Stacked body, method for manufacturing stacked body

Abstract

The present application provides a laminate capable of inhibiting corrosion of a metal pattern that becomes a resonator for electromagnetic waves of a terahertz band, and a method for manufacturing the laminate. The laminate of the present application has a dielectric film, a metal pattern that becomes a resonator for electromagnetic waves of a terahertz band disposed on at least one surface side of the dielectric film, and an organic film disposed on the metal pattern, the organic film having a moisture permeability of 3000 g / (m 2 ·24hr) or less in an environment of a temperature of 40°C and a relative humidity of 90%.

Description

Technical Field

[0001] This invention relates to a laminate and a method for manufacturing a laminate. Background Technology

[0002] Metamaterials are aggregates of microstructures arranged artificially to a wavelength smaller than that of electromagnetic waves. The characteristic optical response exhibited by these aggregates of microstructures can induce effective changes in refractive index. If such metamaterials are fabricated on films with a thickness at the micrometer level, they can be used in optical components for terahertz waves (electromagnetic waves with frequency numbers of 0.1–10 THz and wavelengths of 30–3000 μm).

[0003] Patent Document 1 discloses a sheet-type metamaterial comprising a film-like dielectric substrate, a first wire frame formed on one side of the dielectric substrate by a first truncated metal wire, and a second wire frame formed on the other side of the dielectric substrate by a second truncated metal wire.

[0004] Previous technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2017-157975 Summary of the Invention

[0007] The technical problem to be solved by the invention

[0008] The inventors studied the properties of the sheet-type metamaterial described in Patent Document 1 and found that corrosion easily occurs in the metal truncated wires that form the wireframe disposed on the dielectric substrate. If such corrosion occurs, a change in the effective refractive index occurs, and as a result, the function of the metamaterial sometimes deteriorates.

[0009] The objective of this invention is to provide a laminate capable of suppressing corrosion of a metal pattern that becomes a resonator for electromagnetic waves in the terahertz frequency band.

[0010] Furthermore, the present invention also aims to provide a method for manufacturing a laminate.

[0011] means for solving technical problems

[0012] Based on in-depth research into the above-mentioned issues, the inventors discovered that the following structure can solve these issues.

[0013] (1) A laminated body having:

[0014] Dielectric film;

[0015] A metallic pattern disposed on at least one surface side of a dielectric film, serving as a resonator for electromagnetic waves in the terahertz frequency band; and

[0016] When applied to a metallic pattern, the moisture permeability is 3000 g / (m²) at 40°C and 90% relative humidity. 2 Organic membranes with a lifespan of 24 hours or less.

[0017] (2) The laminated body according to (1), wherein,

[0018] Organic membranes contain heterocyclic compounds.

[0019] (3) The laminate according to (1) or (2), wherein,

[0020] The organic membrane contains polymers with an acid value of less than 20 mg KOH / g.

[0021] (4) The laminate according to any one of (1) to (3), wherein,

[0022] Organic films are formed using curable compositions.

[0023] The curable composition contains a capped isocyanate.

[0024] (5) A laminated body having:

[0025] Dielectric film;

[0026] A first metal pattern composed of a plurality of first metal structures disposed on one surface side of a dielectric film;

[0027] The moisture permeability of the material applied to the first metal pattern at 40°C and 90% relative humidity is 3000 g / (m²). 2 • The first organic membrane (less than 24 hours);

[0028] A second metal pattern, consisting of multiple second metal structures, disposed on the other surface side of the dielectric film; and

[0029] The moisture permeability of the material applied to the second metal pattern at 40°C and 90% relative humidity is 3000 g / (m²). 2 The second organic membrane (less than 24 hours)

[0030] The first and second metal patterns constitute a resonator for electromagnetic waves in the terahertz frequency band.

[0031] (6) The laminate according to (5), wherein,

[0032] When viewed from above, the first metal structure contained in the first metal pattern and the second metal structure contained in the second metal pattern are configured to overlap at least partially.

[0033] (7) The laminate according to (5) or (6), wherein,

[0034] The first and second organic membranes contain heterocyclic compounds.

[0035] (8) The laminate according to any one of (5) to (7), wherein,

[0036] The first and second organic membranes contain polymers with an acid value of less than 20 mg KOH / g.

[0037] (9) The laminate according to any one of (5) to (8), wherein,

[0038] The first organic film and the second organic film are formed using a curable composition.

[0039] The curable composition contains a capped isocyanate.

[0040] (10) An optical element comprising any one of (1) to (9) a laminate.

[0041] (11) A method for manufacturing a laminate, comprising:

[0042] Step 1A involves bonding a patterned film, comprising a dielectric film and a metal pattern disposed on at least one surface side of the dielectric film to a transfer film comprising a temporary support and a curable composition layer, to form a precursor film having, sequentially, a dielectric film, a metal pattern, a curable composition layer, and a temporary support; and

[0043] Step 2A involves curing the curable composition layer to achieve a moisture permeability of 3000 g / (m²) at 40°C and 90% relative humidity. 2 Organic membranes with a lifespan of less than 24 hours

[0044] It further includes the process of stripping the temporary support between process 1A and process 2A or after process 2A.

[0045] (12) The method for manufacturing the laminate according to (11), wherein,

[0046] Organic membranes contain heterocyclic compounds.

[0047] (13) The method for manufacturing a laminate according to (11) or (12), wherein,

[0048] The organic membrane contains polymers with an acid value of less than 20 mg KOH / g.

[0049] (14) The method for manufacturing a laminate according to any one of (11) to (13), wherein,

[0050] The curable composition layer contains a capped isocyanate.

[0051] (15) A method for manufacturing a laminate, comprising:

[0052] Step 1B involves bonding a metal-patterned film to a transfer film comprising a temporary support and a curable composition layer. The metal-patterned film comprises a dielectric film, a first metal pattern composed of multiple first metal structures disposed on one surface of the dielectric film, and a second metal pattern composed of multiple second metal structures disposed on the other surface of the dielectric film. The first and second metal patterns constitute a resonator for electromagnetic waves in the terahertz frequency band, thereby forming a precursor film sequentially comprising a temporary support, a curable composition layer, a first metal pattern, a dielectric film, a second metal pattern, a curable composition layer, and a temporary support.

[0053] Step 2B involves curing the curable composition layer to achieve a moisture permeability of 3000 g / (m²) at 40°C and 90% relative humidity. 2 Organic membranes with a lifespan of less than 24 hours

[0054] Furthermore, it includes a step 3B, which involves stripping the temporary support between step 1B and step 2B or after step 2B.

[0055] (16) The method for manufacturing the laminate according to (15), wherein,

[0056] When viewed from above, the first metal structure contained in the first metal pattern and the second metal structure contained in the second metal pattern are configured to overlap at least partially.

[0057] (17) The method for manufacturing a laminate according to (15) or (16), wherein,

[0058] Organic membranes contain heterocyclic compounds.

[0059] (18) The method for manufacturing the laminate according to any one of (15) to (17) wherein the organic membrane comprises a polymer with an acid value of less than 20 mg KOH / g.

[0060] (19) A method for manufacturing a laminate according to any one of (15) to (18), wherein,

[0061] The curable composition layer contains a capped isocyanate.

[0062] Invention Effects

[0063] According to the present invention, the objective is to provide a laminate capable of suppressing corrosion of a metal pattern that becomes a resonator for electromagnetic waves in the terahertz frequency band.

[0064] Furthermore, according to the present invention, the objective is also to provide a method for manufacturing a laminate. Attached Figure Description

[0065] Figure 1 This is a schematic diagram illustrating an example of the layer structure of a first embodiment of the laminate of the present invention.

[0066] Figure 2 This is a schematic diagram illustrating an example of a metal structure.

[0067] Figure 3 This is a schematic diagram illustrating an example of the layer structure of a second embodiment of the laminate of the present invention.

[0068] Figure 4 This is a schematic diagram illustrating the photomask used in the embodiment. Detailed Implementation

[0069] The present invention will now be described in detail.

[0070] The description of the constituent elements described below is sometimes based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0071] The following explains the meaning of each statement in this specification.

[0072] In this specification, the numerical range indicated by “~” refers to the range including the values ​​recorded before and after “~” as the lower and upper limits.

[0073] In this specification, within a range of values ​​described in stages, the upper or lower limit value recorded within a certain range can be replaced by the upper or lower limit value of other ranges of values ​​described in stages. Furthermore, within the range of values ​​described in this specification, the upper or lower limit value recorded within a certain range can also be replaced by the values ​​shown in the embodiments.

[0074] In this specification, the term "process" includes not only independent processes, but also processes that can achieve the desired purpose of the process, even if they cannot be clearly distinguished from other processes.

[0075] Unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in this specification are obtained as follows: TSKgel GMHxL, TSKgel G4000HxL or TSKgel G2000HxL (all product names manufactured by Tosoh Corporation) are used as columns; THF (tetrahydrofuran) is used as the eluent; a differential refractometer is used as the detector; and polystyrene is used as the standard. The values ​​are converted using polystyrene as the standard measured by a gel permeation chromatography (GPC) analyzer.

[0076] Unless otherwise specified, the molecular weight of compounds with molecular weight distribution in this specification is the weight-average molecular weight (Mw).

[0077] Unless otherwise specified, the hue in this instruction manual is the value measured using a colorimeter (CR-221, manufactured by Minolta Co., Ltd.).

[0078] In this specification, "(meth)acrylic acid" is a concept that includes both acrylic acid and methacrylic acid, and "(meth)acryloyloxy" is a concept that includes both acryloyloxy and methacryloyloxy.

[0079] In addition, in this specification, "alkali solubility" means that the solubility is 0.1g or more in 100g of a 1% by mass aqueous solution of sodium carbonate at 22°C.

[0080] In this specification, "water-soluble" means having a solubility of 0.1g or more in 100g of water at pH 7.0 and a liquid temperature of 22°C. Therefore, for example, a water-soluble resin refers to a resin that meets the above solubility condition.

[0081] In this specification, "solid component" of the composition refers to the component used to form the composition layer formed using the composition. When the composition contains a solvent (organic solvent, water, etc.), it refers to all components other than the solvent. Furthermore, if it is a component that forms the composition layer, even if it is liquid, it is considered a solid component.

[0082] As a characteristic feature of the laminate of the present invention, the use of an organic membrane with a specified permeability can be cited.

[0083] The inventors have discovered for the first time that corrosion occurs in metal patterns composed of multiple metal structures that function as supermaterials, and that corrosion of the metal patterns can be suppressed by using an organic film with specified moisture permeability.

[0084] Implementation Method 1

[0085] The first embodiment of the laminate of the present invention will be described with reference to the accompanying drawings.

[0086] Figure 1 The laminate 10A shown sequentially comprises a dielectric film 12, a metal pattern 14, and an organic film 16. Additionally, in Figure 1 In the middle, the metal pattern 14 is composed of multiple metal structures 18.

[0087] As will be described in detail later, the multiple metal structures 18 constituting the metal pattern 14 can function as resonators for electromagnetic waves in the terahertz frequency band.

[0088] The following is a detailed description of each component that makes up the laminate.

[0089] <Dielectric film>

[0090] As a dielectric film, known dielectric films can be used.

[0091] As a dielectric film, it is preferably an insulator that does not conduct electricity to DC voltage.

[0092] The material constituting the dielectric film is not particularly limited, but resin is preferred from the perspective of operability, etc. That is, a dielectric resin film is preferred as the dielectric film.

[0093] Examples of resins constituting the dielectric resin film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene (PE), polypropylene (PP), polystyrene, ethylene vinyl acetate (EVA), polyolefins such as cyclic olefin polymers (COP) and cyclic olefin copolymers (COC), vinyl resins, polycarbonate (PC), polyamide, polyimide, acrylic resins, and triacetyl cellulose (TAC). Among these, cyclic olefin polymers or cyclic olefin copolymers are preferred.

[0094] Examples of cyclic olefin polymers include those described in paragraphs 0052 to 0071 of Japanese Patent No. 4991170.

[0095] The thickness of the dielectric film is not particularly limited, but is preferably 5 to 100 μm, more preferably 10 to 80 μm, and even more preferably 15 to 50 μm.

[0096] If the dielectric film thickness is 5μm or more, the operability is excellent; if it is less than 100μm, the function of the metamaterial as a metallic pattern is more easily realized.

[0097] Furthermore, the in-plane deviation of the dielectric film thickness is preferably within 1 μm.

[0098] The transmittance of terahertz waves relative to the dielectric film is not particularly limited, but is preferably 75% or more, more preferably 85% or more, and even more preferably 95% or more.

[0099] Dielectric films can be single-layer or multi-layer structures.

[0100] <Metal Pattern>

[0101] The metallic pattern acts as a resonator for electromagnetic waves in the terahertz frequency band (electromagnetic waves with a frequency of 0.1–10 THz and a wavelength of 30–3000 μm). More specifically, the metallic pattern is composed of multiple metallic structures, which act as resonators for electromagnetic waves in the terahertz frequency band.

[0102] The shape or size of the metallic structure is not particularly limited, but it is preferably a shape that, when electromagnetic waves in the terahertz band are incident on the laminate, induces a change in dielectric or magnetic response by generating a charge bias or current within the metallic structure or between adjacent metallic structures through interaction with the electric or magnetic field of the incident electromagnetic waves, and is below the wavelength of the incident electromagnetic waves. Such metallic patterns can function as so-called metamaterials.

[0103] The shape of metal structures is not particularly limited; examples include C-shaped, U-shaped, double-ringed, V-shaped, L-shaped, lattice-shaped, spiral-shaped, square-shaped, circular-shaped, and cross-shaped. More specifically, for example, in... Figure 2 In the example, a plurality of C-shaped metal structures 18A are disposed on the dielectric film 12.

[0104] The types of metals constituting the metal structure are not particularly limited, but preferably include gold, silver, platinum, copper, aluminum, or alloys of one or more thereof, more preferably silver or copper.

[0105] The size of the metal structure is not particularly limited as long as it resonates with electromagnetic waves in the terahertz frequency band, but the maximum length of the metal structure is preferably 1 to 3000 μm, more preferably 5 to 1000 μm.

[0106] The maximum length of the aforementioned metal structure refers to the longest length that can be drawn when a straight line is drawn from one end of the metal structure to the other.

[0107] The placement of the metal structures on the dielectric film is not particularly restricted, as long as the arrangement resonates with electromagnetic waves in the terahertz frequency band.

[0108] Furthermore, when the laminate is used as a thin-film collimating lens for electromagnetic waves in the terahertz band, it is preferable to configure the metal structure in such a way that a refractive index distribution with a refractive index difference of more than twice that of electromagnetic waves in the terahertz band is generated in the in-plane direction of the dielectric film.

[0109] Furthermore, the metal structure can be disposed on the dielectric film to form a periodic structure in which the phase shift of the electromagnetic wave in the terahertz band continuously increases or decreases as the region moves outward from the center of the laminate. When the metal structure is disposed in this way, it can also be disposed in three or more regions arranged in concentric circles from the center of the laminate. In this case, the variation width of the diameter of each concentric circle is preferably 10 to 200 μm.

