
The detailed mechanism is not clear when the photosensitive resin layer contains the dye N, but the adhesion to adjacent layers (for example, the temporary support and the base material) is improved, and the resolution is further excellent.
In the present invention, the pigment "the maximum absorption wavelength of the pigment changes due to an acid, a base or a radical" may refer to any one of an embodiment in which the pigment in a colored state is decolorized by an acid, a base or a radical, an embodiment in which the pigment in a decolorized state is colored by an acid, a base or a radical, and an embodiment in which the pigment in a colored state is changed to a colored state of other hue.
Specifically, the dye N may be a compound that changes color from a decolored state by exposure, or may be a compound that changes color from a decolored state by exposure. In this case, the dye N may be a dye whose state of color development or color removal by the action of acid, alkali or radical generated in the photosensitive resin layer by exposure, or a dye whose state of color development or color removal by the change of state (for example, pH) in the photosensitive resin layer by the acid, alkali or radical. The dye N may be a dye that changes the state of color development or decoloration by directly receiving an acid, an alkali or a radical as a stimulus without exposure.
From the viewpoints of visibility and resolution of the exposed portion and the non-exposed portion, the dye N is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by a radical.
From the viewpoints of visibility and resolution of the exposed portion and the non-exposed portion, the photosensitive resin layer preferably contains both a dye whose maximum absorption wavelength is changed by radicals as the dye N and a photo radical polymerization initiator.
Further, from the viewpoint of visibility of the exposed portion and the non-exposed portion, the dye N is preferably a dye that develops color by an acid, an alkali, or a radical.
Examples of the coloring mechanism of the coloring matter N in the present invention include the following embodiments: a photo radical polymerization initiator, a photo cation polymerization initiator (so-called photoacid generator) or a photo base generator is added to the photosensitive resin layer, and after exposure, a radical reactive dye, an acid reactive dye or a base reactive dye (for example, a leuco dye) develops due to radicals, acids or bases generated by the photo radical polymerization initiator, the photo cation polymerization initiator or the photo base generator.
The maximum absorption wavelength of the dye N in the wavelength range of 400nm to 780nm at the time of color development is preferably 550nm or more, more preferably 550nm to 700nm, and even more preferably 550nm to 650nm, from the viewpoint of visibility of the exposed portion and the non-exposed portion.
The maximum absorption wavelength of the pigment N is obtained by: the transmission spectrum of the dye N-containing solution (liquid temperature: 25 ℃) was measured in a range of 400nm to 780nm using a spectrophotometer (for example, UV3100 (model) manufactured by SHIMADZU CORPORATION) under an atmosphere, and the wavelength (maximum absorption wavelength) at which the intensity of light was the smallest in the above wavelength range was detected.
Examples of the coloring matter which is developed or decolored by exposure to light include colorless compounds.
Examples of the coloring matter to be decolorized by exposure to light include colorless compounds, diarylmethane-based coloring matters, oxazine-based coloring matters, xanthene-based coloring matters, iminonaphthoquinone-based coloring matters, azomethine-based coloring matters, and anthraquinone-based coloring matters.
The coloring matter N is preferably a colorless compound from the viewpoint of visibility of the exposed portion and the non-exposed portion.
Examples of the colorless compound include a colorless compound having a triarylmethane skeleton (so-called triarylmethane-based dye), a colorless compound having a spiropyran skeleton (so-called spiropyran-based dye), a colorless compound having a fluoran parent skeleton (so-called fluoran parent-based dye), a colorless compound having a diarylmethane skeleton (so-called diarylmethane-based dye), a colorless compound having a rhodamine lactam skeleton (so-called rhodamine lactam-based dye), a colorless compound having an indolyl phthalide skeleton (so-called indolyl phthalide-based dye), and a colorless compound having a white gold amine skeleton (so-called white gold amine-based dye).
The colorless compound is preferably a triarylmethane-based dye or a fluoran-based dye, and more preferably a colorless compound having a triphenylmethane skeleton (so-called triphenylmethane-based dye) or a fluoran-based dye.
The colorless compound preferably has a lactone ring, a sulfenamide ring, or a sultone ring from the viewpoint of visibility of the exposed portion and the non-exposed portion.
If the colorless compound has a lactone ring, a sulfenalactone ring, or a sultone ring, these rings can be reacted with a radical generated by a photo radical polymerization initiator or an acid generated by a photo cation polymerization initiator to change the colorless compound to a closed-loop state to decolorize or to change the colorless compound to an open-loop state to develop a color.
The colorless compound is preferably a compound having a lactone ring, a sulfenamide ring, or a sultone ring, and developed by opening the lactone ring, sulfenamide ring, or sultone ring by a radical or an acid, and more preferably a compound having a lactone ring, and developed by opening the lactone ring by a radical or an acid.
Examples of the dye N include the following dyes and colorless compounds.
Specific examples of the dye in pigment N include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsin, methyl violet 2B, methylquinoline red, rose bengal, metamine yellow, bromophenol blue, xylenol blue, methyl orange, para-methyl red, congo red, benzoin violet 4B, alpha-naphthyl red, nile blue 2B, nile blue A, methyl violet, malachite green, fuchsin, victoria pure blue-naphthalene sulfonate, victoria pure blue BOH [ Hodogaya Chemical Co., ltd., oil blue #603 [ Orient Chemical Co., ltd., oil powder #312 [ Orient Chemical Co., ltd ], oil red 5B [ Orient Chemical Co., ltd., oil red #308 [ 0 carrier Chemical, co., ltd. ], oil scarlet #308 [ 0 carrier Chemical ]; ltd. manufactured ], oil red OG (manufactured by Orient Chemical Co., ltd., manufactured by ltd.) oil red RR (manufactured by Orient Chemical Co., ltd.) oil green #502 (manufactured by Orient Chemical Co., ltd.), SPIRON Red BEH SPECIAL (manufactured by Orient Chemical Co., ltd.), meta-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulfonylrhodamine B, gold amine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearamino-4-p-N, N-bis (hydroxyethyl) amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-beta-naphthalene-4-p-diethylaminophenylimino-5-pyrazolone.
Specific examples of the leuco compound in the dye N include p, p', p "-hexamethyltriphenylmethane (so-called leuco crystal violet), pergascript Blue SRB [ Ciba Geigy Co., ltd ], crystal violet lactone, malachite green lactone, benzoyl leucomethylene blue, 2- (N-phenyl-N-methylamino) -6- (N-p-tolyl-N-ethyl) amino fluoran mother substrate, 2-phenylamino-3-methyl-6- (N-ethyl-p-toluidine) fluoran mother substrate, 3, 6-dimethoxy fluoran mother substrate, 3- (N, N-diethylamino) -5-methyl-7- (N, N-dibenzylamin) fluoran mother substrate, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-phenylamino fluoran mother substrate, 3- (N, N-diethylamino) -6-methyl-7-amino fluoran mother substrate, 3- (N, N-diethylamino) -5-methyl-7-amino fluoran mother substrate, n-diethylamino) -7- (4-chloroanilino) fluoran parent, 3- (N, N-diethylamino) -7-chloroborane parent, 3- (N, N-diethylamino) -7-benzylamino fluoran parent, 3- (N, N-diethylamino) -7, 8-benzofluoran parent, 3- (N, N-dibutylamino) -6-methyl-7-anilinofluoran parent, 3- (N, N-dibutylamino) -6-methyl-7-stubble amino fluoran parent, 3-piperidinyl-6-methyl-7-anilinofluoran parent, 3-pyrrolidinyl-6-methyl-7-anilinofluoran parent, 3-bis (1-ethyl-2-methylindol-3-yl) phthalide, 3-bis (1-N-butyl-2-methylindol-3-yl) phthalide, 3-bis (p-dimethylaminophenyl) -6-dimethylaminolactone, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylbenzo-phthalide), 3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide and 3',6' -bis (diphenylamino) spiro isobenzofuran-1 (3H), 9' - [9H ] xanthene-3-one.
The dye N is preferably a dye whose maximum absorption wavelength is changed by radicals, and more preferably a dye which develops color by radicals, from the viewpoints of visibility of an exposed portion and a non-exposed portion, pattern visibility after development, and resolution.
The pigment N is preferably at least 1 selected from the group consisting of leuco crystal violet, crystal violet lactone, brilliant green and victoria pure blue-naphthalene sulfonate.
When the photosensitive resin layer contains a dye, the dye may be contained in 1 or 2 or more types.
When the photosensitive resin layer contains a dye, the content of the dye in the photosensitive resin layer is preferably 0.1 mass% or more, more preferably 0.1 to 10 mass%, still more preferably 0.1 to 5 mass%, and particularly preferably 0.1 to 1 mass% with respect to the total mass of the photosensitive resin layer, from the viewpoints of visibility of an exposed portion and a non-exposed portion, pattern visibility after development, and resolution.
The pigment content refers to the pigment content when all of the pigments N contained in the photosensitive resin layer are in a colored state.
Hereinafter, a method for determining the content of the dye N will be described by taking a dye that develops color by a radical as an example.
2 solutions were prepared in which 0.001g or 0.01g of pigment was dissolved in 100mL of methyl ethyl ketone. To each of the obtained solutions, irgacure (registered trademark) OXE01 (product name, manufactured by BASF Japan ltd.) was added, and 365nm light was irradiated, thereby generating radicals, and all the pigments were set in a color-developed state. Then, under an atmospheric atmosphere, a spectrophotometer [ model: UV3100, SHIMADZU CORPORATION), the absorbance of each solution having a liquid temperature of 25℃was measured, and a calibration curve was prepared.
Next, absorbance of the solution in which all the pigments were developed was measured by the same method as described above except that 3g of the photosensitive resin layer was dissolved in methyl ethyl ketone instead of the pigments. Based on the absorbance of the obtained solution containing the photosensitive resin layer, the content of the pigment contained in the photosensitive resin layer was calculated from the calibration curve.
< thermally crosslinkable Compound >
The photosensitive resin layer preferably contains a thermally crosslinkable compound from the viewpoints of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. In the present invention, the thermally crosslinkable compound having an ethylenically unsaturated group described later is not regarded as a polymerizable compound, but is regarded as a thermally crosslinkable compound.
Examples of the thermally crosslinkable compound include a methylol compound and a blocked isocyanate compound.
Among these, blocked isocyanate compounds are preferable from the viewpoints of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.
Since the blocked isocyanate compound reacts with the hydroxyl group and the carboxyl group, for example, when the resin and/or the polymerizable compound has at least one of the hydroxyl group and the carboxyl group, the hydrophilicity of the formed film decreases, and the function of the film obtained by curing the photosensitive resin layer tends to be enhanced when the film is used as a protective film. The blocked isocyanate compound means "a compound having a structure in which an isocyanate group of an isocyanate is protected (so-called mask) with a blocking agent".
The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 to 160 ℃, more preferably 130 to 150 ℃.
The dissociation temperature of the blocked isocyanate means "the temperature of an endothermic peak accompanying the deprotection reaction of the blocked isocyanate when measured by DSC (Differential scanning calorimetry: differential scanning calorimetry) analysis using a differential scanning calorimeter".
As the differential scanning calorimeter, for example, a differential scanning calorimeter manufactured by Seiko Instruments inc. However, the differential scanning calorimeter is not limited thereto.
Examples of the blocking agent having a dissociation temperature of 100℃to 160℃include active methylene compounds [ malonic acid diesters (malonic acid dimethyl, malonic acid diethyl, malonic acid di-N-butyl, malonic acid di-2-ethylhexyl, etc. ] ], and oxime compounds [ aldoxime, acetyloxime, methylethylketoxime, cyclohexanone oxime, etc. ] having a structure represented by-C (=N-OH) -, in the molecule ].
Among these, the blocking agent having a dissociation temperature of 100 to 160 ℃ preferably contains an oxime compound, more preferably an oxime compound, from the viewpoint of storage stability, for example.
For example, it is preferable that the blocked isocyanate compound has an isocyanurate structure from the viewpoints of improving brittleness of the film, improving adhesion to the transfer object, and the like.
The blocked isocyanate compound having an isocyanurate structure is obtained, for example, by subjecting hexamethylene diisocyanate to isocyanurate protection.
Among the blocked isocyanate compounds having an isocyanurate structure, a compound having an oxime structure using an oxime compound as a blocking agent is preferable in that the dissociation temperature is easily set within a preferable range as compared with a compound having no oxime structure and development residues are easily reduced.
The blocked isocyanate compound may have a polymerizable group.
The polymerizable group is not particularly limited, and a known polymerizable group can be used, and a radical polymerizable group is preferable.
Examples of the polymerizable group include an ethylenically unsaturated group such as a (meth) acryloyloxy group, (meth) acrylamido group and styryl group, and a group having an epoxy group such as a glycidyl group.
Among these, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth) acryloyloxy group, and further preferably an acryloyloxy group.
As the blocked isocyanate compound, commercially available ones can be used.
Examples of the commercial products of the blocked isocyanate compound include Karenz (registered trademark) AOI-BM, karenz (registered trademark) MOI-BM and Karenz (registered trademark) MOI-BP (manufactured by SHOWA DENKO K.K. above) and block-type Duranate series (for example, duranate (registered trademark) TPA-B80E, duranate (registered trademark) SBN-70D, duranate (registered trademark) WM44-L70G and Duranate (registered trademark) WT32-B75P manufactured by Asahi Kasei Chemicals Corporation).
Further, as the blocked isocyanate compound, a compound having the following structure can be used.
[ chemical formula 14]
When the photosensitive resin layer contains a thermally crosslinkable compound, the photosensitive resin layer may contain only 1 thermally crosslinkable compound or may contain 2 or more thermally crosslinkable compounds.
When the photosensitive resin layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound in the photosensitive resin layer is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, based on the total mass of the photosensitive resin layer.
< Polymer having structural Unit having acid group protected by acid-decomposable group >
The positive photosensitive resin layer preferably includes a polymer (hereinafter, also referred to as "polymer X") having a structural unit (hereinafter, also referred to as "structural unit a") having an acid group protected by an acid-decomposable group.
When the positive photosensitive resin layer contains the polymer X, the positive photosensitive resin layer may contain only 1 kind of polymer X or 2 or more kinds of polymers X.
In the polymer X, acid groups protected by acid-decomposable groups are converted into acid groups by deprotection reaction under the action of a catalytic amount of an acidic substance (e.g., an acid) generated by exposure. By generating acid groups in the polymer X, the solubility of the positive photosensitive resin layer in the developer increases.
The polymer X is preferably an addition-polymerization type polymer, more preferably a polymer having a structural unit derived from (meth) acrylic acid or an ester thereof.
Structural units having acid groups protected by acid-decomposable groups
The polymer X preferably has a structural unit (i.e., structural unit a) having an acid group protected by an acid-decomposable group. The polymer X has the structural unit a, so that the sensitivity of the positive photosensitive resin layer can be improved.
The acid group is not limited, and a known acid group can be used.
The acid radical is preferably a carboxyl radical or a phenolic hydroxyl radical.
Examples of the acid-decomposable group include a group relatively easily decomposed by an acid and a group relatively hardly decomposed by an acid.