[0110] exist Figure 1 The invention illustrates a method in which a metal pattern is disposed on only one surface side of the dielectric film, but the invention is not limited to this method and metal patterns can be disposed on both sides of the dielectric film.

[0111] <Organic membrane>

[0112] The organic film serves to prevent corrosion of the aforementioned metal pattern. The organic film is applied to the metal pattern in a manner that covers it.

[0113] The organic membrane has a water vapor transmittance of 3000 g / (m³) under conditions of 40℃ and 90% relative humidity. 2 Membranes with a lifespan of 24 hours or less.

[0114] From the perspective of further suppressing corrosion of the metal pattern (hereinafter referred to as "the aspect of the invention that is even more effective"), the above-mentioned moisture permeability is preferably 2000 g / (m²). 2 • Less than 24hr), more preferably 1000g / (m 2 • Below 24hr. The lower limit is not particularly restricted, but is mostly 150g / (m³). 2 • 24hr) or more, more often 250g / (m 2 ·24hr) or more.

[0115] The method for measuring the above-mentioned humidity permeability is as follows.

[0116] Prepare a test sample consisting of five layers of organic film. Under the test conditions of 40°C and 90% relative humidity, allow the sample to stand for 24 hours. Then, measure the moisture permeability under the same conditions using the method described in JIS Z 0208. Multiply the obtained values ​​by five and calculate the moisture permeability of each layer.

[0117] The above operation was performed on 5 test samples to obtain the 5 values ​​of moisture permeability for each layer, and these values ​​were arithmetically averaged as the moisture permeability of the present invention.

[0118] In addition, as a method for preparing a test sample consisting of five layers of the above-mentioned organic film, for example, as shown in the examples described later, a method can be described that uses a transfer film containing a curable composition layer that can become an organic film, laminates the curable composition layer five times, and performs a curing treatment on the obtained laminate to prepare a test sample consisting of five layers of organic film.

[0119] The thickness of the organic film is not particularly limited, but it is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less, so as not to impair the transmission characteristics of electromagnetic waves. There is no particular limitation on the lower limit, but it is mostly 0.5 μm or more.

[0120] The materials contained in the organic membrane are not particularly limited, but polymers are preferred.

[0121] Examples of polymers include, for example, saturated or unsaturated polyester resins, (meth)acrylic resins, urethane acrylate resins, polyester acrylate resins, polyurethane acrylate resins, epoxy acrylate resins, urethane resins, epoxy resins, vinyl resins, polycarbonate resins, cellulose resins, acetal resins, polyethylene resins, polystyrene resins, polyamide resins, polyimide resins, melamine resins, phenolic resins, and silicone resins.

[0122] As polymers that can be contained in organic films, examples include adhesive polymers that can be contained in curable composition layers, as described later, and polymers of polymeric compounds, which will be detailed later.

[0123] Furthermore, when an organic film is formed using the curable composition layer described later, if the polymer contained in the curable composition layer contains reactive groups, the reactants of the polymer are contained in the organic film.

[0124] The polymer contained in the organic membrane may or may not have acid groups. However, when the polymer has acid groups, the acid value of the polymer is not particularly limited, but is preferably below 1000 mg KOH / g, more preferably below 200 mg KOH / g, and even more preferably below 20 mg KOH / g. When the polymer has acid groups, the lower limit is not particularly limited and is mostly above 0 mg KOH / g.

[0125] In addition, the acid value of the polymer was determined according to the method described in JIS K0070:1992.

[0126] When the organic membrane contains a polymer, the polymer content relative to the total mass of the organic membrane is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 30 to 70% by mass.

[0127] The organic film preferably contains heterocyclic compounds. By including heterocyclic compounds in the organic film, corrosion of the metal pattern is further prevented.

[0128] Examples of heterocyclic compounds that can be included in organic films include those that can be included in the curable composition layer, as described later in the following paragraphs.

[0129] Organic membranes can contain a single heterocyclic compound or two or more heterocyclic compounds.

[0130] When the organic membrane contains heterocyclic compounds, the content of the heterocyclic compounds relative to the total mass of the organic membrane is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass.

[0131] Organic membranes may also contain other components besides the polymers and heterocyclic compounds mentioned above (e.g., surfactants).

[0132] (Other layers)

[0133] The aforementioned laminates may also include other structures besides dielectric films, metal patterns, and organic films.

[0134] Furthermore, metal patterns and organic films can be repeatedly laminated on the organic film.

[0135] <Manufacturing Method of Laminated Materials>

[0136] The manufacturing method of the aforementioned laminates is not particularly limited and can be manufactured using known methods.

[0137] Examples include methods for bonding a prescribed organic film onto the metal pattern of a patterned film (hereinafter also simply referred to as "patterned film A") comprising a dielectric film and a metal pattern disposed on at least one surface side of the dielectric film that serves as a resonator for electromagnetic waves in the terahertz frequency band; methods for coating a curable composition onto patterned film A and performing a curing process as needed to form an organic film; and methods for using a transfer film comprising a temporary support and a curable composition layer comprising prescribed components.

[0138] As a method of using transfer film, a preferred method includes step 1A, which involves bonding a film A with a metal pattern and a transfer film containing a temporary support and a curable composition layer to form a precursor film having a dielectric film, a metal pattern, a curable composition layer and a temporary support in sequence, and step 2A, which involves curing the curable composition layer to obtain the aforementioned organic film, and further includes step 3A, which involves peeling off the temporary support between step 1A and step 2A or after step 2A.

[0139] The method of using transfer film will be described in detail below. Furthermore, the structure of the transfer film itself will be described in detail later.

[0140] (Membrane A with metallic pattern)

[0141] In the method of using a transfer film, a metal-patterned film A can be used, which includes a dielectric film and a metal pattern disposed on at least one surface side of the dielectric film to serve as a resonator for electromagnetic waves in the terahertz frequency band.

[0142] The structure of the metal pattern contained in the metal patterned film A is the same as the structure of the metal pattern in the laminate described above.

[0143] The manufacturing method of the above-mentioned metal patterned film A is not particularly limited. A metal layer is formed on the dielectric film, a specified resist pattern is arranged on the metal layer, the metal layer not covered by the resist pattern is etched away, and the resist pattern is stripped off, thereby manufacturing a metal patterned film.

[0144] (Process 1A)

[0145] Step 1A is a process of bonding a film A with a metallic pattern and a transfer film containing a temporary support and a curable composition layer to form a precursor film having a dielectric film, a metallic pattern, a curable composition layer and a temporary support in sequence.

[0146] In this process, the exposed curable composition layer on the temporary support of the transfer film is brought into contact with the metal-patterned film A for bonding. By performing this bonding, the curable composition layer and the temporary support are disposed on the metal-patterned film A.

[0147] In the above bonding process, it is preferable to press the metal pattern into contact with the surface of the cured composition layer.

[0148] There are no particular limitations on the above-mentioned pressing method, and known transfer methods and lamination methods can be used. Among them, it is preferable to overlap the surface of the curable composition layer onto a dielectric film with a metallic pattern, and then apply pressure and heat based on rollers or the like.

[0149] Lamination can be achieved using known laminators such as vacuum laminators and automatic cutting laminators.

[0150] (Process 2A)

[0151] Step 2A is a step of curing the curable composition layer to obtain an organic film.

[0152] As a curing treatment, the appropriate method is selected depending on the curing composition used. If the curing composition is a thermosetting composition, heat treatment can be selected; if the curing composition is a photocurable composition, exposure treatment can be used. Furthermore, exposure treatment and heat treatment can be performed sequentially or simultaneously.

[0153] The conditions for heat treatment are not particularly limited. The preferred heating temperature is 100–200°C, more preferably 110–180°C, and even more preferably 120–170°C. The preferred heating time is 0.05–5 hours, more preferably 0.08–3 hours, and even more preferably 0.1–1 hour.

[0154] Exposure processing can also involve exposing the image into a pattern. In the case of pattern exposure, development processing can be performed as needed.

[0155] As the light source for exposure, any light source can be appropriately selected as long as it can illuminate light in a wavelength range capable of curing the curable composition (e.g., 365 nm or 405 nm). The dominant wavelength of the exposure light is preferably 365 nm. Furthermore, the dominant wavelength refers to the wavelength with the highest intensity.

[0156] As light sources, examples include various lasers, light-emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps.

[0157] The preferred exposure level is 5–200 mJ / cm. 2 More preferably 10–200 mJ / cm 2 .

[0158] Preferred methods for the light source, exposure amount, and exposure method used in the exposure are described, for example, in paragraphs

[0146] to

[0147] of International Publication No. 2018 / 155193, and are incorporated herein by reference.

[0159] (Process 3A)

[0160] Process 3A is the process of removing the temporary support between process 1A and process 2A or after process 2A.

[0161] There are no particular limitations on the peeling method, and the same mechanism as the covering film peeling mechanism described in paragraphs

[0161] to

[0162] of Japanese Patent Application Publication No. 2010-072589 can be used.

[0162] (Other processes)

[0163] When a pattern has been exposed during the curing process, a developing process can be performed as needed. The developing process is the process of developing the exposed curable composition layer to form a pattern.

[0164] The development of the above-mentioned curable composition layer can be performed using a developer.

[0165] As a developing solution, an alkaline aqueous solution is preferred. Examples of alkaline compounds that can be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

[0166] Examples of development methods include rotary immersion development, spray development, rotational development, and immersion development.

[0167] As a preferred developer for use in this invention, for example, the developer described in paragraph

[0194] of International Publication No. 2015 / 093271 can be cited as an example. As a preferred developing method, for example, the developing method described in paragraph

[0195] of International Publication No. 2015 / 093271 can be cited as an example.

[0168] The pattern (cured film of the curable composition layer) formed by the above process is preferably colorless. Specifically, in L * a * b * In the color system, pattern a * The preferred value is -1.0 to 1.0, and the b of the pattern * The preferred value is -1.0 to 1.0.

[0169] This may include a process of exposing the pattern obtained through the above-described developing process (post-exposure process) and / or a process of heating (post-baking process).

[0170] In cases where both post-exposure and post-drying processes are included, post-drying is preferably performed after post-exposure.

[0171] (Transfer film)

[0172] The transfer film has a temporary support and a curable composition layer disposed on the temporary support. The aforementioned organic film is formed by curing the curable composition layer.

[0173] The structure of the transfer film will be described in detail below.

[0174] (Temporary support)

[0175] The temporary support is a component that supports the cured composition layer described later, and is eventually removed by a peeling process.

[0176] The temporary support is preferably a membrane, more preferably a resin membrane. As a temporary support, a membrane that is flexible and does not undergo significant deformation, shrinkage, or stretching under pressure or under pressure and heat can be used.

[0177] Examples of such membranes include polyethylene terephthalate membranes (e.g., biaxially stretched polyethylene terephthalate membranes), cellulose triacetate membranes, polystyrene membranes, polyimide membranes, and polycarbonate membranes.

[0178] Among these, biaxially stretched polyethylene terephthalate film is preferred as a temporary support.

[0179] Furthermore, it is preferable that the membrane used as a temporary support is free from deformations such as wrinkles and scratches.

[0180] From the perspective of enabling exposure through a temporary support, the temporary support preferably has high transparency, with a transmittance of 60% or more at 365nm, and more preferably 70% or more.

[0181] From the perspective of pattern formation properties during pattern exposure through a temporary support and the transparency of the temporary support, the haze of the temporary support is preferably low. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, and even more preferably 0.1% or less.

[0182] From the viewpoint of pattern formation properties during pattern exposure through a temporary support and the transparency of the temporary support, the number of particles, foreign objects, and defects contained in the temporary support is preferably low. The number of particles, foreign objects, and defects with a diameter of 1 μm or more is preferably 50 per 10 mm. 2 The following is more preferably 10 per 10mm 2 The following is a further preferred option: 3 per 10mm 2 The following is particularly preferred: 0 per 10mm 2 .

[0183] The thickness of the temporary support is not particularly limited, but it is preferably 5 to 200 μm. Considering ease of operation and versatility, it is more preferably 10 to 150 μm, and even more preferably 10 to 50 μm.

[0184] From an operability perspective, a layer containing microparticles (lubricant layer) can be formed on the surface of the temporary support. The lubricant layer can be formed on one side or both sides of the temporary support. The diameter of the particles contained in the lubricant layer can be set to 0.05 to 0.8 μm. Furthermore, the film thickness of the lubricant layer can be set to 0.05 to 1.0 μm.

[0185] Examples of temporary supports include biaxially stretched polyethylene terephthalate (PET) films with a thickness of 16 μm, 12 μm, and 9 μm.

[0186] Preferred methods for temporary supports are described, for example, in paragraphs

[0017] to

[0018] of Japanese Patent Application Publication No. 2014-085643, paragraphs

[0019] to

[0026] of Japanese Patent Application Publication No. 2016-027363, paragraphs

[0041] to

[0057] of International Publication No. 2012 / 081680, and paragraphs

[0029] to

[0040] of International Publication No. 2018 / 179370, the contents of which are incorporated herein by reference.

[0187] (Curing composition layer)

[0188] The transfer film has a curable composition layer. After the curable composition layer is transferred onto a metal pattern, a curing process is performed, thereby forming the aforementioned organic film.

[0189] The curable composition layer can be a thermosetting composition layer or a photocurable composition layer.

[0190] The components contained in the curable composition layer are described in detail below.

[0191] [Adhesive Polymer]

[0192] The curable composition layer may also contain an adhesive polymer.

[0193] As one of the preferred types of adhesive polymers, (meth)acrylic resins are an example of those with excellent alkali developability and film-forming properties.

[0194] Furthermore, in this specification, (meth)acrylic resin refers to a resin having structural units derived from (meth)acrylic compounds. The content of structural units derived from (meth)acrylic compounds relative to all structural units of the (meth)acrylic resin is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more.

[0195] (Meth)acrylic resins can consist solely of structural units derived from (meth)acrylic compounds, or they can contain structural units derived from polymerizable monomers other than (meth)acrylic compounds. Specifically, the maximum content of structural units derived from (meth)acrylic compounds is less than 100% by mass relative to all structural units of the (meth)acrylic resin.

[0196] Examples of (meth)acrylic acid compounds include, for example, (meth)acrylic acid, (meth)acrylates, (meth)acrylamide, and (meth)acrylonitrile.

[0197] Examples of (meth)acrylates include, for example, alkyl (meth)acrylates, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, benzyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate, with alkyl (meth)acrylates being preferred.

[0198] Examples of (meth)acrylamides include, for example, diacetone acrylamide and other acrylamides.

[0199] The alkyl group in an alkyl ester of (meth)acrylate can be either linear or branched. Specific examples include alkyl esters of (meth)acrylate having alkyl groups having 1 to 12 carbon atoms, such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, and dodecyl methacrylate.

[0200] As a (meth)acrylate, an alkyl (meth)acrylate having an alkyl group having 1 to 4 carbon atoms is preferred, and methyl (meth)acrylate or ethyl (meth)acrylate is more preferred.

[0201] (Meth)acrylic resins can have structural units other than those derived from (meth)acrylic compounds.

[0202] As polymerizable monomers forming the above-mentioned structural units, there are no particular restrictions as long as they are compounds other than (meth)acrylic acid compounds that can copolymerize with (meth)acrylic acid compounds. Examples include styrene compounds such as styrene, vinyltoluene, and α-methylstyrene, which may have substituents at the α-position or on the aromatic ring; vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether; maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, and monoisopropyl maleate; fumaric acid, cinnamic acid, α-cyanocinonic acid, itaconic acid, and crotonic acid.

[0203] These polymerizable monomers can be used in one or in combination of two or more.

[0204] Furthermore, from the perspective of further improving alkaline developability, (meth)acrylic resins preferably contain structural units having acid groups. Examples of acid groups include carboxyl, sulfonyl, phosphate, and phosphonic acid groups.

[0205] The (meth)acrylic resin is more preferably a structural unit containing a carboxyl group, and even more preferably a structural unit derived from the above-mentioned (meth)acrylic acid.

[0206] From the perspective of excellent developability, the content of acid-containing structural units (preferably structural units derived from (meth)acrylic acid) in the (meth)acrylic resin is preferably 10% by mass or more relative to the total mass of the (meth)acrylic resin. Furthermore, the upper limit is not particularly limited, but from the perspective of excellent alkali resistance, it is preferably 50% by mass or less, more preferably 40% by mass or less.

[0207] Furthermore, (meth)acrylic resins are more preferably those having structural units derived from the aforementioned alkyl (meth)acrylic esters.

[0208] In the case of having structural units derived from alkyl methacrylates, the content of structural units derived from alkyl methacrylates in the (meth)acrylate resin is preferably 1 to 90% by mass, more preferably 1 to 50% by mass, and even more preferably 1 to 30% by mass, relative to all structural units of the (meth)acrylate resin.

[0209] As a (meth)acrylic resin, a resin having both structural units derived from (meth)acrylic acid and structural units derived from (meth)acrylic acid alkyl esters is preferred, and a resin composed solely of structural units derived from (meth)acrylic acid and structural units derived from (meth)acrylic acid alkyl esters is more preferred.

[0210] Furthermore, as a (meth)acrylic resin, an acrylic resin having structural units derived from methacrylic acid, structural units derived from methyl methacrylate, and structural units derived from ethyl acrylate is preferred.

[0211] Furthermore, from the viewpoint of further improving the effects of the present invention, the (meth)acrylic resin preferably has at least one of the structural units selected from methacrylic acid and structural units selected from alkyl methacrylates, and preferably has both structural units selected from methacrylic acid and structural units selected from alkyl methacrylates.

[0212] From the perspective of further improving the effects of the present invention, the total content of structural units derived from methacrylic acid and structural units derived from alkyl methacrylates in the (meth)acrylic resin is preferably 40% by mass or more, more preferably 60% by mass or more, relative to all structural units of the (meth)acrylic resin. The upper limit is not particularly limited and can be 100% by mass or less, preferably 80% by mass or less.

[0213] Furthermore, from the viewpoint of further enhancing the effects of the present invention, the (meth)acrylic resin preferably has at least one structural unit selected from methacrylic acid and structural units selected from alkyl methacrylates, and at least one structural unit selected from acrylic acid and structural units selected from alkyl acrylates.

[0214] From the perspective of further improving the effects of the present invention, the total content of structural units derived from methacrylic acid and structural units derived from alkyl methacrylates is preferably 60 / 40 to 80 / 20 by mass relative to the total content of structural units derived from acrylic acid and structural units derived from alkyl acrylates.

[0215] In terms of the excellent developability of the cured composition layer after transfer, (meth)acrylic resins preferably have ester groups at the ends.

[0216] Furthermore, the terminal portion of (meth)acrylic resins is composed of a site derived from the polymerization initiator used in the synthesis. (Meth)acrylic resins with ester groups at the terminals can be synthesized using a polymerization initiator that generates free radicals with ester groups.

[0217] Furthermore, alkali-soluble resins can be cited as another preferred type of adhesive polymer.

[0218] For example, from the perspective of developability, the adhesive polymer is preferably an adhesive polymer with an acid value of 60 mg KOH / g or higher.

[0219] Furthermore, for example, from the viewpoint that a strong film can be easily formed by thermal crosslinking with the crosslinking components through heating, the adhesive polymer is more preferably a carboxyl-containing resin with an acid value of 60 mg KOH / g or higher (so-called carboxyl-containing resin), and even more preferably a carboxyl-containing (meth)acrylic resin with an acid value of 60 mg KOH / g or higher (so-called carboxyl-containing (meth)acrylic resin).

[0220] When the adhesive polymer is a resin containing carboxyl groups, thermal crosslinking can be performed by adding thermally crosslinking compounds such as end-capped isocyanate compounds, thereby increasing the three-dimensional crosslinking density. Furthermore, if the carboxyl groups of the resin are dehydrated and hydrophobic, the resistance to damp heat can be improved.

[0221] As for (meth)acrylic resins containing carboxyl groups with an acid value of 60 mg KOH / g or higher, there are no particular restrictions as long as the above acid value condition is met, and they can be appropriately selected from known (meth)acrylic resins.

[0222] For example, acrylic resins containing carboxyl groups with an acid value of 60 mg KOH / g or higher in polymers described in Japanese Patent Application Publication No. 2011-095716 (paragraph

[0025] ) and acrylic resins containing carboxyl groups with an acid value of 60 mg KOH / g or higher in polymers described in Japanese Patent Application Publication No. 2010-237589 (paragraphs

[0033] to

[0052] ) are preferred.

[0223] Other preferred types of adhesive polymers include styrene-acrylic acid copolymers.

[0224] In addition, in this specification, styrene-acrylic acid copolymer refers to a resin having structural units derived from styrene compounds and structural units derived from (meth)acrylic acid compounds, wherein the total content of the aforementioned structural units derived from styrene compounds and the aforementioned structural units derived from (meth)acrylic acid compounds is preferably 30% by mass or more, more preferably 50% by mass or more, relative to all structural units of the copolymer.

[0225] Furthermore, the content of structural units derived from styrene compounds relative to all structural units of the aforementioned copolymer is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 5 to 80% by mass.

[0226] Furthermore, the content of the structural units derived from the (meth)acrylic acid compounds is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20 to 95% by mass, relative to all the structural units of the copolymer.

[0227] From the perspective of further improving the effects of the present invention, the adhesive polymer preferably has an aromatic ring structure, and more preferably contains structural units having an aromatic ring structure.

[0228] Examples of monomers forming structural units with aromatic ring structures include monomers having aralkyl groups, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimers, and styrene trimers). Among these, monomers having aralkyl groups or styrene are preferred. Examples of aralkyl groups include substituted or unsubstituted phenylalkyl groups (excluding benzyl) and substituted or unsubstituted benzyl groups, with substituted or unsubstituted benzyl groups being preferred.

[0229] Examples of monomers containing phenyl alkyl groups include ethyl methacrylate (meth)acrylate.

[0230] Examples of monomers containing a benzyl group include (meth)acrylates such as benzyl (meth)acrylate and benzyl (meth)acrylate chloride; and vinyl monomers such as vinyl benzyl chloride and vinyl benzyl alcohol. Among these, benzyl (meth)acrylate is preferred.

[0231] Furthermore, from the viewpoint of further enhancing the effects of the present invention, the adhesive polymer more preferably has a structural unit represented by the following formula (S) (a structural unit derived from styrene).

[0232] [Chemical Formula 1]

[0233]

[0234] In cases where the adhesive polymer contains structural units having aromatic ring structures, from the perspective of further enhancing the effects of the present invention, the content of structural units having aromatic ring structures relative to all structural units of the adhesive polymer is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, and even more preferably 20 to 60% by mass.

[0235] Furthermore, from the viewpoint of achieving even better results from the present invention, the content of the structural unit having an aromatic ring structure in the adhesive polymer is preferably 5 to 70 mol% relative to all structural units of the adhesive polymer, more preferably 10 to 60 mol%, and even more preferably 20 to 60 mol%.

[0236] Furthermore, considering aspects that enhance the effects of the present invention, the content of the structural unit represented by the above formula (S) in the adhesive polymer is preferably 5 to 70 mol% relative to all structural units of the adhesive polymer, more preferably 10 to 60 mol%, further preferably 20 to 60 mol%, and especially preferably 20 to 50 mol%.

[0237] Furthermore, in this specification, when the content of "structural unit" is specified using a molar ratio, the meaning of "structural unit" is the same as that of "monomer unit." Also, in this specification, the aforementioned "monomer unit" can be modified after polymerization, such as through polymer reactions. The same applies below.

[0238] From the perspective of further enhancing the effects of the present invention, the adhesive polymer preferably has an aliphatic hydrocarbon ring structure. That is, the adhesive polymer preferably contains structural units having an aliphatic hydrocarbon ring structure. The aliphatic hydrocarbon ring structure can be monocyclic or polycyclic. More preferably, the adhesive polymer has a ring structure formed by the fusion of two or more aliphatic hydrocarbon rings.

[0239] Examples of rings that constitute aliphatic hydrocarbon ring structures include tricyclic decane rings, cyclohexane rings, cyclopentane rings, norbornene rings, and isophorone rings.

[0240] In view of the superior effects of the present invention, the ring is preferably formed by the fusion of two or more aliphatic hydrocarbon rings, and more preferably a tetrahydrodicyclopentadiene ring (tricyclic [5.2.1.02, 6]decane ring).

[0241] Examples of monomers that form structural units with aliphatic hydrocarbon ring structures include dicyclopentyl methacrylate, cyclohexyl methacrylate, and isobornyl methacrylate.

[0242] Furthermore, from the viewpoint of further enhancing the effects of the present invention, the adhesive polymer preferably has structural units represented by the following formula (Cy), and more preferably has structural units represented by the above formula (S) and structural units represented by the following formula (Cy).

[0243] [Chemical Formula 2]

[0244]

[0245] In equation (Cy), R M R represents a hydrogen atom or a methyl group. Cy This indicates a monovalent group having an aliphatic hydrocarbon ring structure.

[0246] In equation (Cy) R M Methyl is preferred.

[0247] From the perspective of achieving better results in this invention, R in formula (Cy) Cy Preferably, it is a monovalent group with an aliphatic hydrocarbon ring structure having 5 to 20 carbon atoms, more preferably a monovalent group with an aliphatic hydrocarbon ring structure having 6 to 16 carbon atoms, and even more preferably a monovalent group with an aliphatic hydrocarbon ring structure having 8 to 14 carbon atoms.

[0248] Furthermore, considering the superior effects of the present invention, R of formula (Cy) Cy The aliphatic hydrocarbon ring structure in the sample is preferably a cyclopentane ring structure, a cyclohexane ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornene ring structure, or an isophorone ring structure, more preferably a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure, and even more preferably a tetrahydrodicyclopentadiene ring structure.

[0249] Furthermore, considering the superior effects of the present invention, R of formula (Cy) Cy The aliphatic hydrocarbon ring structure is preferably a ring structure formed by the fusion of two or more aliphatic hydrocarbon rings, and more preferably a ring structure formed by the fusion of two to four aliphatic hydrocarbon rings.

[0250] Furthermore, considering the superior effects of the present invention, R in formula (Cy) Cy Preferably, the oxygen atom of -C(=O)O- in formula (Cy) is a group that is directly bonded to the aliphatic hydrocarbon ring structure, i.e., an aliphatic hydrocarbon cyclic group, more preferably cyclohexyl or dicyclopentyl, and even more preferably dicyclopentyl.

[0251] The adhesive polymer may have one structural unit with an aliphatic hydrocarbon ring structure, or it may have two or more structural units with an aliphatic hydrocarbon ring structure.

[0252] In cases where the adhesive polymer contains structural units having an aliphatic hydrocarbon ring structure, from the perspective of further enhancing the effects of the present invention, the content of structural units having an aliphatic hydrocarbon ring structure relative to all structural units of the adhesive polymer is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and even more preferably 20 to 70% by mass.

[0253] Furthermore, from the perspective of further enhancing the effects of the present invention, the content of structural units having aliphatic hydrocarbon ring structures in the adhesive polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and even more preferably 20 to 50 mol%, relative to all structural units of the adhesive polymer.

[0254] Furthermore, from the viewpoint of achieving even better results from the present invention, the content of the structural unit represented by the above formula (Cy) in the adhesive polymer is preferably 5 to 70 mol% relative to all structural units of the adhesive polymer, more preferably 10 to 60 mol%, and even more preferably 20 to 50 mol%.

[0255] In cases where the adhesive polymer contains structural units having aromatic ring structures and structural units having aliphatic hydrocarbon ring structures, from the perspective of further improving the effects of the present invention, the total content of structural units having aromatic ring structures and structural units having aliphatic hydrocarbon ring structures relative to all structural units of the adhesive polymer is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 40 to 75% by mass.

[0256] Furthermore, from the viewpoint of achieving even better results from the present invention, the total content of structural units having aromatic ring structures and structural units having aliphatic hydrocarbon ring structures in the adhesive polymer is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and even more preferably 40 to 60 mol%, relative to all structural units of the adhesive polymer.

[0257] Furthermore, from the viewpoint of achieving even better results from the present invention, the total content of the structural units represented by the above formula (S) and the structural units represented by the above formula (Cy) in the adhesive polymer is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and even more preferably 40 to 60 mol%, relative to all structural units of the adhesive polymer.

[0258] Furthermore, from the perspective of further superior effects of the present invention, the molar amount nS of the structural unit represented by the above formula (S) and the molar amount nCy of the structural unit represented by the above formula (Cy) in the adhesive polymer preferably satisfy the relationship shown in the following formula (SCy), more preferably satisfy the following formula (SCy-1), and even more preferably satisfy the following formula (SCy-2).

[0259] 0.2≤nS / (nS+nCy)≤0.8 Formula (SCy)

[0260] 0.30≤nS / (nS+nCy)≤0.75 Formula (SCy-1)

[0261] 0.40≤nS / (nS+nCy)≤0.70 Formula (SCy-2)

[0262] From the perspective of further advantages of the present invention, the adhesive polymer preferably contains structural units having acid groups.

[0263] Examples of acid groups include carboxyl, sulfonyl, phosphonic acid, and phosphate groups, with carboxyl being the most preferred.

[0264] As the above-mentioned structural unit having an acid group, the preferred structural unit is the one derived from (meth)acrylic acid, as shown below, and more preferably the structural unit derived from methacrylic acid.

[0265] [Chemical Formula 3]

[0266]

[0267] The adhesive polymer may contain one structural unit with an acid group or two or more structural units with acid groups.

[0268] In cases where the adhesive polymer contains structural units having acid groups, from the perspective of further enhancing the effects of the present invention, the content of structural units having acid groups relative to all structural units of the adhesive polymer is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and even more preferably 10 to 30% by mass.