Examples of the group which is relatively easily decomposed by an acid include acetal-type protecting groups (for example, 1-alkoxyalkyl groups, tetrahydropyranyl groups, and tetrahydrofuranyl groups).
Examples of the group which is relatively hardly decomposed by an acid include a tertiary alkyl group (for example, a tertiary butyl group) and a tertiary alkoxycarbonyl group (for example, a tertiary butoxycarbonyl group).
Among these, an acetal-based protecting group is preferable as the acid-decomposable group.
From the viewpoint of suppressing the variation in the line width of the resin pattern, the molecular weight of the acid-decomposable group is preferably 300 or less.
From the viewpoints of sensitivity and resolution, the structural unit a is preferably a structural unit represented by the following formula A1, a structural unit represented by the formula A2, or a structural unit represented by the formula A3, and more preferably a structural unit represented by the formula A3.
The structural unit represented by formula A3 is a structural unit having a carboxyl group protected by an acetal acid-decomposable group.
[ chemical formula 15]
In the formula A1, R 11 R is R 12 Each independently represents a hydrogen atom, an alkyl group or an aryl group, R 11 R is R 12 At least one of which is alkyl or aryl, R 13 Represents alkyl or aryl, R 11 Or R is 12 And R is R 13 Can be linked to form a cyclic ether, 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, and n represents an integer of 0 to 4.
In the formula A2, R 21 R is R 22 Each independently represents a hydrogen atom, an alkyl group or an aryl group, R 21 R is R 22 At least one of which is alkyl or aryl, R 23 Represents alkyl or aryl, R 21 Or R is 22 And R is R 23 Can be linked to form a cyclic ether, R 24 Each independently represents a hydroxyl 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 cycloalkyl group, and m represents an integer of 0 to 3.
In the formula A3, R 31 R is R 32 Each independently represents a hydrogen atom, an alkyl group or an aryl group, R 31 R is R 32 At least one of which is alkyl or aryl, R 33 Represents alkyl or aryl, R 31 Or R is 32 And R is R 33 Can be linked to form a cyclic ether, R 34 Represents a hydrogen atom or a methyl group, X 0 Represents a single bond or arylene.
In formula A3, R is 31 Or R is 32 In the case of alkyl, R 31 Or R is 32 The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms.
In formula A3, R is 31 Or R is 32 In the case of aryl, R 31 Or R is 32 The aryl group represented is preferably phenyl.
In the formula A3, R 31 R is R 32 Each independently is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In the formula A3, R 33 The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.
In the formula A3, R is 31 ～R 33 The alkyl group and the aryl group may have a substituent.
In formula A3, R is preferably 31 Or R is 32 And R is R 33 And linked to form a cyclic ether. The number of ring members of the cyclic ether is preferably 5 or 6, more preferably 5.
In the formula A3, X 0 Preferably a single bond. Arylene groups may have substituents.
In formula A3, R is from the viewpoint of being able to further lower the glass transition temperature (Tg) of polymer X 34 Preferably a hydrogen atom.
R in formula A3 relative to the total mass of the structural units A contained in the polymer X 34 The content of the structural unit which is a hydrogen atom is preferably 20 mass% or more.
R in the structural unit A, in the formula A3 34 The content of the structural unit which is a hydrogen atom can be determined by 13 C-Nuclear magnetic resonance Spectrometry (NMR) measurement the intensity ratio of the peak intensities calculated by conventional methods was confirmed.
As a preferred embodiment of the formulae A1 to A3, reference can be made to paragraphs [0044] to [0058] of International publication No. 2018/179640.
In the formulae A1 to A3, the acid-decomposable group is preferably a group having a cyclic structure, more preferably a group having a tetrahydrofuran ring structure or a tetrahydrofuran ring structure, further preferably a group having a tetrahydrofuran ring structure, and particularly preferably a tetrahydrofuran group, from the viewpoint of sensitivity.
In the case where the polymer X has the structural unit a, it may have 1 structural unit a alone or 2 or more structural units a.
When the polymer X has the structural unit a, the content of the structural unit a in the polymer X is preferably 10 to 70% by mass, more preferably 15 to 50% by mass, and even more preferably 20 to 40% by mass, relative to the total mass of the polymer X.
If the content of the structural unit a in the polymer X is within the above range, the resolution is further improved.
When the polymer X contains 2 or more structural units a, the content of the structural units a indicates the total content of the structural units a of 2 or more.
The content of the structural unit A in the polymer X can be determined by 13 The C-NMR measurement was confirmed by the intensity ratio of the peak intensities calculated by the conventional method.
Structural units having acid radicals
The polymer X may have a structural unit having an acid group (hereinafter, also referred to as "structural unit B").
The structural unit B is a structural unit having an acid group not protected by an acid-decomposable group, that is, an acid group not having a protecting group. By having the structural unit B in the polymer X, sensitivity at the time of pattern formation becomes good. Further, since the polymer X has the structural unit B, it is easily dissolved in an alkaline developer in a development step after exposure, and therefore, the development time can be shortened.
The acid radical in the structural unit B is a proton dissociative group with a pKa of 12 or less.
From the viewpoint of improving sensitivity, the pKa of the acid group is preferably 10 or less, more preferably 6 or less. The pKa of the acid group is preferably-5 or more.
Examples of the acid group include a carboxyl group, a sulfonamide group, a phosphonic acid group, a sulfo group, a phenolic hydroxyl group, and a sulfonylimide group.
The acid group is preferably a carboxyl group or a phenolic hydroxyl group, and more preferably a carboxyl group.
In the case where the polymer X has the structural unit B, it may have 1 structural unit B alone or may have 2 or more structural units B.
When the polymer X has the structural unit B, the content of the structural unit B in the polymer X is preferably 0.01 to 20 mass%, more preferably 0.01 to 10 mass%, and even more preferably 0.1 to 5 mass% relative to the total mass of the polymer X.
If the content of the structural unit B in the polymer X is within the above range, the resolution is further improved.
When the polymer X has 2 or more structural units B, the content of the structural units B indicates the total content of the 2 or more structural units B.
The content of the structural unit B can be determined by 13 The C-NMR measurement was confirmed by the intensity ratio of the peak intensities calculated by the conventional method.
Other structural units
The polymer X preferably has other structural units (hereinafter, also referred to as "structural unit C") in addition to the structural units a and B described above. By adjusting at least one of the type and the content of the structural unit C, various characteristics of the polymer X can be adjusted. By having the structural unit C in the polymer X, the glass transition temperature, acid value and hydrophilicity and hydrophobicity of the polymer X can be easily adjusted.
Examples of the monomer forming the structural unit C include styrene compounds, alkyl (meth) acrylates, cyclic alkyl (meth) acrylates, aryl (meth) acrylates, unsaturated dicarboxylic acid diesters, bicyclic unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated dicarboxylic anhydrides.
From the viewpoint of adhesion to a substrate, the monomer forming the structural unit C is preferably an alkyl (meth) acrylate, more preferably an alkyl (meth) acrylate having an alkyl group having 4 to 12 carbon atoms.
Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
Examples of the structural unit C include structural units derived from styrene, α -methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, or ethylene glycol monoacetoacetate mono (meth) acrylate.
The structural unit C may be a structural unit derived from the compounds described in paragraphs [0021] to [0024] of Japanese patent application laid-open No. 2004-264623.
From the viewpoint of resolution, the structural unit C preferably contains a structural unit having an alkaline group.
Examples of the basic group include a group having a nitrogen atom.
Examples of the group having a nitrogen atom include an aliphatic amino group, an aromatic amino group, and a nitrogen-containing heteroaromatic group. The basic group is preferably an aliphatic amino group.
The aliphatic amino group may be a primary amino group, a secondary amino group or a tertiary amino group, but from the viewpoint of resolution, a secondary amino group or a tertiary amino group is preferable.
As a monomer forming a structural unit having a basic group, examples thereof include 1,2, 6-pentamethyl-4-piperidine methacrylate, 2- (dimethylamino) ethyl methacrylate, 2, 6-tetramethyl-4-piperidine acrylate, 2, 6-tetramethyl-4-piperidine methacrylate, 2, 6-tetramethyl-4-piperidine acrylate 2- (diethylamino) ethyl methacrylate, 2- (dimethylamino) ethyl acrylate, 2- (diethylamino) ethyl acrylate, N- (3-dimethylamino) propyl methacrylate, N- (3-dimethylamino) propyl acrylate N- (3-diethylamino) propyl methacrylate, N- (3-diethylamino) propyl acrylate, 2- (diisopropylamino) ethyl methacrylate, 2-morpholinoethyl acrylate, N- [3- (dimethylamino) propyl ] acrylamide, 4-aminostyrene, 4-vinylpyridine, 2-vinylpyridine, 3-vinylpyridine, 1-vinylimidazole, 2-methyl-1-vinylimidazole, 1-allylimidazole and 1-vinyl-1, 2, 4-triazole.
Among these, 1,2, 6-pentamethyl-4-piperidinyl methacrylate is preferable as a monomer forming a structural unit having a basic group.
Further, as the structural unit C, a structural unit having an aromatic ring or a structural unit having an aliphatic ring skeleton is preferable from the viewpoint of improving electrical characteristics.
Examples of the monomer forming these structural units include styrene, α -methylstyrene, dicyclopentanyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and benzyl (meth) acrylate, and cyclohexyl (meth) acrylate is preferable.
In the case where the polymer X has the structural unit C, it may have 1 structural unit C alone or may have 2 or more structural units C.
When the polymer X has the structural unit C, the content of the structural unit C in the polymer X is preferably 90 mass% or less, more preferably 85 mass% or less, and further preferably 80 mass% or less, relative to the total mass of the polymer X. The content of the structural unit C in the polymer X is preferably 10 mass% or more, more preferably 20 mass% or more, based on the total mass of the polymer X.
When the content of the structural unit C in the polymer X is within the above range, the resolution and the adhesion to the substrate are further improved.
When the polymer X has 2 or more structural units C, the content of the structural units C indicates the total content of the structural units C of 2 or more.
The content of the structural unit C can be determined by 13 The C-NMR measurement was confirmed by the intensity ratio of the peak intensities calculated by the conventional method.
Preferred examples of the polymer X are shown below. However, the polymer X is not limited to the following examples. The ratio of each structural unit and the weight average molecular weight in the polymer X shown below are appropriately selected to obtain preferable physical properties.
[ chemical formula 16]
The glass transition temperature (Tg) of the polymer X is preferably 90℃or lower, more preferably 20℃to 60℃and still more preferably 30℃to 50 ℃.
When the positive photosensitive resin layer is formed using a photosensitive transfer material described later, the transferability of the positive photosensitive resin layer can be improved if the glass transition temperature of the polymer X is in the above range.
As a method for adjusting Tg of the polymer X within the above range, for example, a method using FOX formula can be cited. The Tg of the target polymer X can be adjusted according to the FOX formula, for example, based on the Tg of the homopolymer of each structural unit and the mass fraction of each structural unit in the target polymer X.
Hereinafter, a FOX formula will be described by taking a copolymer having a first structural unit and a second structural unit as an example.
When the glass transition temperature of the homopolymer of the first structural unit is Tg1, the mass fraction of the first structural unit in the copolymer is W1, the glass transition temperature of the homopolymer of the second structural unit is Tg2, and the mass fraction of the second structural unit in the copolymer is W2, the glass transition temperature Tg0 (unit: K) of the copolymer having the first structural unit and the second structural unit can be estimated according to the following formula.
FOX formula: 1/Tg 0= (W1/Tg 1) + (W2/Tg 2)
Further, the Tg of the polymer X can also be adjusted by adjusting the weight average molecular weight of the polymer X.
The acid value of the polymer X is preferably 0 to 50mgKOH/g, more preferably 0 to 20mgKOH/g, still more preferably 0 to 10mgKOH/g, from the viewpoint of resolution.
The acid number of the polymer represents the mass of potassium hydroxide required to neutralize the acidic component per 1g of polymer. The specific measurement method is described below.
First, a measurement sample was dissolved in a mixed solvent containing tetrahydrofuran and water (volume ratio: tetrahydrofuran/water=9/1). Using a potentiometric titration apparatus [ e.g. model: AT-510,KYOTO ELECTRONICS MANUFACTURING CO, LTD. Manufactured ] and 0.1mol/L aqueous sodium hydroxide solution to neutralize the solution obtained by titration AT 25 ℃. The acid value was calculated by the following formula with the inflection point of the titration pH curve as the titration end point.
A＝56.11×Vs×0.1×f/w
A: acid value (mgKOH/g)
Vs: the amount of 0.1mol/L aqueous sodium hydroxide solution (mL) required for titration
f: titration amount of 0.1mol/L sodium hydroxide aqueous solution
w: the mass (g) of the sample was measured (solid content conversion)
The weight average molecular weight (Mw) of the polymer X is preferably 60,000 or less in terms of polystyrene. When the positive photosensitive resin layer is formed using a photosensitive transfer material described later, the positive photosensitive resin layer can be transferred at a low temperature (for example, 130 ℃ or lower) if the weight average molecular weight of the polymer X is 60,000 or lower.
The weight average molecular weight of the polymer X is preferably 2,000 to 60,000, more preferably 3,000 to 50,000.
The ratio (dispersity) of the number average molecular weight to the weight average molecular weight of the polymer X is preferably 1.0 to 5.0, more preferably 1.05 to 3.5.
The weight average molecular weight of the polymer X was measured by GPC (gel permeation chromatography). As the measuring device, various commercially available devices can be used. Hereinafter, a method for measuring the weight average molecular weight of the GPC-based polymer X will be specifically described.
As a measurement device, HLC (registered trademark) -8220GPC (manufactured by TOSOH CORPORATION) was used.
As the column, a column in which 1 of TSKgel (registered trademark) Super HZM-M (manufactured by 4.6 mmID. Times. 15cm,TOSOH CORPORATION), super HZ4000 (manufactured by 4.6 mmID. Times. 15cm,TOSOH CORPORATION), super HZ3000 (manufactured by 4.6 mmID. Times. 15em,TOSOH CORPORATION) and Super HZ2000 (manufactured by 4.6 mmID. Times. 15cm,TOSOH CORPORATION) were connected in series was used.
As eluent THF (tetrahydrofuran) was used.
For the measurement conditions, the sample concentration was set to 0.2 mass%, the flow rate was set to 0.35mL/min, the sample injection amount was set to 10. Mu.L, and the measurement temperature was set to 40 ℃.
As the detector, a differential Refractive Index (RI) detector is used.
As for the calibration curve, "standard sample TSK standard, polystyrene" manufactured by TOSOH CORPORATION was used: any of the 7 samples "F-40", "F-20", "F-4", "F-1", "A-5000", "A-2500" and "A-1000" were prepared.
When the positive photosensitive resin layer contains the polymer X, the content of the polymer X in the positive photosensitive resin layer is preferably 50 to 99.9 mass%, more preferably 70 to 98 mass%, relative to the total mass of the positive photosensitive resin layer, from the viewpoint of high resolution.
The method for producing the polymer X is not limited, and a known method can be used.
For example, the polymer X can be produced by polymerizing a monomer for forming the structural unit a, and if necessary, a monomer for forming the structural unit B and a monomer for forming the structural unit C in an organic solvent using a polymerization initiator. The polymer X can also be produced by a so-called polymer reaction.