[0269] Furthermore, from the viewpoint of achieving even better results from the present invention, the content of the structural units having acid groups in the adhesive polymer is preferably 5 to 70 mol% relative to all structural units of the adhesive polymer, more preferably 10 to 50 mol%, and even more preferably 20 to 40 mol%.

[0270] Furthermore, from the viewpoint of achieving even better results from the present invention, the content of structural units derived from (meth)acrylic acid in the adhesive polymer is preferably 5 to 70 mol% relative to all structural units of the adhesive polymer, more preferably 10 to 50 mol%, and even more preferably 20 to 40 mol%.

[0271] From the perspective of further improving the effects of the present invention, the adhesive polymer preferably has reactive groups, and more preferably contains structural units having reactive groups.

[0272] As a reactive group, a free radical polymerizable group is preferred, and an olefinically unsaturated group is more preferred. Furthermore, when the adhesive polymer has olefinically unsaturated groups, the adhesive polymer preferably comprises structural units having olefinically unsaturated groups on their side chains. That is, as an adhesive polymer, an adhesive polymer having olefinically unsaturated groups on its side chains is preferred.

[0273] In this specification, "main chain" refers to the longest bonded chain in the molecule of the polymer compound that constitutes the resin, and "side chain" refers to a group of atoms that branch off from the main chain.

[0274] As an olefinic unsaturated group, allyl or (meth)acryloyloxy is more preferred.

[0275] Examples of structural units with reactive groups can be given as shown below, but are not limited to these.

[0276] [Chemical Formula 4]

[0277]

[0278] The adhesive polymer may contain one structural unit with a reactive group or two or more structural units with reactive groups.

[0279] In cases where the adhesive polymer contains structural units having reactive groups, from the perspective of further enhancing the effects of the present invention, the content of structural units having reactive groups relative to all structural units of the adhesive polymer is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and even more preferably 20 to 40% by mass.

[0280] Furthermore, from the viewpoint of achieving even better results from the present invention, the content of structural units having reactive groups in the adhesive polymer is preferably 5 to 70 mol% relative to all structural units of the adhesive polymer, more preferably 10 to 60 mol%, and even more preferably 20 to 50 mol%.

[0281] As a method for introducing reactive groups into adhesive polymers, one can exemplify this by reacting compounds such as epoxy compounds, terminal isocyanate compounds, isocyanate compounds, vinyl sulfone compounds, aldehyde compounds, hydroxymethyl compounds, and carboxylic anhydrides with functional groups such as hydroxyl, carboxyl, primary amino, secondary amino, acetoacetyl, and sulfonyl groups.

[0282] As a preferred example of a method for introducing reactive groups into an adhesive polymer, a method can be described as follows: after synthesizing a polymer having carboxyl groups by polymerization, glycidyl (meth)acrylate reacts with a portion of the carboxyl groups of the obtained polymer by a polymer reaction, thereby introducing (meth)acryloyloxy groups into the polymer. By this method, an adhesive polymer having (meth)acryloyloxy groups in its side chains can be obtained.

[0283] The polymerization reaction described above is preferably carried out at a temperature of 70–100°C, more preferably at a temperature of 80–90°C. The polymerization initiator used in the above polymerization reaction is preferably an azo initiator, such as, more preferably, V-601 (product name) or V-65 (product name) manufactured by FUJIFILM Wako Pure Chemical Corporation. The above polymer reaction is preferably carried out at a temperature of 80–110°C. In the above polymer reaction, a catalyst such as an ammonium salt is preferably used.

[0284] The adhesive polymer can be the polymer shown below. Furthermore, the content ratios (a to d) and weight-average molecular weight Mw of each structural unit shown below can be appropriately changed according to the purpose.

[0285] [Chemical Formula 5]

[0286]

[0287] In addition, the preferred values ​​for a to d in the above-mentioned adhesive polymer are a: 20 to 60 wt%, b: 10 to 50 wt%, c: 5.0 to 25 wt%, and d: 10 to 50 wt%, respectively.

[0288] [Chemical Formula 6]

[0289]

[0290] In addition, the preferred values ​​for a to d in the above-mentioned adhesive polymer are a: 20 to 60 wt%, b: 10 to 50 wt%, c: 5.0 to 25 wt%, and d: 10 to 50 wt%, respectively.

[0291] [Chemical Formula 7]

[0292]

[0293] In addition, the preferred values ​​for a to d in the above-mentioned adhesive polymer are a: 30 to 65 wt%, b: 1.0 to 20 wt%, c: 5.0 to 25 wt%, and d: 10 to 50 wt%, respectively.

[0294] [Chemical Formula 8]

[0295]

[0296] In addition, the preferred proportions of a to d in the above-mentioned adhesive polymer are a: 1.0 to 20 wt%, b: 20 to 60 wt%, c: 5.0 to 25 wt%, and d: 10 to 50 wt%, respectively.

[0297] Furthermore, the adhesive polymer may comprise a polymer (hereinafter also referred to as "polymer X") containing structural units having a carboxylic anhydride structure.

[0298] The carboxylic anhydride structure can be either a chain-like carboxylic anhydride structure or a cyclic carboxylic anhydride structure, preferably a cyclic carboxylic anhydride structure.

[0299] The ring in the cyclic carboxylic anhydride structure is preferably a 5- to 7-membered ring, more preferably a 5-membered or 6-membered ring, and even more preferably a 5-membered ring.

[0300] The structural unit having a carboxylic anhydride structure is preferably a structural unit in which a divalent group obtained by removing two hydrogen atoms from a compound represented by the following formula P-1 is directly or via a divalent linking group bonded to the main chain in the main chain, or a monovalent group obtained by removing one hydrogen atom from a compound represented by the following formula P-1.

[0301] [Chemical Formula 9]

[0302]

[0303] In equation P-1, R A1a Indicates substituent, n 1a R A1a They can be the same or different, Z 1a This indicates a divalent group that forms a ring containing -C(=O)-OC(=O)-, n 1a Represents integers greater than or equal to 0.

[0304] As a result of R A1a The substituents indicated can be, for example, alkyl groups.

[0305] As Z 1a Preferably, it is an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, and even more preferably an alkylene group having 2 carbon atoms.

[0306] n 1a Represents integers greater than or equal to 0. In Z... 1a In the case of alkylene groups having 2 to 4 carbon atoms, n 1a Preferably, it is an integer from 0 to 4, more preferably an integer from 0 to 2, and even more preferably 0.

[0307] In n 1a When representing integers greater than 2, multiple R A1a They can be the same or different. Furthermore, there can be multiple R. A1a They can bond together to form a ring, but it is preferable that they do not bond together to form a ring.

[0308] As a structural unit having a carboxylic anhydride structure, it is preferably a structural unit derived from an unsaturated carboxylic anhydride, more preferably a structural unit derived from an unsaturated cyclic carboxylic anhydride, even more preferably a structural unit derived from an unsaturated aliphatic cyclic carboxylic anhydride, especially preferably a structural unit derived from maleic anhydride or itaconic anhydride, and most preferably a structural unit derived from maleic anhydride.

[0309] The following are specific examples of structural units having a carboxylic anhydride structure, but structural units having a carboxylic anhydride structure are not limited to these specific examples. In the structural units described below, Rx represents a hydrogen atom, a methyl group, a CH2OH group, or a CF3 group, and Me represents a methyl group.

[0310] [Chemical Formula 10]

[0311]

[0312] [Chemical Formula 11]

[0313]

[0314] The structural units with carboxylic anhydride structures in polymer X can be a single type or two or more types.

[0315] The total content of structural units having a carboxylic anhydride structure relative to all structural units of polymer X is preferably 0 to 60 mol%, more preferably 5 to 40 mol%, and even more preferably 10 to 35 mol%.

[0316] Organic membranes may contain only one polymer X or two or more polymer X.

[0317] When the organic membrane contains polymer X, the content of polymer X relative to the total mass of the organic membrane is preferably 0.1 to 30% by mass, more preferably 0.2 to 20% by mass, even more preferably 0.5 to 20% by mass, and even more preferably 1 to 20% by mass.

[0318] Cycloolefin polymers are one of the preferred types of adhesive polymers.

[0319] Examples of cyclic olefin polymers that can be included in the dielectric films described above include cyclic olefin polymers.

[0320] From the perspective of further improving the effects of the present invention, the weight-average molecular weight (Mw) of the adhesive polymer is preferably 5,000 or more, more preferably 10,000 or more, even more preferably 10,000 to 50,000, and particularly preferably 15,000 to 30,000.

[0321] From the perspective of developability, the dispersion of the adhesive polymer is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

[0322] The adhesive polymer may or may not have acid groups, but when the adhesive polymer has acid groups, the acid value of the adhesive polymer is not particularly limited, preferably below 1000 mg KOH / g, more preferably below 200 mg KOH / g, and even more preferably below 20 mg KOH / g. When the polymer has acid groups, the lower limit is not particularly limited, and it mostly exceeds 0 mg KOH / g.

[0323] In addition, the acid value of the adhesive polymer was determined according to the method described in JIS K0070:1992.

[0324] The curable composition layer may contain one adhesive polymer alone or two or more adhesive polymers.

[0325] In the case where the curable composition layer contains an adhesive polymer, the content of the adhesive polymer relative to the total mass of the curable composition layer is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 30 to 70% by mass.

[0326] (Curing compounds)

[0327] Furthermore, the curable composition layer may also contain a curable compound.

[0328] As a curable compound, it is preferred to be a compound that can be cured by light or heat.

[0329] Examples of compounds that can be cured by light or heat include compounds having olefinic unsaturated double bonds, compounds having conjugated diene sites, compounds having maleimide sites, thiols that are cured by olefinic thiols, epoxy compounds, and compounds having crosslinking groups formed by acid action. From the perspective of curability, compounds having olefinic unsaturated double bonds are preferred. From the perspective of both curability and compatibility with alkali-soluble resins, compounds having an acryloyl group within the molecule are more preferred as curable compounds.

[0330] Examples of compounds having olefinic unsaturated double bonds include compounds that have undergone addition of (meth)acrylic acid to one end of a polyepoxide, or compounds that have undergone addition of (meth)acrylic acid to one end and then etherified with other terminal alkyl or allyl groups.

[0331] Examples of such compounds include (meth)acrylates of compounds in which polyethylene glycol is added to a phenyl group, namely phenoxyhexaethylene glycol mono(meth)acrylate; (meth)acrylates of compounds in which polyethylene glycol containing an average of 2 moles of propylene oxide and an average of 7 moles of ethylene oxide is added to nonylphenol, namely 4-n-nonylphenoxyheptaethylene glycol dipropylene glycol (meth)acrylate; (meth)acrylates of compounds in which polyethylene glycol containing an average of 1 mole of propylene oxide and an average of 5 moles of ethylene oxide is added to nonylphenol; and 4-n-nonylphenoxypentaethylene glycol monopropylene glycol (meth)acrylate. Another example is the acrylate of a compound in which polyethylene glycol, with an average addition of 8 moles of ethylene oxide, is added to nonylphenol, namely 4-n-nonylphenoxy octaethylene glycol (meth) acrylate (manufactured by TOAGOSEI CO., LTD., M-114).

[0332] Examples of compounds having olefinic unsaturated double bonds include compounds having (meth)acryloyl groups at both ends of an alkylene oxide chain, or compounds having (meth)acryloyl groups at both ends of an alkylene oxide chain in which ethylene oxide and propylene oxide chains are randomly or block-bonded.

[0333] Examples of such compounds include tetraethylene glycol di(meth)acrylate, pentaethylene glycol di(meth)acrylate, hexaethylene glycol di(meth)acrylate, heptaethylene glycol di(meth)acrylate, octaethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, decaethylene glycol di(meth)acrylate, and compounds having (meth)acryloyl groups at both ends of a 12-molar ethylene oxide chain.

[0334] Furthermore, considering resolution, flexibility, and resistance to plating, a polyoxyalkylene di(meth)acrylate compound comprising at least ethylene oxide and propylene oxide is preferred. Similarly, considering these aspects, the molecular weight of the aforementioned compound is preferably 600–1500, more preferably 900–1300, and even more preferably 1000–1200.

[0335] Examples of poly(meth)acrylate compounds comprising at least ethylene oxide and propylene oxide include, for instance, dimethacrylates in which an average of 12 moles of propylene oxide is added to polypropylene glycol, and an average of 3 moles of ethylene oxide glycol is added to each end, and dimethacrylates in which an average of 18 moles of propylene oxide is added to polypropylene glycol, and an average of 15 moles of ethylene oxide glycol is added to each end.

[0336] Furthermore, it is preferred to have bisphenol A modified with an epoxide and to have (meth)acryloyl groups at both ends.

[0337] Examples of epoxide modification include ethylene oxide modification, propylene oxide modification, butane oxide modification, pentane oxide modification, and hexane oxide modification. Among these compounds, compounds that are ethylene oxide modified with bisphenol A and have (meth)acryloyl groups at both ends are preferred. Examples of such compounds include 2,2-bis(4-((meth)acryloyloxydiethoxy)phenyl)propane (Shin-Nakamura Chemical Co., Ltd. manufactures NK ester BPE-200), 2,2-bis(4-((meth)acryloyloxytriethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxytetraethoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloyloxypentethoxy)phenyl)propane (Shin-Nakamura Chemical Co., Ltd. manufactures NK ester BPE-200). Chemical Co., Ltd. manufactures NK ester BPE-500, 2,2-bis(4-((meth)acryloyloxyhexaethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxyheptaethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxyoctaethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxynonethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxydeaceoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxydeaceoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxy)noneth ...nonethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxy)nonethoxy)nonethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxy)nonethoxy)nonethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxy)nonethoxy)nonethoxy)nonethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxy)nonethoxy)nonethoxy 2,2-Bis(4-((meth)acryloyloxydodecethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxydecaethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxytetraethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxydecaethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxydecaethoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloyloxydecaethoxy)phenyl)propane, etc. 2,2-bis(4-((meth)acryloyloxypolyethoxy)phenyl)propane.

[0338] For compounds having more than two (meth)acryloyl groups in a molecule, an alcohol obtained by adding an alkyl group capable of addition to an alkyl group with more than 3 moles of such a group as a central skeleton to form an alkyl group is obtained as a (meth)acrylate. Examples of compounds capable of forming a central skeleton include glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, and isocyanurate rings.

[0339] In addition to the compounds mentioned above, the following compounds may also be appropriately included.

[0340] Examples include 1,6-hexanediol di(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, 2-di(p-hydroxyphenyl)propane di(meth)acrylate, 2,2-bis[(4-(meth)acryloyloxypoly(oxy)phenyl]propane, 2,2-bis[(4-(meth)acryloyloxypoly(butenoxy)phenyl]propane, glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, polyoxypropyltrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, trimethylolpropane triglycidyl ether tri(meth)acrylate, β-hydroxypropyl-β'-(acryloyloxy)propyl phthalate, nonylphenoxy polypropylene glycol (meth)acrylate, nonylphenoxy polybutylene glycol (meth)acrylate, and polypropylene glycol mono(meth)acrylate.

[0341] Further examples include urethane compounds such as hexamethylene diisocyanate, toluene diisocyanate, or diisocyanate compounds (e.g., 2,2,4-trimethylhexamethylene diisocyanate), compounds having hydroxyl and (meth)acrylate groups in one molecule, and urethane compounds such as those with hydroxypropyl 2-acrylate or oligopropylene glycol monomethacrylate. Specifically, there are reaction products of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (manufactured by Nippon Oil and Fats Company, Limited, BLEMMER PP1000). Also, examples include di or tri(meth)acrylates of isocyanates modified with polypropylene glycol or polycaprolactone. Furthermore, examples include urethane oligomers obtained by reacting the ends of urethane compounds obtained as addition polymers of diisocyanates and polyols with compounds having olefinic unsaturated double bonds and hydroxyl groups.

[0342] Examples of compounds with conjugated diene sites include compounds that have been modified by introducing substituents into butadiene and isoprene to produce non-volatile compounds, polyacetylene and its derivatives, and polyphenylacetylene.

[0343] Examples of compounds having a maleimide site include polymers having a maleimide group in the side chain, compounds having two or more maleimide groups in the molecule, and compounds having both (meth)acryloyl and maleimide groups in the molecule.

[0344] Examples of thiol compounds that are cured by the ethoxylation reaction include pentaerythritol tetrathiopropionate, pentaerythritol tetra(3-mercaptobutyrate), and 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, which contain aliphatic thiol groups.

[0345] Examples of epoxy compounds include epoxy-modified phenolic varnish resins, epoxy-modified cresol phenolic varnish resins, epoxy-modified bisphenol A, compounds obtained by modifying bisphenol A with ethylene oxide or propylene oxide and then further epoxy-modifying it, epoxy resins having a dicyclopentadiene skeleton, and alicyclic epoxy compounds. Among these, compounds having at least one glycidyl ether bond and at least one dicyclopentadiene group in one molecule are preferred.

[0346] Cyclic epoxy compounds have at least one alicyclic epoxy group. The alicyclic epoxy group refers to a monovalent substituent of a fused ring having an epoxy ring and a saturated hydrocarbon ring, preferably a monovalent substituent of a fused ring having an epoxy ring and a cycloalkane ring.

[0347] Examples of commercially available products that are preferred for use as alicyclic epoxides include CELLOXIDE 2000, CELLOXIDE 2021P, CELLOXIDE 3000, CELLOXIDE 8000, CYCLOMER M100, EPOLEAD GT301, EPOLEAD GT401 from Daicel Corporation, 4-vinylcyclohexene diepoxide manufactured by Sigma-Aldrich Co. LLC, D-limonene oxide from NIPPON TERPENE CHEMICALS, INC., and SANSOCIZER E-PS from NewJapan Chemical Co., Ltd.

[0348] These can be used individually or in combination of two or more.

[0349] Examples of compounds having cross-linked groups through the action of acid include amino compounds, such as melamine resin, urea resin, guanidine resin, glycourea-formaldehyde resin, succinamide-formaldehyde resin, and ethylene urea-formaldehyde resin, with alkoxymethylated amino resins being particularly preferred.

[0350] Alkoxymethylated amino resins can be manufactured, for example, by reacting a condensate obtained by reacting melamine or urea with formalin in a boiling aqueous solution with lower alcohols such as methanol, ethanol, propanol, butanol, and isopropanol to form an ether, followed by cooling the reaction solution to precipitate it out.

[0351] Examples of alkoxymethylated amino resins include methoxymethylated melamine resin, ethoxymethylated melamine resin, propoxymethylated melamine resin, butoxymethylated melamine resin, methoxymethylated urea resin, ethoxymethylated urea resin, propoxymethylated urea resin, and butoxymethylated urea resin.

[0352] Alkoxymethylated amino resins can be used alone or in combination of two or more. Preferably, they are methoxymethylated melamine resins, ethoxymethylated melamine resins, propoxymethylated melamine resins, or butoxymethylated melamine resins.

[0353] Specific examples of melamine resins include melamine, hydroxymethyl melamine, etherified hydroxymethyl melamine, benzoguanamine, hydroxymethylbenzoguanamine, etherified hydroxymethylbenzoguanamine, and their condensates. Among these, etherified hydroxymethyl melamine is preferred due to its good chemical resistance. Mixtures of etherified hydroxymethyl melamine and their condensates are commercially available as Nicarak MW-30 (product name) manufactured by SANWA CHEMICAL co., ltd.

[0354] Furthermore, combinations of polyisocyanates and polyols can be used as thermosetting compounds. A urethane bond is formed by the reaction of the isocyanate group with the hydroxyl group of the polyol, generating a urethane polymer as an adhesive.

[0355] Examples of polyvalent isocyanates (isocyanates with two or more functions) include phenylene-1,3-diisocyanate, phenylene-1,4-diisocyanate, 1-methoxyphenylene-2,4-diisocyanate, 1-methylphenylene-2,4-diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, and biphenylene-4,4- Diisocyanate, 3,3-dimethoxyphenylene-4,4-diisocyanate, 3,3-dimethylphenylene-4,4-diisocyanate, diphenylmethane-2,4-diisocyanate, diphenylmethane-4,4-diisocyanate, 3,3-dimethoxydiphenylmethane-4,4-diisocyanate, 3,3-dimethyldiphenylmethane-4,4-diisocyanate, naphthylene-1,5-diisocyanate, cyclobutene-1,3-diisocyanate Ester, cyclopentyl-1,3-diisocyanate, cyclohexyl-1,3-diisocyanate, cyclohexyl-1,4-diisocyanate, 1-methylcyclohexyl-2,4-diisocyanate, 1-methylcyclohexyl-2,6-diisocyanate, 1-isocyanate-3,3,5-trimethyl-5-isocyanate, methylcyclohexane, cyclohexane-1,3-bis(methyl isocyanate), cyclohexane-1,4-bis(methyl isocyanate) Two-terminated isocyanate prepolymers obtained by reacting isophorone diisocyanate, dicyclohexylmethane-2,4-diisocyanate, dicyclohexylmethane-4,4-diisocyanate, ethylene diisocyanate, tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, dodecyl-1,12-diisocyanate, or by reacting an excess of their organic diisocyanates with a 2-functional compound containing active hydrogen.

[0356] It can be used in conjunction with the above-mentioned diisocyanates, for example, simultaneously with phenyl-1,3,5-triisocyanate, diphenylmethane-2,4,4-triisocyanate, diphenylmethane-2,5,4-triisocyanate, triphenylmethane-2,4,4”-triisocyanate, triphenylmethane-4,4,4”-triisocyanate, diphenylmethane-2,4,2,4-tetraisocyanate, diphenylmethane-2,5,2,5-tetraisocyanate, cyclohexane-1,3,5-triisocyanate, cyclohexane-1,3,5-triisocyanate, and cyclohexane-1,3,5-tris(methylisocyanate). Terminal isocyanate prepolymers obtained by reacting trifunctional or higher organic polyisocyanates such as 3,5-dimethylcyclohexane-1,3,5-tris(methylisocyanate), 1,3,5-trimethylcyclohexane-1,3,5-tris(methylisocyanate), dicyclohexylmethane-2,4,2-triisocyanate, and dicyclohexylmethane-2,4,4-triisocyanate with a polyfunctional compound containing active hydrogen.

[0357] Examples of polyols (compounds with hydroxyl groups having two or more functions) include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,4-butanediol, polytetramethylene glycol, glycerol, trimethylolpropane, and pentaerythritol.

[0358] Furthermore, in the case where a combination of polyisocyanate and polyol is included as a thermosetting compound, it is more preferable to include a reaction accelerator that promotes the thermosetting reaction of polyisocyanate and polyol in the adhesive precursor. By adding a reaction accelerator, the reaction between isocyanate and hydroxyl groups can be accelerated, resulting in a good urethane polymer even at low temperatures. As a reaction accelerator, preferred are tetraalkylammonium salts, cyclic amidines such as diazabicyclo(DBU) or diazabicyclononene (DBN) and their salts, cyclic amines such as 1,4-diazabicyclo[2.2.2]octane (DABCO), pyridines, imidazoles, nitrogen-containing heteroaromatic compounds and their salts, alkyltin compounds and their salts, alkylzinc compounds and their salts, zirconium compounds, titanium compounds, alkylaluminum compounds, and borates.

[0359] Furthermore, it is also possible to use thermosetting resins that are cured by alkali cyclization, such as polyimide precursor resins, polyamide-imide precursor resins, and polybenzoxazole precursor resins.

[0360] The curable composition layer may contain a single curable compound or two or more curable compounds.

[0361] When the curable composition layer contains a curable compound, the content of the curable compound relative to the total mass of the curable composition layer is preferably 10% by mass or more, more preferably 25% by mass or more. There is no particular upper limit, but it is preferably 70% by mass or less, more preferably 60% by mass or less.

[0362] [Curing agent]

[0363] When the curable composition layer contains an epoxy compound, the curable composition layer may also contain an epoxy curing agent.

[0364] As epoxy curing agents, anhydride-based curing agents, polyamine-based curing agents, catalytic curing agents, and polycarboxylic acid-based curing agents are preferred.

[0365] Examples of anhydride-based curing agents include maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrotriphthalic anhydride, phthalic anhydride, trimellitic anhydride, and styrene-maleic anhydride copolymer.

[0366] Examples of polyamine-based curing agents include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dicyandiamine, polyamide-based amines (polyamide resins), ketimine compounds, isophorone diamine, m-xylene diamine, m-phenylenediamine, 1,3-bis(aminomethyl)cyclohexane, N-aminoethylpiperazine, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, and diaminodiphenyl sulfone.

[0367] Tertiary amine compounds and imidazole compounds can be cited as examples of catalytic curing agents.

[0368] Examples of polycarboxylic acid curing agents include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 3,6-intramethylenetetrahydrophthalic anhydride, hexachlorointramethylenetetrahydrophthalic anhydride, and methyl-3,6-intramethylenetetrahydrophthalic anhydride.

[0369] When the curable composition layer contains a curing agent, the content of the curing agent relative to the total mass of the curable composition layer is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass.

[0370] [Polymerization initiator]

[0371] The curable composition layer may contain a polymerization initiator.

[0372] As a polymerization initiator, a preferred polymerization initiator is preferably used depending on the type of curable compound, and more preferably a photopolymerization initiator or a thermal polymerization initiator. A photopolymerization initiator is a compound that can decompose upon exposure to generate initiating species such as free radicals and acids, and is a compound that can initiate and promote the polymerization reaction of the polymerizable compound through these initiating species.

[0373] The polymerization can be free radical polymerization, cationic polymerization, or anionic polymerization. If the polymerization initiator contains highly nucleophilic substances in at least a portion of its components, or as impurities or decomposition products, it can sometimes lead to adsorption onto the surface of the phosphor, thus slowing down the reaction rate of the epoxide, or simultaneously affecting the luminous efficiency of the phosphor contained in the phosphor dispersion composition. Therefore, it is preferable to reduce the content of highly nucleophilic components in the polymerization initiator, especially primary and secondary amines.

[0374] Examples of photopolymerization initiators include quinones, aromatic ketones, acetophenones, acylphosphine oxides, benzoin or benzoin derivatives, dialkyl ketals, thioxanones, dialkylaminobenzoates, oxime esters, acridines, hexaaryl biimidazoles, pyrazoline derivatives, N-aryl amino acids or their ester compounds, and halogen compounds.

[0375] Examples of quinones include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthroquinone, 2-methyl-1,4-naphthoquinone, 9,10-phenanthroquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone.

[0376] Examples of aromatic ketones include benzophenone, michidone [4,4'-bis(dimethylamino)benzophenone], 4,4'-bis(diethylamino)benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone.

[0377] Examples of acetophenones include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropane-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)one, 1-hydroxycyclohexylphenylone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-acetone-1. Commercially available examples include Irgacure-907, Irgacure-369, and Irgacure-379 manufactured by Ciba Japan KK.

[0378] Examples of acylphosphine oxides include 2,4,6-trimethylbenzyl diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide. Commercially available examples include Lucirin TPO manufactured by BASF and Irgacure-819 manufactured by Ciba Japan KK.

[0379] Examples of benzoin or benzoin-like compounds include benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin.

[0380] Examples of dialkyl ketals include benzyl dimethyl ketal and benzyl diethyl ketal.

[0381] Examples of thioxanthone derivatives include 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.

[0382] Examples of dialkylaminobenzoic acid esters include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl p-dimethylaminobenzoate, and 2-ethylhexyl 4-(dimethylamino)benzoate.

[0383] Examples of oxime esters include 1-phenyl-1,2-propanedione-2-O-benzoyl oxime and 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime. Commercially available examples include CGI-325, Irgacure-OXE01, and Irgacure-OXE02 manufactured by Ciba Japan KK.

[0384] Furthermore, a photocationic polymerization initiator can also be used as a photopolymerization initiator. Regarding photocationic polymerization initiators, for example, reference can be made to paragraphs

[0019] to

[0024] of Japanese Patent No. 4675719.

[0385] Preferred photocationic polymerization initiators include iodide salts, sulfonium salts, pyridinium salts, and phosphonium salts. Among these, iodide salts or sulfonium salts are preferred due to their excellent thermal stability.

[0386] Iodized salts are compounds whose structure contains I. + The salt formed by the cation portion and the anion portion in any structure is more preferably a diaryl iodide salt having three or more electron-donating groups, at least one of which is an alkoxy group. By introducing an alkoxy group as an electron-donating group into the diaryl iodide salt, it is possible to suppress decomposition over time based on water or nucleophiles or electron transfer caused by heat, thereby expecting to improve stability.

[0387] Examples of usable photocationic polymerization initiators include one or more of the following commercially available products: CPI-110P (hereinafter referred to as photocationic polymerization initiator C), CPI-101A, CPI-110P, and CPI-200K manufactured by San-Apro Ltd.; WPI-113, WPI-116, WPI-124, WPI-169, and WPI-170 manufactured by Wako Pure Chemical Industries, Ltd.; PI-2074 manufactured by Rhodia Co., Ltd.; and Irgacure-250, Irgacure-270, and Irgacure-290 (hereinafter referred to as photocationic polymerization initiator D) manufactured by BASF.

[0388] Examples of thermal polymerization initiators include onium salts such as iodide salts, sulfonium salts, and phosphonium salts; complex salts of boron trifluoride or Lewis acid compounds (e.g., zinc halides, tin halides, aluminum halides, and iron halides) and tertiary amines or nitrogen-containing heteroaromatic compounds; the aforementioned imidazoles; cyclic amidines; and their salts with organic acids.

[0389] The curable composition layer may contain a single polymerization initiator or two or more polymerization initiators.

[0390] When the curable composition layer contains a polymerization initiator, the content of the polymerization initiator relative to the total mass of the curable composition layer is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass.

[0391] [Heterocyclic compounds]

[0392] The curable composition layer may contain heterocyclic compounds.