< other Polymer >
In the case where the positive photosensitive resin layer includes a polymer having a structural unit having an acid group protected with an acid-decomposable group, the positive photosensitive resin layer may include a polymer having no structural unit having an acid group protected with an acid-decomposable group (hereinafter, also referred to as "other polymer") in addition to the polymer having a structural unit having an acid group protected with an acid-decomposable group.
Examples of the other polymer include polyhydroxystyrene.
Examples of commercial products of polyhydroxystyrene include SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA P and SMA 3840F, TOAGOSEI C0. manufactured by Sartomer Company, inc. and ARUFON (registered trademark) UC-3000 manufactured by LTD. ARUFON (registered trademark) UC-3510, ARUFON (registered trademark) UC-3900, ARUFON (registered trademark) UC-3910, ARUFON (registered trademark) UC-3920 and ARUFON (registered trademark) UC-3080 manufactured by BASF corporation, and Joncryl (registered trademark) 690, joncryl (registered trademark) 678, joncryl (registered trademark) 67 and Joncryl (registered trademark) 586 manufactured by BASF corporation.
When the positive photosensitive resin layer contains other polymers, the positive photosensitive resin layer may contain only 1 type of other polymer or may contain 2 or more types of other polymers.
When the positive photosensitive resin layer contains another polymer, the content of the other polymer in the positive photosensitive resin layer is preferably 50 mass% or less, more preferably 30 mass% or less, and even more preferably 20 mass% or less, relative to the total mass of the polymer components.
In the present invention, the "polymer component" refers to a generic term for all polymers contained in the positive photosensitive resin layer. For example, in the case where the positive photosensitive resin layer contains the polymer X and other polymers, the polymer X and other polymers are collectively referred to as "polymer components". Further, the compound corresponding to the crosslinking agent, dispersant and surfactant described later is not contained in the polymer component even if it is a polymer compound.
The content of the polymer component in the positive photosensitive resin layer is preferably 50 to 99.9 mass%, more preferably 70 to 98 mass%, based on the total mass of the positive photosensitive resin layer.
< alkali-soluble resin (Positive type) >)
The positive photosensitive resin layer preferably contains an alkali-soluble resin, more preferably contains an alkali-soluble resin and a quinone diazide compound, and further preferably contains a resin having a structural unit having a phenolic hydroxyl group and a quinone diazide compound.
Examples of the alkali-soluble resin include resins having a hydroxyl group, a carboxyl group, or a sulfo group in the main chain or a side chain.
Examples of the alkali-soluble resin include polyamide resins, polyhydroxystyrenes, polyhydroxystyrene derivatives, styrene-maleic anhydride copolymers, polyvinyl hydroxybenzoates, carboxyl group-containing (meth) acrylic resins, and novolak resins.
As the alkali-soluble resin, for example, polycondensates of m/p-mixed cresols and formaldehyde, and polycondensates of phenol, cresols and formaldehyde are preferable.
The alkali-soluble resin may have a phenolic hydroxyl group (-Ar-OH) and a carboxyl group (-CO) 2 H) Sulfo (-SO) 3 H) Phosphate group (-OPO) 3 H) Sulfonamide (-SO) 2 NH-R) or substituted sulfonamide (e.g., active imide, -SO) 2 NHCOR、-SO 2 NHSO 2 R and-CONHSO 2 R). Here, ar represents a 2-valent aryl group which may have a substituent, and R represents a hydrocarbon group which may have a substituent.
The novolak resin is obtained, for example, by condensing a phenolic compound with an aldehyde compound in the presence of an acid catalyst.
Examples of the phenol compound include o-, m-, and p-cresol, 2,5-, 3,5-, or 3, 4-xylenol, 2,3, 5-trimethylphenol, 2-t-butyl-5-methylphenol, and t-butylhydroquinone.
Examples of the aldehyde compound include aliphatic aldehydes (for example, formaldehyde, acetaldehyde and glyoxal) and aromatic aldehydes (for example, benzaldehyde and salicylaldehyde).
Examples of the acid catalyst include inorganic acids (e.g., hydrochloric acid, sulfuric acid, and phosphoric acid), organic acids (e.g., oxalic acid, acetic acid, and p-toluenesulfonic acid), and divalent metal salts (e.g., zinc acetate).
The condensation reaction can be carried out according to conventional methods.
The condensation reaction is carried out, for example, at a temperature in the range of 60 to 120℃for 2 to 30 hours.
Regarding the condensation reaction, it may be carried out in an appropriate solvent.
As the alkali-soluble resin, a resin having a structural unit having a phenolic hydroxyl group, such as a novolak resin, is preferable.
From the viewpoint of pattern formability, the weight average molecular weight of the alkali-soluble resin is preferably 5.0X10 2 ～2.0×10 5 。
The number average molecular weight of the alkali-soluble resin is preferably 2.0X10 from the viewpoint of pattern formability 2 ～1.0×10 5 。
For example, a polycondensate of phenol and formaldehyde having an alkyl group having 3 to 8 carbon atoms as a substituent, such as a polycondensate of tert-butylphenol and formaldehyde and a polycondensate of octylphenol and formaldehyde described in U.S. Pat. No. 4123279, may be used together.
Further, a fused product of phenol and formaldehyde having an alkyl group having 3 to 8 carbon atoms as a substituent, such as t-butylphenol formaldehyde resin and octylphenol formaldehyde resin described in U.S. Pat. No. 4123279, can be used.
When the positive photosensitive resin layer contains an alkali-soluble resin, the positive photosensitive resin layer may contain only 1 alkali-soluble resin or 2 or more alkali-soluble resins.
When the positive photosensitive resin layer contains an alkali-soluble resin, the content of the alkali-soluble resin in the positive photosensitive resin layer is preferably 30 to 99.9 mass%, more preferably 40 to 99.5 mass%, and even more preferably 70 to 99 mass% relative to the total mass of the positive photosensitive resin layer.
< photoacid generator >
The positive photosensitive resin layer preferably contains a photoacid generator as a photosensitive compound.
Photoacid generators are compounds capable of generating an acid by irradiation with activating light (e.g., ultraviolet rays, extreme ultraviolet rays, X-rays, and electron beams).
The photoacid generator is preferably a compound that generates an acid by being induced by an activating light having a wavelength of 300nm or more, preferably 300nm to 450 nm. The photoacid generator that does not directly induce an activating light having a wavelength of 300nm or more may be preferably used in combination with a sensitizer if it is a compound that generates an acid by inducing an activating light having a wavelength of 300nm or more with a sensitizer.
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 still more preferably a photoacid generator that generates an acid having a pKa of 2 or less.
The lower limit of the pKa of the acid derived from the photoacid generator is not limited, and is preferably-10.0 or more, for example.
Examples of the photoacid generator include an ionic photoacid generator and a nonionic photoacid generator.
Examples of the ionic photoacid generator include onium salt compounds.
Examples of the onium salt compound include a diaryliodonium salt compound, a triarylsulfonium salt compound, and a quaternary ammonium salt compound.
The ionic photoacid generator is preferably an onium salt compound, and particularly preferably at least one of a triarylsulfonium salt compound and a diaryliodonium salt compound.
As the ionic photoacid generator, the ionic photoacid generators described in paragraphs [0114] to [0133] of JP-A2014-85643 can also be preferably used.
Examples of the nonionic photoacid generator include a trichloromethyl s-triazine compound, a diazomethane compound, an imide sulfonate compound, and an oxime sulfonate compound.
The nonionic photoacid generator is preferably an oxime sulfonate compound from the viewpoints of sensitivity, resolution, and adhesion to a substrate.
Specific examples of the trichloromethyl s-triazine compound, the diazomethane compound and the imide sulfonate compound include those described in paragraphs [0083] to [0088] of Japanese patent application laid-open No. 2011-221494.
As the oxime sulfonate compound, those described in paragraphs [0084] to [0088] of International publication No. 2018/179640 can be preferably used.
From the viewpoints of sensitivity and resolution, the photoacid generator is preferably at least 1 compound selected from the group consisting of onium salt compounds and oxime sulfonate compounds, and more preferably an oxime sulfonate compound.
Preferable examples of the photoacid generator include photoacid generators having the following structures.
[ chemical formula 17]
Examples of the photoacid generator having absorption at a wavelength of 405nm include ADEKA ARKLS (registered trademark) SP-601 [ ADEKA CORPORATION ].
From the viewpoints of heat resistance and dimensional stability, the positive photosensitive resin layer preferably contains a quinone diazide compound as an acid generator (preferably a photoacid generator).
The quinone diazide compound can be synthesized, for example, by subjecting a compound having a phenolic hydroxyl group to a condensation reaction with a quinone diazide sulfonyl halide in the presence of a dehydrohalogenating agent.
Examples of the quinone diazide compound include 1, 2-benzoquinone diazide-4-sulfonate, 1, 2-naphthoquinone diazide-5-sulfonate, 1, 2-naphthoquinone diazide-6-sulfonate, 2, 1-naphthoquinone diazide-4-sulfonate, 2, 1-naphthoquinone diazide-5-sulfonate, 2, 1-naphthoquinone diazide-6-sulfonate, sulfonates of other quinone diazide derivatives, 1, 2-benzoquinone diazide-4-sulfonyl chloride, 1, 2-naphthoquinone diazide-5-sulfonyl chloride, 1, 2-naphthoquinone diazide-6-sulfonyl chloride, 2, 1-naphthoquinone diazide-4-sulfonyl chloride, 2, 1-naphthoquinone diazide-5-sulfonyl chloride, and 2, 1-naphthoquinone diazide-6-sulfonyl chloride.
When the positive photosensitive resin layer contains a photoacid generator, the positive photosensitive resin layer may contain 1 photoacid generator alone or 2 or more photoacid generators.
When the positive photosensitive resin layer contains a photoacid generator, the content of the photoacid generator in the positive photosensitive resin layer is preferably 0.1 to 10 mass%, more preferably 0.5 to 5 mass%, relative to the total mass of the positive photosensitive resin layer, from the viewpoints of sensitivity and resolution.
< other ingredients >
The photosensitive resin layer may contain components other than the above.
(surfactant)
From the viewpoint of thickness uniformity, the photosensitive resin layer preferably contains a surfactant.
Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants.
Among these, nonionic surfactants are preferable as the surfactant.
Examples of the surfactant include surfactants described in paragraphs [0017] to [0071] of JP-A-2009-237362 in JP-A-4502784.
As the surfactant, a fluorine-based surfactant or a silicone-based surfactant is preferable.
Commercial products of the fluorine-based surfactant, examples thereof include Megafac (registered trademark) F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-444, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, MFS-578, MFS-579, MFS-586, MFS-587, R-41-LM, R-01, R-40-LM, RS-43, TF-1956, RS-90, R-94 RS-72-K and DS-21 (manufactured by DIC Corporation above), fluorad (registered trademark) FC430, FC431 and FC171 (manufactured by Sumitomo 3MLimited above), surflon (registered trademark) S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393 and KH-40 (manufactured by AGC Inc. above), polyFox (registered trademark) PF636, PF656, PF6320, PF6520 and PF7002 (manufactured by OMNOVA Solutions Inc. above) and Ftergent (registered trademark) 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, AGC Inc, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 [ above manufactured by NEOS corporation ].
As the fluorine-based surfactant, an acrylic compound having a molecular structure having a functional group containing a fluorine atom, and a functional group portion containing a fluorine atom is cleaved to volatilize the fluorine atom when heat is applied, can be suitably used. Examples of such a fluorine-containing surfactant include Megaface DS series (registered trademark) DS-21 manufactured by DIC CORPORATION (refer to chemical industry Japanese newspaper (2016, 2, 22 days)), and daily industry news (2016, 2, 23 days).
As the fluorine-based surfactant, a polymer of a vinyl ether compound containing a fluorine atom and a hydrophilic vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group is also suitably used.
Also, as the fluorine-based surfactant, a block polymer can be used.
As the fluorine-based surfactant, a fluorine-containing polymer compound containing a structural unit derived from a (meth) acrylate compound having a fluorine atom and a structural unit derived from a (meth) acrylate compound having two or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group and propyleneoxy group) can be suitably used.
As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can also be used. Examples of such a fluorine-based surfactant include Megafac (registered trademark) RS-101, RS-102, RS-718K and RS-72-K (the above is manufactured by DIC Corporation).
Examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerin propoxylate and glycerin ethoxylate), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, PLURONIC (registered trademark) Li0, L31, L61, L62, 10R5, 17R2 and 25R2 (manufactured by BASF corporation), TETRONIC (registered trademark) 304, 701, 704, 901, 904 and 150R1 (manufactured by BASF corporation), SOLSPERSE (registered trademark) 20000 [ Japan Lubrizol Corporation ], NCW-101, NCW-1001 and NCW-1002 [ manufactured by FUJIFILM Wako Pure Chemical Corporation ], pionin (registered trademark) D-6112, D-6112-W, D-KEOL [ more than 6 ] and 25R2 (manufactured by BASF corporation), TETRONIC (registered trademark) 304, 701, 704, 901, 904, and 150R1 (manufactured by BASF corporation), SOLSPERSE (registered trademark) 20000 [ Japan Lubrizol Corporation ], NCW-101, NCW-1001 and NCW-1002 [ manufactured by NCW-1002 ] and [ registered trademark ] Pionin (registered trademark) D-6112, D-6112-D-5212-W, D-and D [ 6 ] and [ Tet ] manufactured by Talcet ] and (registered trademark) 400, 35, talct..
In recent years, since environmental suitability of compounds having a linear perfluoroalkyl group having 7 or more carbon atoms is a concern, surfactants using alternative materials of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) are preferred.
Examples of the silicone surfactant include linear polymers composed of siloxane bonds and modified siloxane polymers having an organic group introduced into a side chain or a terminal.
Examples of silicone surfactants include DOWSIL (registered trademark) 8032ADDITIVE, toray Silicone DC PA, toray Silicone SH PA, toray Silicone DC PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH PA and Toray Silicone SH8400 [ Dow Corning Toray Co., ltd., manufacture ], X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001 and KF-6002 [ Shin-Etsu Co., manufacture ], F-4440, TSF-4300, TSF-4445, TSF-4460 and TSIn 4452 [ manufacture ] and manufacture [ Momentive Performance Materials c ] and K307, and BYK-323, and BYK-330H [ BYK.GYE..
When the photosensitive resin layer contains a surfactant, the photosensitive resin layer may contain only 1 kind of surfactant, or may contain 2 or more kinds of surfactant.
When the photosensitive resin layer contains a surfactant, the content of the surfactant in the photosensitive resin layer is preferably 0.001 to 10 mass%, more preferably 0.01 to 3 mass%, based on the total mass of the photosensitive resin layer.
(additive)
The photosensitive resin layer may contain a known additive as required in addition to the above components.
Examples of the additive include a sensitizer, a plasticizer, a heterocyclic compound, an alkoxysilane compound, and a solvent.
Examples of the additive to the negative photosensitive resin layer and/or the positive photosensitive resin layer include metal oxide particles, antioxidants, dispersants, acid-proliferating agents, development promoters, conductive fibers, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, and organic or inorganic deposition inhibitors.