[0393] Heterocyclic compounds can have any heterocyclic ring, whether it is a monocyclic or polycyclic heterocyclic ring.

[0394] Examples of heteroatoms in heterocyclic compounds include nitrogen, oxygen, and sulfur atoms. Heterocyclic compounds preferably have at least one atom selected from nitrogen, oxygen, and sulfur atoms, and more preferably have a nitrogen atom.

[0395] Examples of heterocyclic compounds include triazole compounds, benzotriazole compounds, tetraazole compounds, thiadiazole compounds, triazine compounds, razotanine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, benzoxazole compounds, and pyrimidine compounds (e.g., isonicotinamide).

[0396] In the above, the heterocyclic compound is preferably selected from at least one compound selected from triazole compounds, benzotriazole compounds, tetraazole compounds, thiadiazole compounds, triazine compounds, razotanine compounds, thiazole compounds, benzimidazole compounds, and benzoxazole compounds, and more preferably selected from at least one compound selected from triazole compounds, benzotriazole compounds, tetraazole compounds, thiadiazole compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, and benzoxazole compounds.

[0397] Preferred examples of heterocyclic compounds are shown below. The following compounds can be exemplified as triazole and benzotriazole compounds.

[0398] [Chemical Formula 12]

[0399]

[0400] [Chemical Formula 13]

[0401]

[0402] The following compounds can be cited as examples of tetrazolium compounds.

[0403] [Chemical Formula 14]

[0404]

[0405] [Chemical Formula 15]

[0406]

[0407] The following compounds can be cited as examples of thiadiazole compounds.

[0408] [Chemical Formula 16]

[0409]

[0410] The following compounds can be cited as examples of triazine compounds.

[0411] [Chemical Formula 17]

[0412]

[0413] The following compounds can be cited as examples of cyclotannin compounds.

[0414] [Chemical Formula 18]

[0415]

[0416] The following compounds can be cited as examples of thiazole compounds.

[0417] [Chemical Formula 19]

[0418]

[0419] The following compounds can be cited as examples of benzothiazole compounds.

[0420] [Chemical Formula 20]

[0421]

[0422] The following compounds can be cited as examples of benzimidazole compounds.

[0423] [Chemical Formula 21]

[0424]

[0425] [Chemical Formula 22]

[0426]

[0427] The following compounds can be cited as examples of benzoxazole compounds.

[0428] [Chemical Formula 23]

[0429]

[0430] The curable composition layer may contain a single heterocyclic compound or two or more heterocyclic compounds.

[0431] When the curable composition layer contains a heterocyclic compound, the content of the heterocyclic compound relative to the total mass of the curable composition layer is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass.

[0432] [Terminated isocyanate]

[0433] The curable composition layer may contain end-capped isocyanates.

[0434] A terminated isocyanate compound is defined as "a compound having a structure in which the isocyanate group of the isocyanate is protected (so-called masking) by a terminating agent".

[0435] The dissociation temperature of the capped isocyanate compound is not particularly limited, but is preferably 100–160°C, more preferably 130–150°C.

[0436] The dissociation temperature of capped isocyanates refers to "the temperature of the endothermic peak accompanying the deprotection reaction of capped isocyanates when measured using a differential scanning calorimeter and analyzed by DSC (Differential Scanning Calorimetry)".

[0437] As a differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be preferably used. However, the differential scanning calorimeter is not limited to this.

[0438] Examples of end-capping agents with dissociation temperatures of 100–160°C include active methylene compounds (such as malonate (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)) and oxime compounds (such as formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime, which have an intramolecular structure represented by -C (=N-OH)-).

[0439] Among them, the capping agent with a dissociation temperature of 100 to 160°C is preferably selected from at least one oxime compound, for example, from the viewpoint of storage stability.

[0440] For example, considering factors such as improving the brittleness of the film and enhancing the adhesion between the film and the substrate, the end-capped isocyanate compound preferably has an isocyanurate structure.

[0441] End-capped isocyanate compounds having an isocyanurate structure are obtained, for example, by isocyanuration of hexamethylene diisocyanate.

[0442] Among the isocyanate compounds with an isocyanurate structure, compounds with an oxime structure that allow the oxime compound to be used as a capping agent are preferred, considering that it is easier to set the dissociation temperature within a preferred range and easier to reduce development residue compared to compounds without an oxime structure.

[0443] End-capped isocyanate compounds can have polymerizable groups.

[0444] There are no particular restrictions on the polymerizable group; any known polymerizable group can be used, with free radical polymerizable groups being preferred.

[0445] Examples of polymerizable groups include olefinic unsaturated groups such as (meth)acryloyloxy, (meth)acrylamido, and styryl, as well as groups with epoxy groups such as glycidyl.

[0446] Among them, the polymerizable group is preferably an olefinic unsaturated group, more preferably (meth)acryloyloxy, and even more preferably acryloyloxy.

[0447] As a capped isocyanate compound, it can be used in commercially available products.

[0448] Examples of commercially available isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (manufactured by SHOWA DENKO KK), and the end-capped DURANATE series (e.g., DURANATE (registered trademark) TPA-B80E, DURANATE (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation).

[0449] Furthermore, compounds with the following structure can also be used as end-capped isocyanate compounds.

[0450] [Chemical Formula 24]

[0451]

[0452] The curable composition layer may contain a single type of end-capped isocyanate or two or more types of end-capped isocyanates.

[0453] When the curable composition layer contains end-capped isocyanate, the content of end-capped isocyanate in the curable composition layer is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, relative to the total mass of the curable composition layer.

[0454] [Aliphatic thiols]

[0455] The curable composition layer may contain aliphatic thiol compounds.

[0456] By including an aliphatic thiol compound in the curable composition layer, the aliphatic thiol compound undergoes an olefinic thiol reaction with a free radical polymerizable compound having olefinic unsaturated groups, thereby suppressing the curing shrinkage of the film and relaxing the stress.

[0457] As an aliphatic thiol compound, it is preferred to be a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (i.e., an aliphatic thiol compound with two or more functions).

[0458] In the above, aliphatic thiol compounds are preferred, for example, from the perspective of the adhesion of the formed pattern (especially the adhesion after exposure).

[0459] In this invention, "multifunctional aliphatic thiol compound" refers to an aliphatic compound having two or more thiol groups (also called "mercapto groups") within its molecule.

[0460] As a polyfunctional aliphatic thiol compound, a low molecular weight compound with a molecular weight of 100 or more is preferred. Specifically, the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, and even more preferably 150 to 1,000.

[0461] The number of functional groups in a multifunctional aliphatic thiol compound is preferably 2 to 10, more preferably 2 to 8, and even more preferably 2 to 6, considering the tightness of the formed pattern.

[0462] Examples of polyfunctional aliphatic thiols include trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetra(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolethane tris(3-mercaptobutyrate), tris[(3-mercaptopropionyloxy)ethyl]isocyanurate, and trimethylolpropionyloxyethyl thiocyanate. Propane tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), ethylene glycol dithiopropionate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,2-ethylenedithiol, 1,3-propanedithiol, 1,6-hexamethylenedithiol, 2,2'-(ethylenedithio)bis(ethanedithio)diethylthiol, meso-2,3-dimercaptosuccinic acid, and di(mercaptoethyl) ether.

[0463] In the above, the multifunctional aliphatic thiol compound is preferably at least one compound selected from trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0464] Examples of monofunctional aliphatic thiols include 1-octylthiol, 1-dodecylthiol, β-mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.

[0465] The curable composition layer may contain a single aliphatic thiol compound or two or more aliphatic thiol compounds.

[0466] When the curable composition layer contains an aliphatic thiol compound, the content of the aliphatic thiol compound relative to the total mass of the curable composition layer is preferably 5% by mass or more, more preferably 5 to 50% by mass, even more preferably 5 to 30% by mass, and particularly preferably 8 to 20% by mass.

[0467] [surfactant]

[0468] The curable composition layer may also contain surfactants.

[0469] As surfactants, examples include those described in paragraph

[0017] of Japanese Patent No. 4502784 and paragraphs

[0060] to

[0071] of Japanese Unexamined Patent Publication No. 2009-237362.

[0470] As surfactants, fluorinated surfactants or silicone surfactants are preferred. Commercially available fluorinated surfactants include, for example, MEGAFACE F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, etc. MFS-330, EXP.MFS-578, EXP.MFS-578-2, EXP.MFS-579, EXP.MFS-586, EXP.MFS-587, EXP.MFS-628, EXP.MFS-6 31. EXP.MFS-603, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (above, DIC Fluorad FC430, FC431, FC171 (and above, manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (and above, manufactured by AGC Inc.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (and above, manufactured by OMNOVA Solutions Inc.), Ftergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (and above, manufactured by Neos Corporation), U-120E (manufactured by UNICHEM CO., LTD.), etc.

[0471] Furthermore, acrylic compounds are preferred as fluorinated surfactants. These compounds have a molecular structure containing functional groups with fluorine atoms, which, upon heating, are cleaved, causing the fluorine atoms to volatilize. Examples of such fluorinated surfactants include the MEGAFACE DS series manufactured by DIC Corporation (The Chemical Daily Co., Ltd. (February 22, 2016), NIKKEI BUSINESS DAILY (February 23, 2016)), such as MEGAFACE DS-21.

[0472] Furthermore, polymers of fluorinated vinyl ether compounds having fluorinated alkyl or fluorinated alkylene ether groups and hydrophilic vinyl ether compounds are preferred as fluorinated surfactants.

[0473] Furthermore, as a fluorinated surfactant, it can also be used with end-capped polymers.

[0474] Furthermore, as a fluorinated surfactant, it is preferable to use a fluorinated polymer compound that contains structural units derived from (meth)acrylate compounds having fluorine atoms and structural units derived from (meth)acrylate compounds having two or more (preferably five or more) alkeneoxy groups (preferably ethoxy or propoxy groups).

[0475] Furthermore, as a fluorinated surfactant, it can also be used on fluorinated polymers with olefinically unsaturated groups on their side chains. Examples include MEGAFACE RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DICCorporation).

[0476] From the perspective of improving environmental adaptability, surfactants derived from perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) and other compounds with straight-chain perfluoroalkyl groups having 7 or more carbon atoms are preferred as fluorinated surfactants.

[0477] Examples of hydrocarbon-based surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylated and propoxylated derivatives (e.g., glycerol propoxylated, glycerol ethoxylated, etc.), polyoxyethylene lauryl ether, polyoxyethylene octadecyl ether, polyoxyethylene oil-based ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitol fatty acid esters.

[0478] Specific examples include Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, HYDROPALAT WE 3323 (and above, manufactured by BASF), Solsperse 20000 (and above, manufactured by Lubrizol Japan Limited.), NCW-101, NCW-1001, NCW-1002 (and above, manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-1105, D-6112, D-6112-W, D-6315 (and above, manufactured by Takemoto Oil & Fat Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (and above, manufactured by Nissin Chemical Co., Ltd.), etc.

[0479] Examples of silicone surfactants include linear polymers composed of siloxane bonds and modified siloxane polymers with organic groups introduced into the side chains or ends.

[0480] Specific examples of silicone-based surfactants include EXP.S-309-2, EXP.S-315, EXP.S-503-2, EXP.S-505-2 (and above, manufactured by DIC Corporation), DOWSIL 8032ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (and above, manufactured by Dow Corning Toray). (manufactured by Co., Ltd.) and models 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, KF-6001, KF-6002, KP-101, KP-103, KP-104, KP-1 05. KP-106, KP-109, KP-112, KP-120, KP-121, KP-124, KP-125, KP-301, KP-306, KP-310, KP-322, K P-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, KP-652 (above, Shin-Etsu (Manufactured by Silicone Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (and above, manufactured by Momentive Performance Materials Inc.), BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378 (and above, manufactured by BYK Chemie Co., Ltd.), etc.

[0481] The curable composition layer may contain a single surfactant or two or more surfactants.

[0482] When the curable composition layer contains a surfactant, the surfactant content relative to the total mass of the curable composition layer is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass, and even more preferably 0.1 to 0.8% by mass.

[0483] [Hydrogen-donating compounds]

[0484] The curable composition layer may contain a hydrogen-donating compound.

[0485] Hydrogen-donating compounds can further enhance the sensitivity of photopolymerization initiators to photochemical rays and inhibit the polymerization hindrance of polymerizable compounds caused by oxygen.

[0486] Examples of hydrogen-donating compounds include amines, such as those described in the Journal of Polymer Society, Vol. 10, p. 3173 (1972), Japanese Patent Publication No. 44-020189, Japanese Patent Application Publication No. 51-082102, Japanese Patent Application Publication No. 52-134692, Japanese Patent Application Publication No. 59-138205, Japanese Patent Application Publication No. 60-084305, Japanese Patent Application Publication No. 62-018537, Japanese Patent Application Publication No. 64-033104, and Research Disclosure No. 33825.

[0487] Examples of hydrogen-donating compounds include triethanolamine, ethyl p-dimethylaminobenzoate, p-formyldimethylaniline, and p-methylthiodimethylaniline.

[0488] Furthermore, examples of hydrogen-donating compounds include amino acid compounds (such as N-phenylglycine), organometallic compounds (such as tributyltin acetate) disclosed in Japanese Patent Publication No. 48-042965, hydrogen donors disclosed in Japanese Patent Publication No. 55-034414, and sulfur compounds (such as trithianes) disclosed in Japanese Patent Application Publication No. 6-308727.

[0489] The curable composition layer may contain a single hydrogen-donating compound or two or more hydrogen-donating compounds.

[0490] When the curable composition layer contains a hydrogen-donating compound, from the perspective of improving the curing speed by balancing the polymerization growth rate and chain transfer, the content of the hydrogen-donating compound relative to the total mass of the curable composition layer is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass, and even more preferably 0.05 to 3% by mass.

[0491] [Other ingredients]

[0492] The curable composition layer may contain components other than those already described (hereinafter also referred to as "other components"). Examples of other components include, for instance, particles (e.g., metal oxide particles) and colorants.

[0493] Furthermore, as other components, examples include the heat-resistant polymerizer described in paragraph

[0018] of Japanese Patent No. 4502784 and other additives described in paragraphs

[0058] to

[0071] of Japanese Patent Application Publication No. 2000-310706.

[0494] The curable composition layer may contain particles for the purpose of adjusting refractive index, light transmittance, etc. Examples of particles include metal oxide particles.

[0495] Metals in metal oxide particles also include half-metals such as B, Si, Ge, As, Sb, and Te.

[0496] The average primary particle size, for example, considering the transparency of the pattern, is preferably 1 to 200 nm, more preferably 3 to 80 nm. The average primary particle size is calculated by measuring the particle size of any 200 particles using an electron microscope and then arithmetically averaging the results. Furthermore, if the particle shape is not spherical, the longest side is used as the particle size.

[0497] The curable composition layer may contain a single type of particle or two or more types of particles. Furthermore, when the curable composition layer contains particles, it may contain only one type of particle with different metal types and sizes, or it may contain two or more types of particles with different metal types and sizes.