The preferred embodiments of these additives are described in paragraphs [0165] to [0184] of Japanese unexamined patent publication No. 2014-85643, respectively, and these descriptions are incorporated herein by reference.
When the photosensitive resin layer contains additives, the photosensitive resin layer may contain only 1 kind of additive, or may contain 2 or more kinds of additive.
The photosensitive resin layer may contain a sensitizer.
The sensitizer is not particularly limited, and known sensitizers, dyes and pigments can be used.
Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2, 4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.
When the photosensitive resin layer contains a sensitizer, the content of the sensitizer in the photosensitive resin layer can be appropriately selected according to the purpose, but is preferably 0.01 to 5 mass%, more preferably 0.05 to 1 mass% with respect to the total mass of the photosensitive resin layer from the viewpoints of improving the sensitivity to a light source and improving the curing speed based on the balance between the polymerization speed and chain transfer.
The photosensitive resin layer may contain at least 1 selected from plasticizers and heterocyclic compounds.
Examples of the plasticizer and the heterocyclic compound include those described in paragraphs [0097] to [0103] and [0111] to [0118] of International publication No. 2018/179640.
The photosensitive resin layer (preferably, a positive photosensitive resin layer) may contain an alkoxysilane compound.
Examples of alkoxysilane compounds include gamma-aminopropyl trimethoxysilane, gamma-aminopropyl triethoxysilane, gamma-glycidoxypropyl trialkoxysilane, gamma-glycidoxypropyl alkyl dialkoxysilane, gamma-methacryloxypropyl trialkoxysilane, gamma-methacryloxypropyl alkyl dialkoxysilane, gamma-chloropropyl trialkoxysilane, gamma-mercaptopropyl trialkoxysilane, beta- (3, 4-epoxycyclohexyl) ethyl trialkoxysilane and vinyl trialkoxysilane.
Among these, preferred alkoxysilane compounds are trialkoxysilane compounds, more preferred are γ -glycidoxypropyl trialkoxysilane and γ -methacryloxypropyl trialkoxysilane, further preferred are γ -glycidoxypropyl trialkoxysilane, and particularly preferred is 3-glycidoxypropyl trimethoxysilane.
When the photosensitive resin layer contains an alkoxysilane compound, the content of the alkoxysilane compound in the photosensitive resin layer is preferably 0.1 to 50% by mass, more preferably 0.5 to 40% by mass, and even more preferably 1.0 to 30% by mass, relative to the total mass of the photosensitive resin layer, from the viewpoints of adhesion to a substrate and etching resistance.
The photosensitive resin layer may contain a solvent. When the photosensitive resin composition for forming the photosensitive resin layer contains a solvent, the solvent may remain in the photosensitive resin layer.
(impurities etc.)
The photosensitive resin layer may contain a predetermined amount of impurities.
Examples of the impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen, and ions of these.
Among these, halide ions, sodium ions and potassium ions are easily mixed as impurities, and therefore, the following contents are preferable.
The content of impurities in the photosensitive resin layer is preferably 80 mass ppm or less, more preferably 10 mass ppm or less, and further preferably 2 mass ppm or less, relative to the total mass of the photosensitive resin layer. The lower limit may be 1 ppb by mass or more, or 0.1 ppm by mass or more, relative to the total mass of the photosensitive resin layer.
As a method for setting the content of impurities in the photosensitive resin layer within the above range, there is given: a method of selecting a raw material having a small impurity content as a raw material of a photosensitive resin composition for forming a photosensitive resin layer; a method for preventing impurities from being mixed in when the photosensitive resin layer is manufactured; and a method of cleaning and removing. In this way, the content of impurities in the photosensitive resin layer can be set within the above-described range.
The impurities can be quantified by a known method such as ICP (Inductively Coupled P asa: inductively coupled plasma) emission spectrometry, atomic absorption spectrometry, or ion chromatography.
The photosensitive resin layer preferably contains a small amount of a compound such as benzene, formaldehyde, trichloroethylene, 1, 3-butadiene, carbon tetrachloride, chloroform, N-dimethylformamide, N-dimethylacetamide, and hexane.
The content of these compounds relative to the total mass of the photosensitive resin layer is preferably 100 mass ppm or less, more preferably 20 mass ppm or less, and still more preferably 4 mass ppm or less. The lower limit can be set to 10 ppb by mass or more and 100 ppb by mass or more relative to the total mass of the photosensitive resin layer.
The content of these compounds can be suppressed by the same method as the content of impurities of the above-mentioned metals. The content of these compounds can be determined by a known method.
The content of water in the photosensitive resin layer is preferably 0.01 to 1.0 mass%, more preferably 0.05 to 0.5 mass%, relative to the total mass of the photosensitive resin layer, from the viewpoint of improving reliability and lamination.
(residual monomer)
The photosensitive resin layer may contain residual monomers corresponding to each structural unit of the alkali-soluble resin described above.
The content of the residual monomer is preferably 5,000 mass ppm or less, more preferably 2,000 mass ppm or less, and still more preferably 500 mass ppm or less, relative to the total mass of the alkali-soluble resin, from the viewpoints of pattern formability and reliability. The lower limit is not particularly limited, but is preferably 1 mass ppm or more, more preferably 10 mass ppm or more.
From the viewpoints of pattern formability and reliability, the residual monomer of each structural unit of the alkali-soluble resin is preferably 3,000 mass ppm or less, more preferably 600 mass ppm or less, and still more preferably 100 mass ppm or less, relative to the total mass of the photosensitive resin layer. The lower limit is not particularly limited, but is preferably 0.1 mass ppm or more, more preferably 1 mass ppm or more.
The residual monomer amount of the monomer in synthesizing the alkali-soluble resin by the polymer reaction is also preferably within the above range. For example, in the case where the alkali-soluble resin is synthesized by reacting glycidyl acrylate with a carboxylic acid side chain, the content of glycidyl acrylate is preferably set within the above range.
The amount of the residual monomer can be measured by a known method such as liquid chromatography or gas chromatography.
Physical properties and the like
The thickness of the photosensitive resin layer is preferably 0.1 μm to 300. Mu.m, more preferably 0.2 μm to 100. Mu.m, still more preferably 0.5 μm to 50. Mu.m, still more preferably 0.5 μm to 15. Mu.m, particularly preferably 0.5 μm to 10. Mu.m, and most preferably 0.5 μm to 8. Mu.m.
When the thickness of the photosensitive resin layer is within the above range, the developability of the photosensitive resin layer is further improved, and the resolution can be further improved.
Further, from the viewpoint of resolution and further exhibiting the effects of the present invention, the thickness of the photosensitive resin layer is preferably 10 μm or less, more preferably 5.0 μm or less, still more preferably 0.5 μm to 4.0 μm, and particularly preferably 0.5 μm to 3.0 μm.
The thickness of each layer of the photosensitive transfer material was measured as follows: a cross section in a direction perpendicular to the main surface of the photosensitive transfer material was observed by a scanning electron microscope (SEM: scanning Flectron Microscope), the thickness of each layer was measured at 10 or more points based on the obtained observation image, and the average thickness was calculated by arithmetic average.
The light transmittance of the photosensitive resin layer at 365nm is preferably 10% or more, more preferably 30% or more, and still more preferably 50% or more. The upper limit is not particularly limited, but is preferably 99.9% or less.
[ method of Forming photosensitive resin layer ]
The method for forming the photosensitive resin layer is not particularly limited as long as the layer containing the above components can be formed.
Examples of the method for forming the photosensitive resin layer include the following methods: in the case of the negative photosensitive resin layer, the negative photosensitive resin layer is formed by preparing a photosensitive resin composition containing a polymerizable compound, a photopolymerization initiator, an alkali-soluble resin, a solvent, and the like, applying the photosensitive resin composition to the surface of a temporary support or the like, and drying a coating film of the photosensitive resin composition.
Examples of the photosensitive resin composition used for forming the photosensitive resin layer include a composition containing a polymerizable compound, a photopolymerization initiator, an alkali-soluble resin, any of the above components, and a solvent. The photosensitive resin composition preferably contains a solvent to adjust the viscosity of the photosensitive resin composition, and thus the photosensitive resin layer is easily formed.
The solvent contained in the photosensitive resin composition is not particularly limited as long as it can dissolve or disperse the alkali-soluble resin, the polymerizable compound, the photopolymerization initiator, and any of the above components, and a known solvent can be used.
Examples of the solvent include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (e.g., methanol and ethanol), ketone solvents (e.g., acetone and methyl ethyl ketone), aromatic hydrocarbon solvents (e.g., toluene), aprotic polar solvents (e.g., N-dimethylformamide), cyclic ether solvents (e.g., tetrahydrofuran), ester solvents, amide solvents, and lactone solvents, and mixed solvents containing 2 or more of these solvents.
The photosensitive resin composition preferably contains at least 1 selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent.
The photosensitive resin composition is more preferably a mixed solvent containing at least 1 selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent and at least 1 selected from the group consisting of a ketone solvent and a cyclic ether solvent, and still more preferably a mixed solvent containing at least 3 selected from the group consisting of at least 1 selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, a ketone solvent and a cyclic ether solvent.
Examples of the alkylene glycol ether solvent include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether and dipropylene glycol dialkyl ether.
Examples of the alkylene glycol ether acetate solvent include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate and dipropylene glycol monoalkyl ether acetate.
As the solvent, the solvents described in paragraphs [0092] to [0094] of international publication No. 2018/179640 and the solvents described in paragraph [0014] of japanese patent application laid-open publication No. 2018-177889 can be used, and these descriptions are incorporated herein by reference.
When the photosensitive resin composition contains a solvent, the solvent may be contained in 1 or 2 or more types.
When the photosensitive resin composition contains a solvent, the content of the solvent in the photosensitive resin composition is preferably 50 to 1,900 parts by mass, more preferably 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content in the photosensitive resin composition.
The method for producing the photosensitive resin composition is not particularly limited, and examples thereof include the following methods: the photosensitive resin composition is prepared by previously preparing a solution in which each component is dissolved in the above solvent, and mixing the obtained solution at a predetermined ratio.
From the viewpoint of particle removability, the photosensitive resin composition is preferably filtered using a filter before forming the photosensitive resin layer, more preferably using a filter having a pore size of 0.2 to 10 μm, even more preferably using a filter having a pore size of 0.2 to 7 μm, and particularly preferably using a filter having a pore size of 0.2 to 5 μm.
The material and shape of the filter are not particularly limited, and known materials and shapes can be used.
The filtration is preferably performed 1 or more times, and more preferably performed several times.
The method of applying the photosensitive resin composition is not particularly limited, as long as it is applied by a known method.
Examples of the method for applying the photosensitive resin composition include slit coating, spin coating, curtain coating, and inkjet coating.
Examples of the method for drying the coating film of the photosensitive resin composition include natural drying, heat drying, and reduced pressure drying. These drying methods may be applied singly or in combination of plural.
As the drying method, heat drying and/or reduced pressure drying are preferable.
Here, "drying" means removing at least a part of the solvent contained in the photosensitive resin composition.
The drying temperature is preferably 80℃or higher, more preferably 90℃or higher. The upper limit is not particularly limited, but is preferably 130℃or lower, more preferably 120℃or lower. The drying may be performed by continuously changing the temperature.
The drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and still more preferably 60 seconds or more. The upper limit is not particularly limited, but is preferably 600 seconds or less, more preferably 300 seconds or less.
The photosensitive resin layer can be formed by applying a photosensitive resin composition to a protective film described later and drying the same.
The photosensitive transfer material of the present invention may have another layer between the temporary support and the photosensitive resin layer from the viewpoints of resolution and releasability of the temporary support.
[ protective film ]
The photosensitive transfer material preferably has a protective film.
In addition, the protective film is not included in the transfer layer.
The protective film is preferably in direct contact with the photosensitive resin layer.
Examples of the material constituting the protective film include a resin film and paper.
From the viewpoints of strength and flexibility, the material constituting the protective film is preferably a resin film.
Examples of the resin film include a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film.
Among these, a polyethylene film, a polypropylene film, or a polyethylene terephthalate film is preferable as the resin film.
The thickness of the protective film is not particularly limited, but is preferably 5 μm to 100 μm, more preferably 10 μm to 50 μm.
From the viewpoints of conveyability, defect suppression of the resin pattern, and resolution, the arithmetic average roughness Ra of the surface of the protective film on the side opposite to the photosensitive resin layer side is preferably equal to or less than the arithmetic average roughness Ra of the surface of the protective film on the photosensitive resin layer side, and more preferably smaller than the arithmetic average roughness Ra of the surface of the protective film on the photosensitive resin layer side.
The arithmetic average roughness Ra of the surface of the protective film on the side opposite to the photosensitive resin layer side is preferably 300nm or less, more preferably 100nm or less, still more preferably 70nm or less, and particularly preferably 50nm or less, from the viewpoints of transport property and winding property. Further, from the viewpoint of further excellent resolution, the arithmetic average roughness Ra of the photosensitive resin layer side surface in the protective film is preferably 300nm or less, more preferably 100nm or less, still more preferably 70nm or less, and particularly preferably 50hm or less.
When the Ra value of the surface of the protective film is within the above range, the uniformity of the thicknesses of the photosensitive resin layer and the formed resin pattern can be further improved.
The lower limit of the Ra value of the surface of the protective film is not particularly limited, but both surfaces are preferably 1nm or more, more preferably 10nm or more, and still more preferably 20nm or more, respectively.
The peeling force of the protective film is preferably smaller than that of the temporary support.
Thickness of photosensitive transfer material
The thickness of the photosensitive transfer material is preferably 5 μm to 55. Mu.m, more preferably 10 μm to 50. Mu.m, still more preferably 20 μm to 40. Mu.m.
The thickness of the photosensitive transfer material is measured by a method conforming to the above-described measuring method of the thickness of each layer.
From the viewpoint of further exhibiting the effects of the present invention, the thickness of the layer of the photosensitive transfer material other than the temporary support and the protective film is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 8 μm or less, and particularly preferably 2 μm or more and 8 μm or less.
From the viewpoint of further exhibiting the effect of the present invention, the total thickness of the photosensitive resin layer, the water-soluble resin layer, and the thermoplastic resin layer in the photosensitive transfer material is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 8 μm or less, and particularly preferably 2 μm or more and 8 μm or less.
[ method for producing photosensitive transfer Material ]
The method for producing the photosensitive transfer material used in the present invention is not particularly limited, and a known method can be applied.
As a method for producing the photosensitive transfer material used in the present invention, for example, a method including a step of forming a coating film by applying a photosensitive resin composition to the surface of a temporary support and a step of forming a photosensitive resin layer by drying the formed coating film can be cited from the viewpoint of excellent productivity.
In the case where the photosensitive transfer material used in the present invention has a protective film on the surface of the photosensitive resin layer on the side opposite to the temporary support side, for example, the protective film is bonded by pressure to the photosensitive resin layer formed as described above, whereby the photosensitive transfer material having a structure of the temporary support/photosensitive resin layer/protective film can be produced.
The method for bonding the protective film and the photosensitive resin layer is not particularly limited, and a known method can be used. In the case of bonding the protective film and the photosensitive resin layer, for example, a known laminator such as a vacuum laminator or an automatic laminator can be used.
The laminator preferably includes any heatable roller such as a rubber roller and is capable of pressurizing and heating.
The photosensitive transfer material manufactured by the above method can be wound up to be manufactured and stored in a roll form. The photosensitive transfer material in a roll form can be provided as it is in the step of bonding the photosensitive transfer material to a substrate in a roll-to-roll manner.
(electronic device and method for manufacturing the same)
The electronic device according to the present invention includes the laminate according to the present invention.
The method for manufacturing an electronic device according to the present invention is not particularly limited as long as it is a method for manufacturing an electronic device having the laminate according to the present invention.
The embodiments of the method for manufacturing an electronic device, the specific mode of each step, the order of performing each step, and the like are preferably the same as those described in the above-described "method for manufacturing a laminate".
The method of manufacturing an electronic device may be any method that is known in the art, except for forming wiring for an electronic device by the above method.
The method for manufacturing an electronic device may include any step (other step) other than the above.
The electronic device is not particularly limited, but various wiring forming applications of a semiconductor package, a printed circuit board, a sensor substrate, a conductive film such as a touch panel, an electromagnetic shield material, a film heater, a liquid crystal sealing material, a structure in the field of micromachines or microelectronics, and the like are preferable.
Among these, touch panels are particularly preferred as the electronic devices.
As the electronic device, a flexible display device, particularly a flexible touch panel, is suitably exemplified.
Fig. 2 and 3 show an example of a pattern of a mask for manufacturing a touch panel.
In the pattern a shown in fig. 2 and the pattern B shown in fig. 3, GR is a non-image portion (light shielding portion), EX is an image portion (exposure portion), and DL virtually shows an alignment frame. In the method for manufacturing a touch panel, for example, the photosensitive resin layer is exposed through a mask having a pattern a shown in fig. 2, whereby a touch panel having a circuit wiring having a pattern a corresponding to EX can be manufactured. Specifically, the method described in FIG. 1 of International publication No. 2016/190405 can be used. In one example of the manufactured touch panel, the central portion (pattern portion of the quadrangle connection) of the exposure portion EX is a portion where the transparent electrode (electrode for the touch panel) is formed, and the peripheral portion (thin line portion) of the exposure portion EX is a portion where the wiring of the peripheral lead-out portion is formed.
By the above method for manufacturing an electronic device, an electronic device having at least wiring for an electronic device is manufactured, and for example, a touch panel having at least wiring for a touch panel is preferably manufactured.
The touch panel preferably has a transparent substrate, electrodes, and an insulating layer or a protective layer.
As a detection method in the touch panel, a known method such as a resistive film method, a capacitive method, an ultrasonic method, an electromagnetic induction method, and an optical method can be given.
Among these, the capacitive method is preferable as a detection method in the touch panel.
Examples of the Touch panel type include a so-called in-line type (for example, a Touch panel described in fig. 5, 6, 7, and 8 of japanese patent application laid-open publication No. 2012-517051), a so-called out-line type (for example, a Touch panel described in fig. 19 of japanese patent application laid-open publication No. 2013-168125, and a Touch panel described in fig. 1 and 5 of japanese patent application laid-open publication No. 2012-89102), an OGS (One Glass Solution: a monolithic glass solution), a TOL (Touch-on-Lens: a blanket Touch) type (for example, a Touch panel described in fig. 2 of japanese patent application laid-open publication No. 2013-54727), and various types of external hanging (so-called GG, g1.g2, GFF, GF2, GF1, G1F, and the like), and other configurations (for example, a Touch panel described in fig. 6 of japanese patent application laid-open publication No. 2013-164871).
Examples of the touch panel include the touch panel described in paragraph [0229] of JP-A2017-120435.
Examples
The present invention will be described in further detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment steps and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Accordingly, the scope of the present invention should not be construed as being limited by the embodiments shown below. Unless otherwise specified, "parts" and "%" are based on mass.
[ preparation of silver particles ]
200mL of toluene [ FUJIFILM Wako Pure Chemical Corporation primary reagent ] and 11g of butylamine [ FUJIFILM Wako Pure Chemical Corporation primary reagent ] were mixed and sufficiently stirred using a magnetic stirrer. In addition, the molar ratio of amine added was 2.5 with respect to silver. Here, 10g of a special reagent manufactured by TOYO chemistry INDUSTRIES, INC. was added while stirring. After dissolving silver nitrate, 10g of DISPERBYK-111 as a polymer dispersant and 10g of hexane [ FUJIFILM Wako Pure Chemical Corporation-made special reagent ] were added. Here, a 0.02g/mL aqueous solution of sodium borohydride prepared by adding 1g of sodium borohydride [ FUJIFILM Wako Pure Chemical Corporation ] to 50mL of ion-exchanged water was added dropwise to obtain a liquid containing silver microparticles. After stirring for 1 hour, 200mL of methanol [ special reagent manufactured by FUJIFILM Wako Pure Chemical Corporation ] was added to aggregate silver particles, and the silver particles were precipitated. After the silver microparticles were completely precipitated by centrifugation, toluene and methanol were removed as supernatants, and the excess organic matters were removed to obtain about 6g of silver microparticles.
[ preparation of copper particles ]
To a 200mL three-necked flask, 10.0g (0.1 mol) of copper hydroxide [ FUJIFILM Wako Pure Chemical Corporation, manufactured), 31.5g (0.2 mol) of pelargonic acid [ Tokyo Chemical Industry co., manufactured by ltd., etc.), and 18.5g (20 mL) of propylene glycol monomethyl ether [ PGME, KANTO CHEMICAL co., manufactured by inc were weighed and mixed. The obtained mixture was heated to 100℃while stirring, and the temperature was maintained for 20 minutes. Subsequently, 40.5g (0.4 mol) of hexylamine (boiling point: manufactured by ltd. At 130 ℃ and Tokyo Chemical Industry co., stirring was performed while heating at 100 ℃ for 10 minutes. After cooling the liquid temperature of the obtained mixed solution to 10 ℃ using an ice bath, a solution obtained by dissolving 10.0g (0.2 mol) of hydrazine-hydrate (KANTO CHEMICAL co., inc. Manufactured) in 18.5g (20 mL) of PGME (KANTO CHEMICAL co., inc. Manufactured) was added in the ice bath and stirred for 10 minutes to obtain a reaction solution. Then, the reaction solution was heated to 100℃and the temperature was maintained for 10 minutes. Subsequently, after cooling the reaction solution to 30 ℃, 33g (50 mL) of hexane (KANTO CHEMICAL co., inc. Manufactured) was added. After centrifugation, the supernatant was removed. The precipitate was washed with hexane to obtain 6.5g of hexylamine-coated copper particles.
[ preparation of Material X ]
The following components were mixed to prepare a material X as a resin material.
Composition of material X
Benzyl methacrylate/methacrylic acid/acrylic acid copolymer (mass ratio of structural units: 74.5/10/15.5, acid value: 186mgKOH/g, weight average molecular weight: 60,000): 9.4 parts by mass
Arofix (registered trademark) M-1960 [ polymerizable compound, TOAGOSEI co., ltd. Manufactured ]: 4.5 parts by mass
Arofix (registered trademark) M-350 [ polymerizable compound, TOAGOSEI co., ltd. Manufactured ]: 4.9 parts by mass
Omnirad (registered trademark) 184 [ photopolymerization initiator, IGM Resins b.v. manufactured ]: 0.30 part by mass
Benzophenone [ photopolymerization initiator, FUJIFILM Wako Pure Chemical Corporation production ]: 0.30 part by mass
Omnirad (registered trademark) 819 [ photopolymerization initiator, manufactured by IGM Resins b.v. ]: 0.96 part by mass
DISPERBYK-111 [ manufactured by BYK Japan KK ] polymer dispersant: 0.12 part by mass
353 parts by mass of propylene glycol monomethyl ether acetate [ SHOWA DENKO K.K. ] produced
[ preparation of conductive ink ]
(1) Preparation of ink 1
After the following components were preliminarily kneaded, the following components were kneaded with three rolls to prepare ink 1.
Silver particles: 100 parts by mass
Material X:60.8 parts by mass
Propylene glycol monomethyl ether acetate [ manufactured by SHOWA DENKO k.k. ]: 173 parts by mass
(2) Preparation of ink 2
After the following components were preliminarily kneaded, the following components were kneaded with three rolls to prepare ink 2.
Copper particles: 85.1 parts by mass
Material X:60.8 parts by mass
Propylene glycol monomethyl ether acetate [ manufactured by SHOWA DENKO k.k. ]: 173 parts by mass
(3) Preparation of ink 3
After the following components were preliminarily kneaded, the following components were kneaded with three rolls to prepare ink 3.
Silver particles: 100 parts by mass
Material Y (resin material) [ product name: duranate (registered trademark) WM44-L70G, blocked isocyanate compound, manufactured by Asahi Kasei Chemicals Corporation): 4.7 parts by mass
Propylene glycol monomethyl ether acetate [ manufactured by SHOWA DENKO k.k. ]: 228 parts by mass
(4) Preparation of ink 4
After the following components were preliminarily kneaded, the following components were kneaded with three rolls to prepare ink 4.
Silver particles: 100 parts by mass
Material X:122 parts by mass
Propylene glycol monomethyl ether acetate [ manufactured by SHOWA DENKO k.k. ]: 111 parts by mass
(5) Preparation of ink 5
After the following components were preliminarily kneaded, the following components were kneaded with three rolls to prepare ink 5.
Silver particles: 100 parts by mass
Material X:162 parts by mass
Propylene glycol monomethyl ether acetate [ manufactured by SHOWA DENKO k.k. ]: 71 parts by mass
(6) Preparation of ink 6
After the following components were preliminarily kneaded, the following components were kneaded with three rolls to prepare ink 6.
Silver particles: 100 parts by mass
Material X:20.3 parts by mass
Propylene glycol monomethyl ether acetate [ manufactured by SHOWA DENKO k.k. ]: 213 parts by mass
[ preparation of photosensitive resin composition P ]
The following components were mixed to prepare a photosensitive resin composition P.
Composition of photosensitive resin composition P
Propylene glycol monomethyl ether acetate solution of copolymer of styrene/methacrylic acid/methyl methacrylate (solid content concentration: 30.0% by mass, ratio of monomers: 52% by mass/29% by mass/19% by mass, mw:70,000): 23.4 parts by mass
BPE-500 [ ethoxylated bisphenol a dimethacrylate, shin-Nakamura Chemical co., ltd. ]: 4.1 parts by mass
NK Ester HD-N [ 1, 6-hexanediol dimethacrylate, shin-Nakamura Chemical Co., ltd. ]: 2.2 parts by mass
B-CIM [ 2,2 '-bis (2-chlorophenyl) -4,4',5 '-tetraphenyl-1, 2' -biimidazole, photopolymerization initiator, KUROGANE KASEI co., manufactured by ltd: 0.25 part by mass
SB-PI 701 [ 4,4' -bis (diethylamino) benzophenone, sensitizer, available from SANYO transfer CO., LTD. ]: 0.04 part by mass
TDP-G [ phenothiazine, kawaguchi Chemical Industry Co., LTD. ]: 0.0175 part by mass
1-phenyl-3-pyrazolidinone [ FUJIFILM Wako Pure Chemical Corporation ] manufactured: 0.0011 part by mass
Colorless crystal violet [ Tokyo ChemicalIndustry co., ltd. ]: 0.051 mass portion
N-phenylcarbamoylmethyl-N-carboxymethylaniline [ FUJIFILM Wako Pure Chemical Corporation ]: 0.02 part by mass
1,2, 4-triazole [ Tokyo Chemical Industry co., ltd. ]: 0.75 part by mass
MEGAFACE F-552 [ fluorine-based surfactant, manufactured by DIC Corporation ]: 0.05 part by mass
Methyl ethyl ketone [ MEK, SANKYO CHEMICAL co., ltd. ]: 40.4 parts by mass
Propylene glycol monomethyl ether acetate [ manufactured by SHOWA DENKO k.k. ]: 26.7 parts by mass
Methanol [ Mitsubishi Gas Chemicai Company, inc: 2 parts by mass
[ production of photosensitive transfer Material P ]
The photosensitive resin composition P prepared as described above was applied to the surface of a temporary support (polyethylene terephthalate film, thickness: 16 μm, haze: 0.12%) using a slit nozzle in such a manner that the application width was 1.0m and the film thickness after drying was 5.0 μm, and dried at 100 ℃ for 2 minutes, thereby forming a photosensitive resin layer P. Then, a protective film (polypropylene film, thickness: 12 μm) was attached to the exposed surface of the photosensitive resin layer P formed on the surface of the temporary support, thereby obtaining a photosensitive transfer material P (layer structure: temporary support/photosensitive resin layer P/protective film).
[ example 1 ]
< preparation of conductive substrate >
Ink 1 of the conductive ink prepared as above was applied to a substrate by an inkjet method so that the application width became 1.2m and the wet film thickness became 42 μm [ product name: lumiror (registered trademark) #100-U34, polyester film, manufactured by TORAY INDUSTRIES, INC.). After drying the coating film, the coating film was calcined at 140 ℃ for 30 minutes, thereby producing a conductive substrate [ layer structure: substrate/conductive layer).
< preparation of laminate >
After peeling the protective film from the photosensitive transfer material P produced as described above, the photosensitive transfer material (layer structure: temporary support/photosensitive resin layer) was bonded to the exposed surface of the conductive layer of the conductive substrate under lamination conditions of a roll temperature of 90 ℃, a line pressure of 0.8MPa and a line speed of 3.0 m/min, to obtain a laminate.
A glass mask having a line and space pattern with a line width and a space width of 6 μm and a take-out terminal pattern connected thereto was adhered to a temporary support of the obtained laminate, and then an ultra-high pressure mercury lamp (model: USH-2004MB, manufactured by USHIO INC. The line and space patterns have a space width corresponding to the distance L between the line patterns finally obtained.
In addition, the exposure conditions were determined as follows.
The exposure was set as follows: in using an ultra-high pressure mercury lamp [ model: USH-2004MB, manufactured by USH [ OINC ], and exposed through the above glass mask, left for 1 hour and then developed, and at this time, the residual pattern width in the line 6 μm/space 6 μm pattern portion was in the range of 5.9 μm to 6.1. Mu.m.
In the following examples and comparative examples, exposure conditions were also determined from the same point of view.
The temporary support was peeled off from the laminate after 1 hour of exposure, and a 1.0 mass% aqueous potassium carbonate solution (liquid temperature: 30 ℃) was used as a developer, followed by development with showering for 30 seconds, whereby uncured portions were removed, and a resist pattern was formed.
The surface of the developed laminate on the side where the resist pattern was formed was sprayed with 30 mass% aqueous nitric acid (liquid temperature: 45 ℃ C., pH: 0.6) for 60 seconds by spraying, and the conductive layer in the portion where the resist pattern was not present on the surface was subjected to etching treatment, whereby the resin component in the conductive layer was left and silver was removed.