[0498] The curable composition layer preferably does not contain particles or the content of particles is more than 0% by mass and less than 35% by mass relative to the total mass of the curable composition layer, more preferably it does not contain particles or the content of particles is more than 0% by mass and less than 10% by mass relative to the total mass of the curable composition layer, even more preferably it does not contain particles or the content of particles is more than 0% by mass and less than 5% by mass relative to the total mass of the curable composition layer, particularly preferably it does not contain particles or the content of particles is more than 0% by mass and less than 1% by mass relative to the total mass of the curable composition layer, and most preferably it does not contain particles.

[0499] The curable composition layer may contain trace amounts of colorants (e.g., pigments and dyes), but preferably does not contain colorants, for example, from the perspective of transparency.

[0500] When the curable composition layer contains a colorant, the content of the colorant relative to the total mass of the curable composition layer is preferably less than 1% by mass, more preferably less than 0.1% by mass.

[0501] [Impurities, etc.]

[0502] The cured composition layer may contain a specified amount of impurities.

[0503] Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and their ions. Among these, halide ions, sodium ions, and potassium ions are easily introduced as impurities, and therefore are preferably set to the following concentrations.

[0504] The impurity content in the curable composition layer, by weight, is preferably 80 ppm or less, more preferably 10 ppm or less, and even more preferably 2 ppm or less. The impurity content in the curable composition layer, by weight, can be set to 1 ppb or more, and can be set to 0.1 ppm or more.

[0505] As a method for setting impurities within the aforementioned range, examples include selecting raw materials with low impurity content as the raw materials for the curable composition layer, preventing impurity contamination during the formation of the curable composition layer, and cleaning and removing impurities. By using these methods, the amount of impurities can be kept within the aforementioned range.

[0506] For example, impurities can be quantified using known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0507] The content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the curable composition layer is preferably low. As a mass basis, the content of these compounds in the curable composition layer is preferably 100 ppm or less, more preferably 20 ppm or less, and even more preferably 4 ppm or less. The lower limit can be set to 10 ppb or more, and can be set to 100 ppb or more, as a mass basis. The content of these compounds can be controlled by the same method as for impurities of the aforementioned metals. Furthermore, quantification can be performed using known methods.

[0508] From the perspective of improving reliability and lamination, the water content in the curable composition layer is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass.

[0509] [Thickness of the curable composition layer]

[0510] From the perspective of coatability, the upper limit of the thickness of the curable composition layer is preferably 20.0 μm or less, more preferably 15.0 μm or less, and even more preferably 12.0 μm or less.

[0511] The lower limit of the thickness of the curable composition is preferably 0.05 μm or more.

[0512] The thickness of the cured composition layer was calculated as the average of five arbitrary points measured by cross-sectional observation using a scanning electron microscope (SEM).

[0513] [Color of the cured composition layer]

[0514] The curable composition layer is preferably colorless. The curable composition layer a * The preferred value is -1.0 to 1.0, and the b value of the curable composition layer is... * The preferred value is -1.0 to 1.0.

[0515] The hue of the cured composition layer can be determined using a colorimeter (CR-221, manufactured by Minolta Co., Ltd.).

[0516] [Manufacturing method of transfer film]

[0517] The manufacturing method of transfer film is not particularly restricted and can use well-known methods.

[0518] From a productivity standpoint, a method in which the curable composition is applied to a temporary support and dried as needed to form a layer of the curable composition is preferred (hereinafter, this method is referred to as the "coating method").

[0519] The curable composition used in the coating method preferably includes components constituting the curable composition layer (e.g., polymeric compounds, polymers, heterocyclic compounds, polymerization initiators, end-capped isocyanate compounds, etc.) and solvents.

[0520] Organic solvents are preferred as solvents. Examples of organic solvents include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (also known as 1-methoxy-2-propyl acetate), diethylene glycol ethyl methyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam, n-propanol, and 2-propanol. A mixture of methyl ethyl ketone and propylene glycol monomethyl ether acetate or a mixture of diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate is preferred as a solvent.

[0521] Furthermore, organic solvents with boiling points of 180–250°C (high-boiling-point solvents) can also be used as solvents as needed.

[0522] The curable composition may contain a single solvent or two or more solvents.

[0523] When the curable composition contains a solvent, the total solid content of the curable composition relative to the total mass of the curable composition is preferably 5 to 80% by mass, more preferably 5 to 40% by mass, and even more preferably 5 to 30% by mass.

[0524] When the curable composition contains a solvent, for example from the perspective of coatability, the viscosity of the curable composition at 25°C is preferably 1 to 50 mPa·s, more preferably 2 to 40 mPa·s, and even more preferably 3 to 30 mPa·s. The viscosity is measured using a viscometer. As a viscometer, it is preferable to use, for example, a viscometer manufactured by TOKI SANGYO CO., LTD. (product name: VISCOMETER TV-22). However, the viscometer is not limited to the one described above.

[0525] When the curable composition contains a solvent, for example from the perspective of coatability, the surface tension of the curable composition at 25°C is preferably 5 to 100 mN / m, more preferably 10 to 80 mN / m, and even more preferably 15 to 40 mN / m. The surface tension is measured using a surface tension meter. As a surface tension meter, it is preferable to use, for example, a surface tension meter manufactured by Kyowa Interface Science Co., Ltd. (product name: Automatic Surface Tensiometer CBVP-Z). However, the surface tension meter is not limited to the one described above.

[0526] Examples of coating methods for curable compositions include printing, spraying, roller coating, bar coating, curtain coating, spin coating, and stencil coating (i.e., slot coating).

[0527] Examples of drying methods include natural drying, heat drying, and vacuum drying. These methods can be used individually or in combination.

[0528] In this invention, "drying" means removing at least a portion of the solvent contained in the composition.

[0529] Furthermore, when the transfer film has a protective film, the transfer film can be manufactured by attaching the protective film to the curable composition layer.

[0530] There are no particular limitations on the method of applying the protective film to the curable composition layer, and well-known methods can be cited.

[0531] As a device for bonding a protective film to a curable composition layer, known laminators such as vacuum laminators and automatic cutting laminators can be cited.

[0532] The laminator is equipped with any heatable roller, such as a rubber roller, and preferably one that can be pressurized and heated.

[0533] Implementation Method 2

[0534] The second embodiment of the laminate of the present invention will be described with reference to the accompanying drawings.

[0535] Figure 3 The laminate 20 shown has a dielectric film 22, a first metal pattern 24 disposed on one surface of the dielectric film 22, a first organic film 26 disposed on the first metal pattern 24, a second metal pattern 28 disposed on the other surface of the dielectric film 22, and a first organic film 30 disposed on the first metal pattern 28.

[0536] like Figure 3 As shown, the first metal pattern 24 is composed of multiple first metal structures 32, and the second metal pattern 28 is composed of multiple second metal structures 34.

[0537] In the stack 20, the first metal pattern 24 and the second metal pattern 28 form a resonator for electromagnetic waves in the terahertz frequency band. More specifically, the first metal structure 32 in the first metal pattern 24 and the second metal structure 34 in the second metal pattern 28 resonate for electromagnetic waves in the terahertz frequency band, and the first metal structure 32 and the second metal structure 34 can function as a resonator.

[0538] The dielectric film included in the second embodiment is the same component as the dielectric film included in the first embodiment, and their description is omitted.

[0539] Furthermore, the first organic membrane and the second organic membrane included in the second embodiment are the same components as the organic membrane included in the first embodiment, and their description is omitted.

[0540] The various characteristics of the shape, size, and material of the first metal structure constituting the first metal pattern and the second metal structure constituting the second metal pattern included in the second embodiment can be exemplified by the various characteristics described in the metal structure constituting the metal pattern included in the first embodiment.

[0541] In addition, considering the resonance of electromagnetic waves in the terahertz band, when viewing the laminate from above, it is preferable that the first metal structure contained in the first metal pattern and the second metal structure contained in the second metal pattern are arranged in a manner that at least partially overlaps.

[0542] Furthermore, when the stacked body is viewed from above, the first metal structure contained in the first metal pattern and the second metal structure contained in the second metal pattern can be arranged in a non-overlapping manner, but the deviation is preferably less than 20 μm.

[0543] <Manufacturing Method of Laminated Materials>

[0544] The manufacturing method of the second embodiment of the laminate is not particularly limited, but preferably includes a step 1B in which a metal-patterned film (hereinafter also simply referred to as "metal-patterned film B") comprising a dielectric film, a first metal pattern disposed on one surface of the dielectric film and composed of a plurality of first metal structures, and a second metal pattern disposed on the other surface of the dielectric film and composed of a plurality of second metal structures, is laminated with a transfer film comprising a temporary support and a curable composition layer to form a precursor film having a temporary support, a curable composition layer, a first metal pattern, a dielectric film, a second metal pattern, a curable composition layer and a temporary support in sequence, and a step 2B in which the curable composition layer is cured to obtain an organic film, and a step 3B in which the temporary support is peeled off between step 1B and step 2B or after step 2B.

[0545] The manufacturing method described above will be explained in detail below.

[0546] (Membrane B with metallic pattern)

[0547] In the above method, a film B with a metallic pattern can be used.

[0548] The structure of the metal pattern contained in the metal patterned membrane B is the same as the structure of the metal pattern in the laminate described above.

[0549] The manufacturing method of the above-mentioned metal patterned film B is not particularly limited. Metal layers are formed on both sides of the dielectric film, a specified resist pattern is arranged on the metal layers, the metal layers not covered by the resist pattern are etched away, and the resist pattern is stripped off, thereby manufacturing the metal patterned film B.

[0550] (Process 1B)

[0551] Step 1B involves bonding a metal-patterned film B with a transfer film containing a temporary support and a curable composition layer to form a precursor film having, in sequence, a temporary support, a curable composition layer, a first metal pattern, a dielectric film, a second metal pattern, a curable composition layer, and a temporary support.

[0552] In this process, two transfer films are prepared, and the transfer film is attached to both sides of film B with the metallic pattern.

[0553] The bonding method can be exemplified by the method described in step 1A above.

[0554] (Process 2B)

[0555] Step 2B is a step of curing the curable composition layer to obtain an organic film.

[0556] By performing this process, a first organic film is formed on a first metal pattern, and a second organic film is formed on a second metal pattern.

[0557] Regarding the curing process, the method described in step 2A above can be cited as an example.

[0558] (Process 3B)

[0559] Process 3B is the process of removing the temporary support between process 1B and process 2B, or after process 2B.

[0560] There are no particular limitations on the peeling method, and the same mechanism as the covering film peeling mechanism described in paragraphs

[0161] to

[0162] of Japanese Patent Application Publication No. 2010-072589 can be used.

[0561] "use"

[0562] The laminate of the present invention is applicable to a variety of uses. In particular, the laminate of the present invention is preferably used as a sheet-type component included in an optical element. That is, the optical element of the present invention includes the above-described laminate.

[0563] Examples of optical components include flat lens, diffraction grating, wavelength film, polarizer, and sensor.

[0564] The size of the laminate is not particularly limited; the appropriate and optimal size is selected based on the intended use. For example, the preferred area of ​​the laminate is 1 cm². 2 The above, preferably 5cm 2 above.

[0565] Example

[0566] The following examples and comparative examples illustrate the features of the present invention in more detail. The materials, amounts, proportions, processing methods, and processing order shown in the following examples can be appropriately modified without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be limited by the specific examples shown below.

[0567] Furthermore, in the following embodiments, the weight-average molecular weight of the resin is the weight-average molecular weight calculated using polystyrene based on gel permeation chromatography (GPC). Also, the theoretical acid value was used.

[0568] Manufacturing of films with metallic patterns

[0569] (Membrane 1 with metallic pattern)

[0570] A COP film was manufactured using the method described in Japanese Patent No. 4991170. The thickness of the COP film was 50 μm.

[0571] Next, after ultrasonically cleaning (45kHz) the surface of the COP film, a film cut to a size of 10cm was installed inside a sputtering apparatus. Argon gas was introduced after depressurization of the apparatus, and Cu was used to sputter the target material. Copper layers with a thickness of 50nm were formed on both sides sequentially.

[0572] Next, the photosensitive transfer component (negative transfer material 1) shown in Japanese Patent Application Publication No. 2020-204757 is unfolded, and the cover film is peeled off from the photosensitive transfer component. Then, the photosensitive transfer component and the COP film with the aforementioned copper layer are laminated together to expose the photosensitive resin layer and copper layer exposed by the peeling off of the cover film, thereby obtaining a laminate. This lamination process is performed under conditions of a roller temperature of 100°C, a linear pressure of 1.0 MPa, and a linear speed of 4.0 m / min.

[0573] From the temporary support sides of the obtained laminate, across Figure 4 The photomask shown is irradiated with 100 mJ / cm 2 The photosensitive resin layer was exposed using an ultra-high pressure mercury lamp (main exposure wavelength: 365nm).

[0574] Figure 4 The photomask 40 shown has a plurality of rectangular openings 42 arranged at equal intervals in both the width and length directions. The length L of each opening 42 is 313 μm, and the width W is 54 μm. The distance D1 between the openings in the length direction is 94 μm, and the distance D2 between the openings in the width direction is 86 μm.

[0575] After the temporary supports on both sides of the exposed laminate were peeled off, the laminate was sprayed with a 1.0% sodium carbonate aqueous solution at a liquid temperature of 25°C for 30 seconds to form a resist pattern on the copper layer.

[0576] The obtained laminate was then etched for 30 seconds at 23°C using a copper etching solution (Cu-02: manufactured by KANTO CHEMICAL CO., INC.), followed by stripping the resist pattern using propylene glycol monomethyl ether acetate, thereby obtaining a film 1 with a metallic pattern formed by copper patterns on both the surface and back. The transmission characteristics of the obtained metallic patterned film 1 were measured using terahertz time-domain spectroscopy (THz-TDS). The sample was fixed (NA ~ 1 / 6) in an aperture of Φ10 mm and irradiated with a terahertz beam at 25°C and 20% humidity. The polarization direction was aligned with the long axis of the pattern. A steep valley (recess) in transmittance and phase reversal were observed near 320 GHz, suggesting that the metallic patterns arranged on both sides of the COP film resonate.

[0577] (Membrane 2 with metallic pattern)

[0578] Instead of a COP film with silver layers on both sides, a COP film with copper layers on both sides was used. Otherwise, a metal-patterned film 2 was manufactured in the same order as described above (film 1 with metal patterns). The transmittance characteristics of the metal patterns disposed on both sides of the COP film in the obtained metal-patterned film 2 were measured using the same method as in the case of film 1 with metal patterns, and it was confirmed that resonance with electromagnetic waves in the terahertz frequency band was achieved.

[0579] In addition, a COP film with silver layers on both sides is manufactured by the following method.

[0580] After ultrasonically cleaning (45 kHz) the surface of the COP film, a conductive metal nano-ink DryCureAg-J (10% by mass aqueous solution of silver nanoparticles) manufactured by C-INK Co., Ltd. was coated on both sides of the COP film, and then heated at 120°C for 60 minutes to obtain a silver layer.