The laminate after the etching treatment was immersed in a 3 mass% aqueous sodium hydroxide solution (liquid temperature: 50 ℃) for 70 seconds, and the resist pattern remaining in the laminate was peeled off, to obtain a laminate of example 1.
As a result of the laminate of example 1 obtained by visual inspection, it was confirmed that there were conductive portions having a linear pattern on the substrate and a layer containing a resin (i.e., a resin layer) between the conductive portions. Further, it was confirmed that the area where the conductive portions are adjacent via the resin layer was 70% or more of the total length of the conductive portions.
In the result of measuring the volume resistivity of the conductive part, the volume resistivity is less than 1×10 4 Ωcm。
In the result of measuring the volume resistivity of the resin layer, it was 1X 10 8 And omega cm above.
No silver was detected from the resin layer as a result of measurement by SEM-EDX (energy dispersive X-ray spectroscopy; the same applies hereinafter).
Example 2
< preparation of conductive substrate >
A conductive substrate [ layer structure ] was produced in the same manner as in example 1, except that ink 4 was used as the conductive ink: substrate/conductive layer).
< preparation of laminate >
The same operation as in example 1 was performed to obtain a laminate.
A glass mask having a line and space pattern with a line width and a space width of 8 μm and a take-out terminal pattern connected thereto was adhered to a temporary support of the obtained laminate, and then an ultra-high pressure mercury lamp (model: USH-2004MB, manufactured by USHIO INC.
The temporary support was peeled off from the laminate after 1 hour of exposure, and a 1.0 mass% aqueous potassium carbonate solution (liquid temperature: 30 ℃) was used as a developer, followed by development with showering for 30 seconds, whereby uncured portions were removed, and a resist pattern was formed.
The surface of the developed laminate on the side where the resist pattern was formed was sprayed with 30 mass% aqueous nitric acid (liquid temperature: 45 ℃ C., pH: 0.6) for 60 seconds by spraying, and the conductive layer in the portion where the resist pattern was not present on the surface was subjected to etching treatment, whereby the resin component in the conductive layer was left and silver was removed.
The laminate after the etching treatment was immersed in a 3 mass% aqueous sodium hydroxide solution (liquid temperature: 50 ℃) for 70 seconds, and the resist pattern remaining in the laminate was peeled off, to obtain a laminate of example 2.
As a result of visual inspection of the laminate of example 2 obtained, it was confirmed that there were conductive portions having a linear pattern on the substrate and a layer containing a resin (i.e., a resin layer) between the conductive portions. Further, it was confirmed that the area where the conductive portions are adjacent via the resin layer was 70% or more of the total length of the conductive portions.
In the result of measuring the volume resistivity of the conductive part, the volume resistivity is less than 1×10 4 Ωcm。
In the result of measuring the volume resistivity of the resin layer, it was 1X 10 8 And omega cm above.
No silver was detected from the resin layer as a result of measurement by SEM-EDX.
Example 3
< preparation of conductive substrate >
A conductive substrate [ layer structure ] was produced in the same manner as in example 1, except that ink 5 was used as the conductive ink: substrate/conductive layer).
< preparation of laminate >
The same operation as in example 1 was performed to obtain a laminate.
A glass mask having a line and space pattern with a line width and a space width of 4 μm and a take-out terminal pattern connected thereto was adhered to a temporary support of the obtained laminate, and then an ultra-high pressure mercury lamp (model: USH-2004MB, manufactured by USHIO INC.
The temporary support was peeled off from the laminate after 1 hour of exposure, and a 1.0 mass% aqueous potassium carbonate solution (liquid temperature: 30 ℃) was used as a developer, followed by development with showering for 30 seconds, whereby uncured portions were removed, and a resist pattern was formed.
The surface of the developed laminate on the side where the resist pattern was formed was sprayed with 30 mass% aqueous nitric acid (liquid temperature: 45 ℃ C., pH: 0.6) for 60 seconds by spraying, and the conductive layer in the portion where the resist pattern was not present on the surface was subjected to etching treatment, whereby the resin component in the conductive layer was left and silver was removed.
The laminate after the etching treatment was immersed in a 3 mass% aqueous sodium hydroxide solution (liquid temperature: 50 ℃) for 70 seconds, and the resist pattern remaining in the laminate was peeled off, to obtain a laminate of example 3.
As a result of visual inspection of the laminate of example 3, it was confirmed that the conductive portions having a linear pattern were present on the substrate and that a layer containing a resin (i.e., a resin layer) was present between the conductive portions. Further, it was confirmed that the area where the conductive portions are adjacent via the resin layer was 70% or more of the total length of the conductive portions.
In the result of measuring the volume resistivity of the conductive part, the volume resistivity is less than 1×10 4 Ωcm。
In the result of measuring the volume resistivity of the resin layer, it was 1X 10 8 And omega cm above.
No silver was detected from the resin layer as a result of measurement by SEM-EDX.
Example 4
< preparation of conductive substrate >
A conductive substrate [ layer structure ] was produced in the same manner as in example 1, except that ink 2 was used as the conductive ink: substrate/conductive layer).
< preparation of laminate >
The same operation as in example 1 was performed to obtain a laminate.
A glass mask having a line and space pattern with a line width and a space width of 16 μm and a take-out terminal pattern connected thereto was adhered to a temporary support of the obtained laminate, and then an ultra-high pressure mercury lamp (model: USH-2004MB, manufactured by USHIO INC.
The temporary support was peeled off from the laminate after 1 hour of exposure, and a 1.0 mass% aqueous potassium carbonate solution (liquid temperature: 30 ℃) was used as a developer, followed by development with showering for 30 seconds, whereby uncured portions were removed, and a resist pattern was formed.
The surface of the developed laminate on the side where the resist pattern was formed was sprayed with 30 mass% aqueous nitric acid (liquid temperature: 45 ℃ C., pH: 0.6) for 60 seconds by spraying, and the conductive layer in the portion where the resist pattern was not present on the surface was subjected to etching treatment, whereby the resin component in the conductive layer was left and copper was removed.
The laminate after the etching treatment was immersed in a 3 mass% aqueous sodium hydroxide solution (liquid temperature: 50 ℃) for 70 seconds, and the resist pattern remaining in the laminate was peeled off, to obtain a laminate of example 4.
As a result of visual inspection of the laminate of example 4, it was confirmed that the conductive portions having a linear pattern were present on the substrate and that a layer containing a resin (i.e., a resin layer) was present between the conductive portions. Further, it was confirmed that the area where the conductive portions are adjacent via the resin layer was 70% or more of the total length of the conductive portions.
In the result of measuring the volume resistivity of the conductive part, the volume resistivity is less than 1×10 4 Ωcm。
In the result of measuring the volume resistivity of the resin layer, it was 1X 10 8 And omega cm above.
No copper was detected from the resin layer as a result of measurement by SEM-EDX.
Example 5
< preparation of conductive substrate >
A conductive substrate [ layer structure ] was produced in the same manner as in example 1: substrate/conductive layer).
< preparation of laminate >
The same operation as in example 1 was performed to obtain a laminate.
A glass mask having a line and gap pattern with a line width and a space width of 18 μm and a take-out terminal pattern connected thereto was adhered to a temporary support of the obtained laminate, and then an ultra-high pressure mercury lamp (model: USH-2004MB, manufactured by USHIO INC.
The temporary support was peeled off from the laminate after 1 hour of exposure, and a 1.0 mass% aqueous potassium carbonate solution (liquid temperature: 30 ℃) was used as a developer, followed by development with showering for 30 seconds, whereby uncured portions were removed, and a resist pattern was formed.
The surface of the developed laminate on the side where the resist pattern was formed was sprayed with 30 mass% aqueous nitric acid (liquid temperature: 45 ℃ C., pH: 0.6) for 60 seconds by spraying, and the conductive layer in the portion where the resist pattern was not present on the surface was subjected to etching treatment, whereby the resin component in the conductive layer was left and silver was removed.
The laminate after the etching treatment was immersed in a 3 mass% aqueous sodium hydroxide solution (liquid temperature: 50 ℃) for 70 seconds, and the resist pattern remaining in the laminate was peeled off, to obtain a laminate of example 5.
As a result of visual inspection of the laminate of example 5, it was confirmed that the conductive portions having a linear pattern were present on the substrate and that a layer containing a resin (i.e., a resin layer) was present between the conductive portions. Further, it was confirmed that the area where the conductive portions are adjacent via the resin layer was 70% or more of the total length of the conductive portions.
In the result of measuring the volume resistivity of the conductive part, the volume resistivity is less than 1×10 4 Ωcm。
In the result of measuring the volume resistivity of the resin layer, it was 1X 10 8 And omega cm above.
No silver was detected from the resin layer as a result of measurement by SEM-EDX.
Example 6
< preparation of conductive substrate >
Ink 1 of the conductive ink prepared as above was applied to a substrate by an inkjet method so that the application width became 1.2m and the wet film thickness became 21 μm [ product name: lumiror (registered trademark) #100-U34, polyester film, manufactured by TORAY INDUSTRIES, INC.). After drying the coated film, the coated film was calcined at 140℃for 30 minutes, thereby producing a conductive substrate (layer structure: substrate/conductive layer).
< preparation of laminate >
The same operation as in example 1 was performed to obtain a laminate.
A glass mask having a line and space pattern with a line width and a space width of 10 μm and a take-out terminal pattern connected thereto was adhered to a temporary support of the obtained laminate, and then an ultra-high pressure mercury lamp (model: USH-2004MB, manufactured by USHIO INC.
The temporary support was peeled off from the laminate after 1 hour of exposure, and a 1.0 mass% aqueous potassium carbonate solution (liquid temperature: 30 ℃) was used as a developer, followed by development with showering for 30 seconds, whereby uncured portions were removed, and a resist pattern was formed.
The surface of the developed laminate on the side where the resist pattern was formed was sprayed with 30 mass% aqueous nitric acid (liquid temperature: 45 ℃ C., pH: 0.6) for 60 seconds by spraying, and the conductive layer in the portion where the resist pattern was not present on the surface was subjected to etching treatment, whereby the resin component in the conductive layer was left and silver was removed.
The laminate after the etching treatment was immersed in a 3 mass% aqueous sodium hydroxide solution (liquid temperature: 50 ℃) for 70 seconds, and the resist pattern remaining in the laminate was peeled off, to obtain a laminate of example 6.
As a result of visual inspection of the laminate of example 6, it was confirmed that the conductive portions having a linear pattern were present on the substrate and that a layer containing a resin (i.e., a resin layer) was present between the conductive portions. Further, it was confirmed that the area where the conductive portions are adjacent via the resin layer was 70% or more of the total length of the conductive portions.
In the result of measuring the volume resistivity of the conductive part, the volume resistivity is less than 1×10 4 Ωcm。
In the result of measuring the volume resistivity of the resin layer, it was 1X 10 8 And omega cm above.
No silver was detected from the resin layer as a result of measurement by SEM-EDX.
Example 7
< preparation of conductive substrate >
Ink 1 of the conductive ink prepared as above was applied to a substrate by an inkjet method so that the application width became 1.2m and the wet film thickness became 13 μm [ product name: lumiror (registered trademark) #100-U34, polyester film, manufactured by TORAY INDUSTRIES, INC.). After drying the coated film, the coated film was calcined at 140℃for 30 minutes, thereby producing a conductive substrate (layer structure: substrate/conductive layer).
< preparation of laminate >
The same operation as in example 1 was performed to obtain a laminate.
A glass mask having a line and space pattern with a line width and a space width of 10 μm and a take-out terminal pattern connected thereto was adhered to a temporary support of the obtained laminate, and then an ultra-high pressure mercury lamp (model: USH-2004MB, manufactured by USHIO INC.
The temporary support was peeled off from the laminate after 1 hour of exposure, and a 1.0 mass% aqueous potassium carbonate solution (liquid temperature: 30 ℃) was used as a developer, followed by development with showering for 30 seconds, whereby uncured portions were removed, and a resist pattern was formed.
The surface of the developed laminate on the side where the resist pattern was formed was sprayed with 30 mass% aqueous nitric acid (liquid temperature: 45 ℃ C., pH: 0.6) for 60 seconds by spraying, and the conductive layer in the portion where the resist pattern was not present on the surface was subjected to etching treatment, whereby the resin component in the conductive layer was left and silver was removed.
The laminate after the etching treatment was immersed in a 3 mass% aqueous sodium hydroxide solution (liquid temperature: 50 ℃) for 70 seconds, and the resist pattern remaining in the laminate was peeled off, to obtain a laminate of example 7.
As a result of visual inspection of the laminate of example 7, it was confirmed that the conductive portions having a linear pattern were present on the substrate and that a layer containing a resin (i.e., a resin layer) was present between the conductive portions. Further, it was confirmed that the area where the conductive portions are adjacent via the resin layer was 70% or more of the total length of the conductive portions.
In the result of measuring the volume resistivity of the conductive part, the volume resistivity is less than 1×10 4 Ωcm。
In the result of measuring the volume resistivity of the resin layer, it was 1X 10 8 And omega cm above.
No silver was detected from the resin layer as a result of measurement by SEM-EDX.
Example 8
< preparation of conductive substrate >
A conductive substrate [ layer structure ] was produced in the same manner as in example 1, except that ink 6 was used as the conductive ink: substrate/conductive layer).
< preparation of laminate >
The same operation as in example 1 was performed to obtain a laminate.
A glass mask having a line and space pattern with a line width and a space width of 12 μm and a take-out terminal pattern connected thereto was adhered to a temporary support of the obtained laminate, and then an ultra-high pressure mercury lamp (model: USH-2004MB, manufactured by USHIO INC.
The temporary support was peeled off from the laminate after 1 hour of exposure, and a 1.0 mass% aqueous potassium carbonate solution (liquid temperature: 30 ℃) was used as a developer, followed by development with showering for 30 seconds, whereby uncured portions were removed, and a resist pattern was formed.
The surface of the developed laminate on the side where the resist pattern was formed was sprayed with 30 mass% aqueous nitric acid (liquid temperature: 45 ℃ C., pH: 0.6) for 60 seconds by spraying, and the conductive layer in the portion where the resist pattern was not present on the surface was subjected to etching treatment, whereby the resin component in the conductive layer was left and silver was removed.
The laminate after the etching treatment was immersed in a 3 mass% aqueous sodium hydroxide solution (liquid temperature: 50 ℃) for 70 seconds, and the resist pattern remaining in the laminate was peeled off, to obtain a laminate of example 8.
As a result of visual inspection of the laminate of example 8, it was confirmed that the conductive portions having a linear pattern were present on the substrate and that a layer containing a resin (i.e., a resin layer) was present between the conductive portions. Further, it was confirmed that the area where the conductive portions are adjacent via the resin layer was 70% or more of the total length of the conductive portions.
In the result of measuring the volume resistivity of the conductive part, the volume resistivity is less than 1×10 4 Ωcm。
In the result of measuring the volume resistivity of the resin layer, it was 1X 10 8 And omega cm above.
No silver was detected from the resin layer as a result of measurement by SEM-EDX.