[0581] <Adhesive Polymers>

[0582] Resins P-100 and P-101, as shown in Table 1, containing structural units derived from each compound, were prepared.

[0583] Table 1 shows the amount (mass%), weight-average molecular weight (Mw), dispersity, and acid value of each structural unit of the synthesized resin.

[0584] The abbreviations are listed in Table 1.

[0585] St: Styrene

[0586] • MAA-GMA: A structural unit formed by adding glycidyl methacrylate to a structural unit derived from methacrylic acid.

[0587] MAA: Methacrylic acid

[0588] • DCPMA: Dicyclopentyl methacrylate

[0589] MMA: Methyl methacrylate

[0590] Furthermore, the repeating unit represented by the above GMA-MAA is represented by the following formula.

[0591] [Chemical Formula 25]

[0592]

[0593] [Table 1]

[0594]

[0595] Synthesis of the capped isocyanate compound Q-1

[0596] Under a nitrogen atmosphere, 453 g of butanone oxime (manufactured by Idemitsu Kosan Co., Ltd.) was dissolved in 700 g of methyl ethyl ketone. Under ice-cold conditions, 500 g of 1,3-bis(methyl isocyanate)cyclohexane (cis, trans isomer mixture, manufactured by Mitsui Chemicals, Inc., Takenate 600) was added dropwise over 1 hour, and the reaction was allowed to proceed for another hour after the addition. The temperature was then raised to 40°C, and the reaction was allowed to continue for another hour. 1 The reaction was confirmed to be complete by 1H-NMR (Nuclear Magnetic Resonance) and HPLC (mgh Performance Liquid Chromatography), yielding a methyl ethyl ketone solution of the capped isocyanate compound Q-1 (refer to the formula below).

[0597] <Synthesis of capped isocyanate compounds Q-2 to Q-4>

[0598] Following the method for synthesizing the terminal isocyanate compound Q-1, methyl ethyl ketone solutions of terminal isocyanate compounds Q-2 to Q-4 (refer to the formula below) were obtained.

[0599] [Table 2]

[0600]

[0601] <Preparation of Curing Compositions>

[0602] Curable compositions A-1 to A-6 with the compositions shown in Table 3 below were prepared. In Table 3, the values ​​of each component represent the content of each component (mass of solid component). Methyl ethyl ketone and 1-methoxy-2-propyl acetate were appropriately added to prepare curable compositions such that the content of methyl ethyl ketone in the solvent was 60% by mass and the concentration of solid component was 25% by mass.

[0603] [Table 3]

[0604]

[0605] Curable composition B-1 with the composition shown in Table 5 below was prepared.

[0606] [Table 4]

[0607]

[0608] Curable composition B-2 with the composition shown in Table 5 below was prepared.

[0609] In addition, the curable composition B-2 is a two-component combination of liquid A and liquid B.

[0610] [Table 5]

[0611]

[0612] <Preparation of transfer films in Examples 1-10 and Comparative Example 1>

[0613] Using a slit nozzle, any one of the curable compositions A-1 to A-6 and B-1 to B-2 was applied to a Lumirror 16KS40 (16 μm thick, manufactured by Toray Industries, Inc., polyethylene terephthalate film) serving as a temporary support. The solvent was then evaporated in a drying zone at 100°C, thereby forming a layer of the curable composition on the temporary support. The amount of curable composition applied was adjusted to achieve the thickness of the organic film as described in Table 6. Next, a protective film (Lumirror 16KS40 (manufactured by Toray Industries, Inc.)) was pressed onto the layer of the curable composition, thus producing the transfer films used in Examples 1-10 and Comparative Example 1.

[0614] The protective film of each transfer film in the examples and comparative examples is peeled off, and the surface of the exposed curable composition layer is brought into contact with the metal pattern of the film with the metal pattern. The film is then laminated (bonded) such that the curable composition layer covers the metal pattern, thereby forming a laminate in which the curable composition layer and the temporary support are disposed on the film with the metal pattern.

[0615] In addition, the above lamination was performed using a vacuum laminator manufactured by MCK Corporation under the conditions of a dielectric film temperature of 40°C, a rubber roller temperature of 100°C, a linear pressure of 3 N / cm, and a conveying speed of 2 m / min.

[0616] Subsequently, using a proximity exposure machine equipped with an ultra-high pressure mercury lamp (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.), the exposure was performed through a temporary support at an exposure dose of 120 mJ / cm². 2 (i-rays) were used for exposure. In addition, the light with a wavelength of 365nm was the dominant wavelength in the exposure light during irradiation.

[0617] Afterwards, a post-baking process at 145°C for 30 minutes was performed, thus forming a laminate.

[0618] However, when using composition B-2, the above-mentioned exposure treatment was not performed, but only a heat treatment was performed at 145°C for 30 minutes.

[0619] In addition, the above treatment was performed using a film in Comparative Example 1 that did not have a curable composition layer formed.

[0620] <Evaluation>

[0621] (Moisture permeability)

[0622] The moisture permeability of the test samples of the organic films of each example and comparative example, which were stacked with 5 layers, was measured using the method described in JIS Z 0208 (under the following conditions: temperature 40°C, relative humidity 90%, for 24 hours).

[0623] More specifically, the water permeability is calculated using the following method.

[0624] First, the samples were prepared using the following method. Transfer films for each example and comparative example were laminated five times onto a commercially available Teflon (registered trademark) mesh (transparent film substrate temperature: 40°C, rubber roller temperature: 110°C, linear pressure: 3 N / cm, conveyor speed: 2 m / min). Then, using a proximity exposure machine with a polyultra-high pressure mercury lamp (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.), the distance between the exposure mask and the temporary support was set to 125 μm, and the exposure dose was 100 mJ / cm through the temporary support. 2 The sample was exposed to i-rays and then heated (and dried) at 150°C for 60 minutes as the measurement sample.

[0625] After the obtained evaluation samples were left to stand at 40°C and 90% relative humidity for 24 hours, the water permeability was determined under the same conditions (40°C and 90% relative humidity) using the method described in JIS Z 0208. The obtained water permeability value was then multiplied by 5 to determine the water permeability of each organic film layer.

[0626] The above operation was performed on five test samples to obtain the water permeability values ​​for each of the five layers. These values ​​were then arithmetically averaged to obtain the water permeability (WVTR) of this invention. The obtained water permeability (WVTR) was evaluated according to the evaluation criteria described later.

[0627] In addition, when using composition B-2, the evaluation sample was manufactured by performing a heat treatment at 145°C for only 30 minutes without performing the above-mentioned exposure treatment.

[0628] A: WVTR is 1000g / (m 2 ·24hr and below

[0629] B: WVTR exceeds 1000g / (m 2 ·24hr) and 2000g / (m 2 ·24hr and below

[0630] C: WVTR exceeds 2000g / (m 2 ·24hr) and 3000g / (m 2 ·24hr and below

[0631] D: WVTR exceeds 3000g / (m 2 ·24hr)

[0632] (Corrosive)

[0633] A 5cm droplet was placed on the surface of the organic film side of the laminate obtained in each embodiment and comparative example. 3 A 50 g / L salt solution is evenly spread to a depth of 50 cm. 2 Afterwards, the moisture was allowed to evaporate at room temperature, and the mixture was then subjected to a HAST test apparatus EHS-221MD (manufactured by ESPEC Corp.) at 110°C and 85% relative humidity for 32 hours. Following this, the salt water was wiped off, and the surface condition of the metallic patterns in the laminate was observed and evaluated according to the following scoring system.

[0634] A, B, and C represent the levels required for practical applications.

[0635] A: There is absolutely no discoloration or roughness of copper or silver.

[0636] B: Slight discoloration or roughness is observed in a portion of the copper or silver.

[0637] C: Slight discoloration or roughness is observed on the entire surface of copper or silver.

[0638] D: Significant discoloration or roughness is observed across the entire surface of the copper or silver.

[0639] In Table 6, the "Membrane" column indicates the type of membrane with a metallic pattern, "1" indicates membrane 1 with a metallic pattern, and "2" indicates membrane 2 with a metallic pattern.

[0640] In Table 6, the "Heterocyclic Compounds" column indicates whether the organic membrane contains heterocyclic compounds. "Yes" means that the organic membrane contains heterocyclic compounds, and "No" means that the organic membrane does not contain heterocyclic compounds.

[0641] In Table 6, the “acid value” column indicates whether the acid value of the polymer contained in the organic membrane is below 20 mg KOH / g. “A” indicates below 20 mg KOH / g, and “B” indicates above 20 mg KOH / g.

[0642] In Table 6, the “Thickness (μm)” column indicates the thickness (μm) of the organic film.

[0643] [Table 6]

[0644]

[0645] As shown in Table 1, the laminate of the present invention exhibits the desired effect.

[0646] By comparing Examples 8 and 9, superior results were obtained when the organic membrane contained heterocyclic compounds.

[0647] By comparing Examples 8 and 10, it was found that when the acid value of the polymer contained in the organic membrane was below 20 mg KOH / g, a better effect was obtained.

[0648] Symbol Explanation

[0649] 10, 20 - laminate, 12, 22 - dielectric film, 14 - metal pattern, 16 - organic film, 18, 18A - metal structure, 24 - first metal pattern, 26 - first organic film, 28 - second metal pattern, 30 - second organic film, 32 - first metal structure, 34 - second metal structure, 40 - photomask, 42 ​​- opening.

Claims

1. A laminated body having: Dielectric film; A metallic pattern disposed on at least one surface side of the dielectric film, serving as a resonator for electromagnetic waves in the terahertz frequency band; and The moisture permeability of the metal pattern disposed thereon, under an environment of 40°C and 90% relative humidity, is 3000 g / (m²). 2 Organic membranes with a lifespan of 24 hours or less, The metal pattern is composed of multiple metal structures. The organic film is formed using a curable composition. The curable composition comprises a capped isocyanate. The curable composition comprises an adhesive polymer having structural units represented by the following formula (S) and structural units represented by the following formula (Cy). In equation (Cy), R M R represents a hydrogen atom or a methyl group. Cy This indicates a monovalent group having an aliphatic hydrocarbon ring structure.

2. The laminated body according to claim 1, wherein, The organic membrane contains heterocyclic compounds.

3. The laminate according to claim 1 or 2, wherein, The organic membrane contains a polymer with an acid value of less than 20 mg KOH / g.

4. A laminated body having: Dielectric film; A first metal pattern, consisting of a plurality of first metal structures, disposed on one surface side of the dielectric film; The moisture permeability of the material disposed on the first metal pattern at an environment of 40°C and 90% relative humidity is 3000 g / (m²). 2 The first organic membrane (within 24 hours); A second metal pattern, composed of a plurality of second metal structures, disposed on the other surface side of the dielectric film; and The moisture permeability of the material disposed on the second metal pattern is 3000 g / (m²) in an environment with a temperature of 40°C and a relative humidity of 90%. 2 The second organic membrane (within 24 hours) The first metal pattern and the second metal pattern constitute a resonator for electromagnetic waves in the terahertz frequency band. The first organic film and the second organic film are formed using a curable composition. The curable composition comprises a capped isocyanate. The curable composition comprises an adhesive polymer having structural units represented by the following formula (S) and structural units represented by the following formula (Cy). In equation (Cy), R M R represents a hydrogen atom or a methyl group. Cy This indicates a monovalent group having an aliphatic hydrocarbon ring structure.

5. The laminated body according to claim 4, wherein, When viewed from above, the first metal structure contained in the first metal pattern and the second metal structure contained in the second metal pattern are arranged in a manner that at least partially overlaps.

6. The laminate according to claim 4 or 5, wherein, The first organic membrane and the second organic membrane contain heterocyclic compounds.

7. The laminate according to claim 4 or 5, wherein, The first organic membrane and the second organic membrane contain polymers with an acid value of less than 20 mg KOH / g.

8. An optical element comprising a laminate according to any one of claims 1 to 7.

9. A method for manufacturing a laminate, comprising: Step 1A involves bonding a metal-patterned film, which includes a dielectric film and a metal pattern disposed on at least one surface side of the dielectric film to serve as a resonator for electromagnetic waves in the terahertz frequency band, to a transfer film containing a temporary support and a curable composition layer, thereby forming a precursor film having the dielectric film, the metal pattern, the curable composition layer, and the temporary support in sequence. and Step 2A involves curing the curable composition layer to obtain a moisture permeability of 3000 g / (m²) at an environment of 40°C and 90% relative humidity. 2 Organic membranes with a lifespan of 24 hours or less, Furthermore, it includes a step of peeling off the temporary support between step 1A and step 2A, or after step 2A. The metal pattern is composed of multiple metal structures. The curable composition layer comprises a capped isocyanate. The curable composition layer comprises an adhesive polymer having structural units represented by the following formula (S) and structural units represented by the following formula (Cy). In equation (Cy), R M R represents a hydrogen atom or a methyl group. Cy This indicates a monovalent group having an aliphatic hydrocarbon ring structure.

10. The method for manufacturing a laminate according to claim 9, wherein, The organic membrane contains heterocyclic compounds.

11. The method for manufacturing a laminate according to claim 9 or 10, wherein, The organic membrane contains a polymer with an acid value of less than 20 mg KOH / g.

12. A method for manufacturing a laminate, comprising: Step 1B involves bonding a metal-patterned film to a transfer film comprising a temporary support and a curable composition layer. The metal-patterned film comprises a dielectric film, a first metal pattern disposed on one surface of the dielectric film and composed of a plurality of first metal structures, and a second metal pattern disposed on the other surface of the dielectric film and composed of a plurality of second metal structures. The first metal pattern and the second metal pattern constitute a resonator for electromagnetic waves in the terahertz frequency band, thereby forming a precursor film having the temporary support, the curable composition layer, the first metal pattern, the dielectric film, the second metal pattern, the curable composition layer, and the temporary support in sequence. and Step 2B involves curing the curable composition layer to obtain a moisture permeability of 3000 g / (m²) at an environment of 40°C and 90% relative humidity. 2 Organic membranes with a lifespan of 24 hours or less, Furthermore, it includes a step 3B, between step 1B and step 2B, or after step 2B, of peeling off the temporary support. The curable composition layer comprises a capped isocyanate. The curable composition layer comprises an adhesive polymer having structural units represented by the following formula (S) and structural units represented by the following formula (Cy). In equation (Cy), R M R represents a hydrogen atom or a methyl group. Cy This indicates a monovalent group having an aliphatic hydrocarbon ring structure.

13. The method for manufacturing a laminate according to claim 12, wherein, When viewed from above, the first metal structure contained in the first metal pattern and the second metal structure contained in the second metal pattern are arranged in a manner that at least partially overlaps.

14. The method for manufacturing a laminate according to claim 12 or 13, wherein, The organic membrane contains heterocyclic compounds.

15. The method for manufacturing a laminate according to claim 12 or 13, wherein, The organic membrane contains a polymer with an acid value of less than 20 mg KOH / g.

Images