Example 9
< preparation of conductive substrate >
Ink 3 of the conductive ink prepared as above was applied to a substrate by an inkjet method so that the application width became 1.2m and the wet film thickness became 21 μm [ product name: lumiror (registered trademark) #100-U34, polyester film, manufactured by TORAY INDUSTRIES, INC.). After drying the coated film, the coated film was calcined at 140℃for 30 minutes, thereby producing a conductive substrate (layer structure: substrate/conductive layer).
< preparation of laminate >
The same operation as in example 1 was performed to obtain a laminate.
A glass mask having a line and space pattern with a line width and a space width of 10 μm and a take-out terminal pattern connected thereto was adhered to a temporary support of the obtained laminate, and then an ultra-high pressure mercury lamp (model: USH-2004MB, manufactured by USHIO INC.
The temporary support was peeled off from the laminate after 1 hour of exposure, and a 1.0 mass% aqueous potassium carbonate solution (liquid temperature: 30 ℃) was used as a developer, followed by development with showering for 30 seconds, whereby uncured portions were removed, and a resist pattern was formed.
The surface of the developed laminate on the side where the resist pattern was formed was sprayed with 30 mass% aqueous nitric acid (liquid temperature: 45 ℃ C., pH: 0.6) for 60 seconds by spraying, and the conductive layer in the portion where the resist pattern was not present on the surface was subjected to etching treatment, whereby the resin component in the conductive layer was left and silver was removed.
The laminate after the etching treatment was immersed in a 3 mass% aqueous sodium hydroxide solution (liquid temperature: 50 ℃) for 70 seconds, and the resist pattern remaining in the laminate was peeled off, to obtain a laminate of example 9.
As a result of the laminate of example 9 obtained by visual inspection, it was confirmed that there were conductive portions having a linear pattern on the substrate and a layer containing a resin (i.e., a resin layer) between the conductive portions. Further, it was confirmed that the area where the conductive portions are adjacent via the resin layer was 70% or more of the total length of the conductive portions.
In the result of measuring the volume resistivity of the conductive part, the volume resistivity is less than 1×10 4 Ωcm。
In the result of measuring the volume resistivity of the resin layer, it was 1X 10 8 And omega cm above.
No silver was detected from the resin layer as a result of measurement by SEM-EDX.
Comparative example 1
< preparation of conductive substrate >
In an intermittent vacuum vapor deposition apparatus [ model: EBH-800, manufactured by ALBAX CO.LTD ] a substrate (product name: lumirror100-U34, polyester film, TORAYINDUSTRIES, INC.. Next, silver was placed in an amount of a target thickness on the evaporation boat. Then, vacuum pumping was performed until the degree of vacuum reached was 9.0X10 -3 Pa or less, and then heating the evaporation boat to perform vacuum evaporation on the substrate surface. By the above method, a conductive base material (layer structure: base material/conductive layer) was produced.
< preparation of laminate >
The same operation as in example 9 was performed to obtain a laminate of comparative example 1.
Example 10
< preparation of conductive substrate >
A conductive substrate (layer structure: substrate/conductive layer) was produced in the same manner as in comparative example 1, except that the amount of silver placed on the evaporation boat was changed.
< preparation of laminate >
The same operation as in example 1 was performed to obtain a laminate.
A glass mask having a line and space pattern with a line width and a space width of 8 μm and a take-out terminal pattern connected thereto was adhered to a temporary support of the obtained laminate, and then an ultra-high pressure mercury lamp (model: USH-2004MB, manufactured by USHIO INC.
The temporary support was peeled off from the laminate after 1 hour of exposure, and a 1.0 mass% aqueous potassium carbonate solution (liquid temperature: 30 ℃) was used as a developer, followed by development with showering for 30 seconds, whereby uncured portions were removed, and a resist pattern was formed.
The surface of the developed laminate on the side where the resist pattern was formed was sprayed with 30 mass% aqueous nitric acid (liquid temperature: 45 ℃ C., pH: 0.6) for 60 seconds by spraying, and the conductive layer in the portion where the resist pattern was not present on the surface was subjected to etching treatment, whereby the resin component in the conductive layer was left and silver was removed.
The laminate after the etching treatment was immersed in a 3 mass% aqueous sodium hydroxide solution (liquid temperature: 50 ℃) for 70 seconds, and the resist pattern remaining in the laminate was peeled off.
After the resist pattern was peeled off, the material X was applied to the side of the substrate having the conductive layer so that the film thickness became 0.2 μm, and then an ultra-high pressure mercury lamp (model: USH-2004MB, manufactured by USHIO INC. The exposure was set to 100mJ/cm 2 。
The exposed laminate was left to stand in an atmosphere of 25℃and 60% RH for 1 hour.
The laminate after being left to stand WAs subjected to development treatment and cleaning treatment using a developing machine (model: YCD-500 WA) manufactured by YAMAGATA MACHINERY CO., LTD. To obtain a laminate of example 10.
In addition, when the development treatment was performed, a 1.0 mass% aqueous sodium carbonate solution (liquid temperature: 30 ℃ C.) was used, and spray development treatment (spray nozzle: compact cone nozzle, spray pressure: 0.10MPa, spray flow rate: 1000mL/min, spray angle: 90 ℃ C.) was performed while supplying a new liquid. The development time was set to 60 seconds. Further, immediately after the development treatment, a cleaning treatment (so-called rinsing treatment) was performed using pure water. In the cleaning treatment, a spray cleaning treatment (spray nozzle: compact cone nozzle, spray pressure: 0.10MPa, spray flow rate: 1000mL/min, spray angle: 90 °) using pure water (liquid temperature: 30 ℃) was performed.
As a result of visual inspection of the laminate of example 10, it was confirmed that there were conductive portions having a linear pattern on the substrate and a layer containing a resin (i.e., a resin layer) between the conductive portions. Further, it was confirmed that the area where the conductive portions are adjacent via the resin layer was 70% or more of the total length of the conductive portions.
In the result of measuring the volume resistivity of the conductive part, the volume resistivity is less than 1×10 4 Ωcm。
In the result of measuring the volume resistivity of the resin layer, it was 1X 10 8 And omega cm above.
No silver was detected from the resin layer as a result of measurement by SEM-EDX.
Example 11
< preparation of conductive substrate >
In an intermittent vacuum vapor deposition apparatus [ model: EBH-800, manufactured by ALBAX CO.LTD ] a substrate (product name: lumirror100-U34, polyester film, TORAY INDUSTRIES, INC.). Next, copper was placed in an amount of a target thickness on the evaporation boat. Then, vacuum pumping was performed until the degree of vacuum reached was 9.0X10 -3 Pa or less, and then heating the evaporation boat to perform vacuum evaporation on the substrate surface. By the above method, a conductive base material (layer structure: base material/conductive layer) was produced.
< preparation of laminate >
The same operation as in example 1 was performed to obtain a laminate.
A glass mask having a line and space pattern with a line width and a space width of 14 μm and a take-out terminal pattern connected thereto was adhered to a temporary support of the obtained laminate, and then an ultra-high pressure mercury lamp (model: USH-2004MB, manufactured by USHIO INC.
The temporary support was peeled off from the laminate after 1 hour of exposure, and a 1.0 mass% aqueous potassium carbonate solution (liquid temperature: 30 ℃) was used as a developer, followed by development with showering for 30 seconds, whereby uncured portions were removed, and a resist pattern was formed.
The surface of the developed laminate on the side where the resist pattern was formed was sprayed with 30 mass% aqueous nitric acid (liquid temperature: 45 ℃ C., pH: 0.6) for 60 seconds by spraying, and the conductive layer in the portion where the resist pattern was not present on the surface was subjected to etching treatment, whereby the resin component in the conductive layer was left and copper was removed.
The laminate after the etching treatment was immersed in a 3 mass% aqueous sodium hydroxide solution (liquid temperature: 50 ℃) for 70 seconds, and the resist pattern remaining in the laminate was peeled off.
After the resist pattern was peeled off, the material X was applied to the side of the substrate having the conductive layer so that the film thickness became 0.2 μm, and then an ultra-high pressure mercury lamp (model: USH-2004MB, manufactured by USHIO INC. The exposure was set to 100mJ/cm 2 。
The exposed laminate was left to stand in an atmosphere of 25℃and 60% RH for 1 hour.
The laminate after being left to stand WAs subjected to development treatment and cleaning treatment using a developing machine (model: YCD-500 WA) manufactured by YAMAGATA MACHINERY CO., LTD. To obtain a laminate of example 11.
In addition, when the development treatment was performed, a 1.0 mass% aqueous sodium carbonate solution (liquid temperature: 30 ℃ C.) was used, and spray development treatment (spray nozzle: compact cone nozzle, spray pressure: 0.10MPa, spray flow rate: 1000mL/min, spray angle: 90 ℃ C.) was performed while supplying a new liquid. The development time was set to 60 seconds. Further, immediately after the development treatment, a cleaning treatment (so-called rinsing treatment) was performed using pure water. In the cleaning treatment, a spray cleaning treatment (spray nozzle: compact cone nozzle, spray pressure: 0.10MPa, spray flow rate: 1000mL/min, spray angle: 90 °) using pure water (liquid temperature: 30 ℃) was performed.
As a result of visual inspection of the laminate of example 11, it was confirmed that the conductive portions having a linear pattern were present on the substrate and that a layer containing a resin (i.e., a resin layer) was present between the conductive portions. Further, it was confirmed that the area where the conductive portions are adjacent via the resin layer was 70% or more of the total length of the conductive portions.
In the result of measuring the volume resistivity of the conductive part, the volume resistivity is less than 1×10 4 Ωcm。
In the result of measuring the volume resistivity of the resin layer, it was 1X 10 8 And omega cm above.
No copper was detected from the resin layer as a result of measurement by SEM-EDX.
Example 12
< preparation of conductive substrate >
Ink 3 of the conductive ink prepared as above was applied to a substrate by an inkjet method so that the application width became 1.2m and the wet film thickness became 21 μm [ product name: lumiror (registered trademark) #100-U34, polyester film, manufactured by TORAY INDUSTRIES, INC.). After drying the coated film, the coated film was calcined at 140℃for 30 minutes, thereby producing a conductive substrate (layer structure: substrate/conductive layer).
< preparation of laminate >
The same operation as in example 1 was performed to obtain a laminate.
A glass mask having a line and space pattern with a line width and a space width of 10 μm and a take-out terminal pattern connected thereto was adhered to a temporary support of the obtained laminate, and then an ultra-high pressure mercury lamp (model: USH-2004MB, manufactured by USHIO INC.
The temporary support was peeled off from the laminate after 1 hour of exposure, and a 1.0 mass% aqueous potassium carbonate solution (liquid temperature: 30 ℃) was used as a developer, followed by development with showering for 30 seconds, whereby uncured portions were removed, and a resist pattern was formed.
The surface of the developed laminate on the side where the resist pattern was formed was sprayed with 30 mass% aqueous nitric acid (liquid temperature: 45 ℃ C., pH: 0.6) for 60 seconds by spraying, and the conductive layer in the portion where the resist pattern was not present on the surface was subjected to etching treatment, whereby the resin component in the conductive layer was left and silver was removed.
The laminate after the etching treatment was immersed in a 3 mass% aqueous sodium hydroxide solution (liquid temperature: 50 ℃) for 70 seconds, and the resist pattern remaining in the laminate was peeled off.
After the resist pattern was peeled off, the material X was applied to the side of the substrate having the conductive layer so that the film thickness became 0.3 μm, and then an ultra-high pressure mercury lamp (model: USH-2004MB, manufactured by USHIO INC. The exposure was set to 100mJ/cm 2 。
The exposed laminate was left to stand in an atmosphere of 25℃and 60% RH for 1 hour.
The laminate after being left to stand WAs subjected to development treatment and cleaning treatment using a developing machine (model: YCD-500 WA) manufactured by YAMAGATA MACHINERY CO., LTD. To obtain a laminate of example 12.
In addition, when the development treatment was performed, a 1.0 mass% aqueous sodium carbonate solution (liquid temperature: 30 ℃ C.) was used, and spray development treatment (spray nozzle: compact cone nozzle, spray pressure: 0.10MPa, spray flow rate: 1000mL/min, spray angle: 90 ℃ C.) was performed while supplying a new liquid. The development time was set to 60 seconds. Further, immediately after the development treatment, a cleaning treatment (so-called rinsing treatment) was performed using pure water. In the cleaning treatment, a spray cleaning treatment (spray nozzle: compact cone nozzle, spray pressure: 0.10MPa, spray flow rate: 1000mL/min, spray angle: 90 °) using pure water (liquid temperature: 30 ℃) was performed.
As a result of visual inspection of the laminate of example 12, it was confirmed that the conductive portions having a linear pattern were present on the substrate and that a layer containing a resin (i.e., a resin layer) was present between the conductive portions. Further, it was confirmed that the area where the conductive portions are adjacent via the resin layer was 70% or more of the total length of the conductive portions.
In the result of measuring the volume resistivity of the conductive part, the volume resistivity is less than 1×10 4 Ωcm。
In the result of measuring the volume resistivity of the resin layer, it was 1X 10 8 And omega cm above.
No silver was detected from the resin layer as a result of measurement by SEM-EDX.
Comparative example 2
< preparation of conductive substrate >
In an intermittent vacuum vapor deposition apparatus [ model: EBH-800, manufactured by ALBAX CO.LTD ] a substrate (product name: lumirror100-U34, polyester film, TORAY INDUSTRIES, INC.). Next, copper was placed in an amount of a target thickness on the evaporation boat. Then, vacuum pumping was performed until the degree of vacuum reached was 9.0X10 -3 Pa or less, and then heating the evaporation boat to perform vacuum evaporation on the substrate surface. By the above method, a conductive base material (layer structure: base material/conductive layer) was produced.
< preparation of laminate >
The same operation as in example 1 was performed to obtain a laminate.
A glass mask having a line and space pattern with a line width and a space width of 10 μm and a take-out terminal pattern connected thereto was adhered to a temporary support of the obtained laminate, and then an ultra-high pressure mercury lamp (model: USH-2004MB, manufactured by USHIO INC.
The temporary support was peeled off from the laminate after 1 hour of exposure, and a 1.0 mass% aqueous potassium carbonate solution (liquid temperature: 30 ℃) was used as a developer, followed by development with showering for 30 seconds, whereby uncured portions were removed, and a resist pattern was formed.
The surface of the developed laminate on the side where the resist pattern was formed was sprayed with 30 mass% aqueous nitric acid (liquid temperature: 45 ℃ C., pH: 0.6) for 60 seconds by spraying, and the conductive layer in the portion where the resist pattern was not present on the surface was subjected to etching treatment, whereby the resin component in the conductive layer was left and copper was removed.
The laminate after the etching treatment was immersed in a 3 mass% aqueous sodium hydroxide solution (liquid temperature: 50 ℃) for 70 seconds, and the resist pattern remaining in the laminate was peeled off, to obtain a laminate of comparative example 2.
Comparative example 3
< preparation of conductive substrate >
A conductive substrate (layer structure: substrate/conductive layer) was produced in the same manner as in comparative example 1.
< preparation of laminate >
The same operation as in example 1 was performed to obtain a laminate.
A glass mask having a line and space pattern with a line width and a space width of 10 μm and a take-out terminal pattern connected thereto was adhered to a temporary support of the obtained laminate, and then an ultra-high pressure mercury lamp (model: USH-2004MB, manufactured by USHIO INC.
The temporary support was peeled off from the laminate after 1 hour of exposure, and a 1.0 mass% aqueous potassium carbonate solution (liquid temperature: 30 ℃) was used as a developer, followed by development with showering for 30 seconds, whereby uncured portions were removed, and a resist pattern was formed.
The surface of the developed laminate on the side where the resist pattern was formed was sprayed with 30 mass% aqueous nitric acid (liquid temperature: 45 ℃ C., pH: 0.6) for 60 seconds by spraying, and the conductive layer in the portion where the resist pattern was not present on the surface was subjected to etching treatment, whereby the resin component in the conductive layer was left and silver was removed.
The laminate after the etching treatment was immersed in a 3 mass% aqueous sodium hydroxide solution (liquid temperature: 50 ℃) for 70 seconds, and the resist pattern remaining in the laminate was peeled off.
After the resist pattern was stripped, the material X was applied to the side of the substrate having the conductive layer so that the film thickness became 1.1. Mu.m, and then the use of ultra-high pressure was performed from the side of the substrate opposite to the side having the conductive layer with the conductive layer as a maskMercury lamp (model number: USH-2004MB, manufactured by USHIO INC. The exposure was set to 100mJ/cm 2 。
The exposed laminate was left to stand in an atmosphere of 25℃and 60% RH for 1 hour.
The laminate after being left to stand WAs subjected to development treatment and cleaning treatment using a developing machine (model: YCD-500 WA) manufactured by YAMAGATA MACHINERY CO., LTD. To obtain a laminate of comparative example 3.
In addition, when the development treatment was performed, a 1.0 mass% aqueous sodium carbonate solution (liquid temperature: 30 ℃ C.) was used, and spray development treatment (spray nozzle: compact cone nozzle, spray pressure: 0.10MPa, spray flow rate: 1000mL/min, spray angle: 90 ℃ C.) was performed while supplying a new liquid. The development time was set to 60 seconds. Further, immediately after the development treatment, a cleaning treatment (so-called rinsing treatment) was performed using pure water. In the cleaning treatment, a spray cleaning treatment (spray nozzle: compact cone nozzle, spray pressure: 0.10MPa, spray flow rate: 1000mL/min, spray angle: 90 °) using pure water (liquid temperature: 30 ℃) was performed.
[ measurement ]
[ thickness of conductive portion M ]
The thickness M of the conductive portion was calculated for each of the laminates of examples 1 to 12 and comparative examples 1 to 3.
The laminate was cut using an ultra-thin microtome to produce a cross section of the conductive portion pattern of the wire and the gap. In the production, the laminate is cut so that the cross section is substantially perpendicular to the longitudinal direction of the pattern. The thickness of the center portion in the width direction of the pattern of the conductive portion in the cross section was measured using a scanning electron microscope (SEM, model: JSM-7200F) manufactured by JEOL co., ltd. And observing the manufactured cross section under the condition of an acceleration voltage of 5 kV. The above-described production and measurement were repeated 5 times (in other words, 5 cross sections were produced, and the thickness of the central portion in the width direction of the pattern of the conductive portion in each cross section was measured), and the obtained 5 measured values were arithmetically averaged, whereby the thickness M of the conductive portion was calculated. The results are shown in tables 1 and 2.
[ thickness of resin layer R ]
The thickness R of the resin layer was calculated for each of the laminates of examples 1 to 12 and comparative example 3.
The laminate was cut using an ultra-thin microtome to produce a cross section of the conductive portion pattern of the wire and the gap. In the production, the laminate is cut so that the cross section is substantially perpendicular to the longitudinal direction of the pattern. Next, in order to impart conductivity to the spacers of the residual resin component, carbon coating is performed. Next, the thickness of the central portion in the width direction of the pattern of the spacer portion (i.e., the resin layer) in which the resin component remained in the cross section was measured using a scanning electron microscope (SEM, model: JSM-7200F) manufactured by JEOL co., ltd and observing the manufactured cross section under the condition of an acceleration voltage of 5 kV. The above production and measurement were repeated 5 times (in other words, 5 cross sections were produced, carbon coating was performed on the produced spacers of the residual resin component of each cross section, and then the thickness in the widthwise central portion of the pattern of the spacers in each cross section was measured), and the obtained 5 measured values were arithmetically averaged, whereby the thickness R of the resin layer was calculated. The results are shown in tables 1 and 2.
[ distance between Linear patterns L ]
The distance L between the linear patterns was calculated for each laminate of examples 1 to 12 and comparative examples 1 to 3.
The laminate was cut using an ultra-thin microtome to produce a cross section of the conductive portion pattern of the wire and the gap. In the production, the laminate is cut so that the cross section is substantially perpendicular to the longitudinal direction of the pattern. Next, in order to impart conductivity to the spacers of the residual resin component, carbon coating is performed. Next, the width of the spacer portion of the remaining resin component in the cross section (i.e., the width of the resin layer existing between the conductive portions) was measured using a scanning electron microscope (SEM, model: JSM-7200F) manufactured by JEOL co., ltd. And observing the manufactured cross section under the condition of an acceleration voltage of 5 kV. The above-mentioned production and measurement were repeated 5 times (in other words, 5 cross sections were produced, carbon coating was performed on the produced spacers of the residual resin component of each cross section, and then the widths of the above-mentioned spacers of each cross section were measured), and the obtained 5 measured values were arithmetically averaged, whereby the distance L between the linear patterns was calculated. The results are shown in tables 1 and 2.
[ evaluation ]
The following evaluations were performed on the respective laminates of examples 1 to 12 and comparative examples 1 to 3.
1. Lamination suitability
OCA (Optical Clear Adhesive) film (model number: 8215. 3M Japan Limited) as a sample for evaluation.
The sample for evaluation immediately after bonding, the sample for evaluation after being left in an atmosphere of 25 ℃ and 55% rh for 30 minutes (hereinafter, also referred to as "after a lapse of time after bonding"), and the sample for evaluation after being left in a convection oven of 50 ℃ for 30 minutes (hereinafter, also referred to as "after heating") were observed by an optical microscope at a magnification of 50 times, and evaluated according to the following evaluation criteria. The results are shown in tables 1 and 2.
The wiring board is preferably "3", "4" or "5", more preferably "4" or "5", and particularly preferably "5".
Evaluation criterion-
5: immediately after bonding, there was no air bubble between the OCA film and the conductive portion pattern of the laminate.
4: immediately after bonding, minute bubbles exist between the OCA film and the conductive portion pattern of the laminate, but disappear after a period of time after bonding.
3: after a lapse of time from the lamination, minute bubbles exist between the OCA film and the conductive portion pattern of the laminate, but disappear after heating.
2: after heating, there are microscopic bubbles between the OCA film and the conductive portion pattern of the laminate.
1: after heating, coarse bubbles exist between the OCA film and the conductive portion pattern of the laminate.
2. Inhibiting migration
Whether or not migration was suppressed was evaluated based on the degree of dimensional change of the conductive portion pattern before and after the passage of the current.
The laminate in which the electrodes were connected to the terminals of the conductive pattern was placed in a constant temperature bath having an in-bath temperature of 85 ℃ and an in-bath humidity of 85% RH, and a Direct Current (DC) voltage of 5V was applied for 50 hours. After the voltage was applied, the width of the conductive portion pattern was measured using an optical microscope having a magnification of 500 times, and the rate of change of the width of the conductive portion pattern (hereinafter, also referred to as "rate of change of width") was calculated and compared with that before the voltage was applied, and the evaluation was performed according to the following evaluation criteria. The results are shown in tables 1 and 2.
The smaller the width change rate, the more suppressed the occurrence of migration.
The wiring board is preferably "3", "4" or "5", more preferably "4" or "5", and particularly preferably "5".
Evaluation criterion-
5: the width change rate is less than 10 percent
4: the width change rate is more than or equal to 10 percent and less than 15 percent
3: the width change rate is more than or equal to 15 percent and less than 20 percent
2: the width change rate is more than or equal to 20 percent and less than 25 percent
1: width change rate of 25% or less
TABLE 1
TABLE 2
As shown in tables 1 and 2, it was confirmed that the laminate of examples was excellent in lamination suitability and suppressed in migration.
On the other hand, it was confirmed that the laminate of the comparative example could not achieve both excellent lamination suitability and suppression of migration.
Symbol description
100-laminate, 30-substrate, 40-conductive part, 50-resin layer, GR-light shielding part (non-image part), EX-exposure part (image part), DL-alignment frame.

Claims (12)

1. A laminate having a substrate and a conductive portion,
the conductive portion has a region adjacent via a resin layer,
the thickness M of the conductive part and the thickness R of the resin layer satisfy the following formula (1),
0＜R/M＜1/2 (1)。
2. the laminate according to claim 1, wherein,
the thickness M of the conductive part and the thickness R of the resin layer satisfy the following formula (1-2),
1/10∈＜/M＜1/3 (1-2)。
3. the laminate according to claim 1 or 2, wherein,
the thickness M of the conductive part is 0.1-2.0 μm.
4. The laminate according to claim 1 or 2, wherein,
the conductive portion includes at least one of a metal monomer and a metal alloy,
The metal monomer is at least 1 selected from gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc and manganese,
the metal alloy is an alloy composed of 2 or more metal elements selected from gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc and manganese.
5. The laminate according to claim 1 or 2, wherein,
the conductive portion includes a resin and at least one of a metal monomer and a metal alloy,
the metal monomer is at least 1 selected from gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc and manganese,
the metal alloy is an alloy composed of 2 or more metal elements selected from gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc and manganese.
6. The laminate according to claim 1 or 2, wherein,
the conductive part has a linear pattern and,
the distance L between the linear patterns is 1-20 μm.
7. The laminate according to claim 1 or 2, wherein,
the conductive part has a linear pattern and,
the distance L between the linear patterns and the thickness R of the resin layer satisfy the following formula (2),
0＜L×R＜10 (2)。
8. the laminate according to claim 1 or 2, wherein,
the conductive portion includes the same resin as the resin included in the resin layer.
9. A laminate having a substrate and a conductive portion,
the conductive portion has a region adjacent via a resin layer,
the thickness M of the conductive part and the thickness R of the resin layer satisfy the following formula (1),
the thickness M of the conductive part is 0.1-2.0 μm,
the conductive portion includes at least one of a metal monomer and a metal alloy,
the metal monomer is at least 1 selected from gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc and manganese,
the metal alloy is an alloy composed of more than 2 metal elements selected from gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc and manganese,
the conductive portion contains the same resin as the resin contained in the resin layer,
the conductive part has a linear pattern and,
the distance L between the linear patterns is 1-20 mu m,
the distance L between the linear patterns and the thickness R of the resin layer satisfy the following formula (2),
0＜R/M＜1/2 (1)，
0＜L×R＜10 (2)。
10. a method of manufacturing the laminate according to any one of claims 1 to 9, comprising, in order:
a step of preparing a substrate having a layer A containing a metal nano-body and a resin;
forming a resist on the layer a;
patterning the resist;
etching the layer a with the patterned resist as a mask so that at least a part of the resin contained in the layer a remains; and
And removing the patterned resist to form a conductive portion.
11. A method of manufacturing the laminate according to any one of claims 1 to 9, comprising, in order:
a step of preparing a substrate having a layer B containing a metal;
a step of forming a resist on the layer B;
patterning the resist;
etching the layer B using the patterned resist as a mask;
a step of removing the patterned resist to form a conductive portion;
forming a negative photosensitive resin layer between adjacent conductive portions; and
And exposing the negative photosensitive resin layer.
12. The method for producing a laminate according to claim 11, wherein,
the step of forming a negative photosensitive resin layer between the conductive portions is a step of forming a negative photosensitive resin layer between the conductive portions on the side opposite to the base material and the adjacent conductive portions,
the step of exposing the negative photosensitive resin layer is a step of exposing the substrate from a side opposite to a side having the conductive portion with the conductive portion as a mask,
the method for producing a laminate further includes a step of removing the unexposed negative photosensitive resin layer.
CN202310938196.8A 2022-07-29 2023-07-28 Laminate and method for producing laminate Pending CN117476271A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022-122237 2022-07-29
JP2022122237A JP2024018718A (en) 2022-07-29 2022-07-29 Laminate and method for producing laminate

Publications (1)

Publication Number Publication Date
CN117476271A true CN117476271A (en) 2024-01-30

Family

ID=89629957

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310938196.8A Pending CN117476271A (en) 2022-07-29 2023-07-28 Laminate and method for producing laminate

Country Status (2)

Country Link
JP (1) JP2024018718A (en)
CN (1) CN117476271A (en)

Also Published As

Publication number Publication date
JP2024018718A (en) 2024-02-08

Similar Documents

Publication Publication Date Title
CN115480450A (en) Substrate having conductive pattern, method for manufacturing same, method for manufacturing electronic device, and protective film for metal nanoparticles
CN116802558A (en) Method for producing laminated body, method for producing circuit wiring, method for producing electronic device, and photosensitive transfer material
CN116018262A (en) Photosensitive transfer material, method for producing resin pattern, etching method, and method for producing electronic device
CN117476271A (en) Laminate and method for producing laminate
CN115335771A (en) Photosensitive transfer material, method for producing resin pattern, and method for producing circuit wiring
CN117806081A (en) Laminate and method for producing laminate
CN117621587A (en) Laminate and method for producing laminate
WO2022181016A1 (en) Method for producing conductive pattern and method for producing electronic device
WO2024024864A1 (en) Photosensitive transfer material, method for manufacturing same, method for manufacturing resin pattern, and method for manufacturing circuit wiring
CN117465091A (en) Laminate and electronic device
WO2023127755A1 (en) Method for producing resist pattern, method for producing laminate, and photosensitive transfer material for direct imaging exposure
WO2022181455A1 (en) Transfer film, and method for manufacturing conductor pattern
US20240049386A1 (en) Laminate and electronic device
WO2022163301A1 (en) Photosensitive transfer material, resin pattern manufacturing method, circuit wiring manufacturing method, and touch panel manufacturing method
WO2022181456A1 (en) Transfer film and method for manufacturing conductor pattern
JP2022184720A (en) Manufacturing method of substrate having conductive pattern, manufacturing method of electronic device, substrate having conductive pattern, and protective film for metal nano substance
TW202413096A (en) Photosensitive transfer material, and method for manufacturing thereof, method for manufacturing resin pattern, and method for manufacturing circuit wiring
CN116356321A (en) Method for manufacturing vapor deposition mask
CN116360208A (en) Photosensitive transfer material for vapor deposition mask production and method for producing vapor deposition mask
TW202229012A (en) Transfer material and production method of laminate body
TW202231479A (en) Transfer material and method for producing laminate
CN116194845A (en) Photomask, exposure method, method for producing resin pattern, and method for producing photomask
JP2024018901A (en) Laminate, and electronic device
CN116670588A (en) Photosensitive transfer material, method for producing resin pattern, method for producing laminate, method for producing circuit wiring, and method for producing electronic device
CN115542669A (en) Laminate, transfer film, pattern forming method, and method for manufacturing circuit board

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication