WO2023042737A1 - 積層体、積層体の製造方法 - Google Patents
積層体、積層体の製造方法 Download PDFInfo
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- WO2023042737A1 WO2023042737A1 PCT/JP2022/033671 JP2022033671W WO2023042737A1 WO 2023042737 A1 WO2023042737 A1 WO 2023042737A1 JP 2022033671 W JP2022033671 W JP 2022033671W WO 2023042737 A1 WO2023042737 A1 WO 2023042737A1
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- metal pattern
- film
- curable composition
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- composition layer
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Images
Classifications
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/002—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of materials engineered to provide properties not available in nature, e.g. metamaterials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/10—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material
- B32B3/18—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material characterised by an internal layer formed of separate pieces of material which are juxtaposed side-by-side
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
- C08K5/3447—Five-membered rings condensed with carbocyclic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01P—WAVEGUIDES; RESONATORS, LINES, OR OTHER DEVICES OF THE WAVEGUIDE TYPE
- H01P11/00—Apparatus or processes specially adapted for manufacturing waveguides or resonators, lines, or other devices of the waveguide type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q15/00—Devices for reflection, refraction, diffraction or polarisation of waves radiated from an antenna, e.g. quasi-optical devices
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
Definitions
- the present invention relates to a laminate and a method for manufacturing the laminate.
- Metamaterials are made by artificially arranging aggregates of microstructures smaller than the wavelength of electromagnetic waves, and by utilizing the characteristic optical response exhibited by these aggregates of microstructures, effective refractive index changes can be achieved. can be induced. If such a metamaterial can be formed on a film with a thickness on the order of microns, it can be applied to optical elements for terahertz waves (electromagnetic waves with a frequency of 0.1 to 10 THz (wavelength of 30 to 3000 ⁇ m)).
- Patent Literature 1 a film-shaped dielectric substrate, a first wire array formed of a metal first cut wire formed on one surface of the dielectric substrate, and a wire array formed on the other surface of the dielectric substrate
- a sheet-type metamaterial has been proposed that includes a second wire array composed of second cut wires made of metal.
- the inventors of the present invention have studied the properties of the sheet-type metamaterial described in Patent Document 1, and found that the metal cut wires constituting the wire array arranged on the dielectric substrate are susceptible to corrosion. . When such corrosion occurs, the effective refractive index changes, and as a result, the function as a metamaterial may deteriorate.
- An object of the present invention is to provide a laminate that can suppress corrosion of a metal pattern serving as a resonator against electromagnetic waves in the terahertz band. Moreover, this invention also makes it a subject to provide the manufacturing method of a laminated body.
- a dielectric film a dielectric film; a metal pattern arranged on at least one surface side of the dielectric film and serving as a resonator for electromagnetic waves in the terahertz band; and an organic film having a moisture permeability of 3000 g/(m 2 ⁇ 24 hr) or less in an environment of a temperature of 40° C. and a relative humidity of 90%, arranged on the metal pattern.
- the organic film contains a heterocyclic compound.
- the organic film contains a polymer having an acid value of 20 mgKOH/g or less.
- an organic film is formed using a curable composition; The laminate according to any one of (1) to (3), wherein the curable composition contains a blocked isocyanate.
- a dielectric film a dielectric film; a first metal pattern composed of a plurality of first metal structures arranged on one surface side of the dielectric film; a first organic film having a moisture permeability of 3000 g/(m 2 ⁇ 24 hr) or less in an environment of a temperature of 40° C.
- a second metal pattern composed of a plurality of second metal structures arranged on the other surface side of the dielectric film; a second organic film arranged on the second metal pattern and having a moisture permeability of 3000 g/(m 2 24 hr) or less in an environment of a temperature of 40° C. and a relative humidity of 90%;
- the first metal structure included in the first metal pattern and the second metal structure included in the second metal pattern are arranged so as to at least partially overlap when the laminate is viewed in plan.
- the first organic film and the second organic film are formed using a curable composition;
- An optical element comprising the laminate according to any one of (1) to (9).
- Step 1A of forming a precursor film having a dielectric film, a metal pattern, a curable composition layer, and a temporary support in this order by laminating a transfer film containing a composition layer; and a step 2A of subjecting the curable composition layer to a curing treatment to obtain an organic film having a moisture permeability of 3000 g/(m 2 ⁇ 24 hr) or less in an environment of a temperature of 40°C and a relative humidity of 90%.
- a method for producing a laminate further comprising a step of peeling off the temporary support between step 1A and step 2A or after step 2A.
- (12) The method for producing a laminate according to (11), wherein the organic film contains a heterocyclic compound.
- (14) The method for producing a laminate according to any one of (11) to (13), wherein the curable composition layer contains blocked isocyanate.
- a method for producing a laminate further comprising step 3B of peeling off the temporary support between step 1B and step 2B or after step 2B.
- the first metal structures included in the first metal pattern and the second metal structures included in the second metal pattern overlap at least partially when the metal patterned film is viewed in plan.
- a numerical range represented by "to” means a range including the numerical values before and after “to” as lower and upper limits.
- the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of the numerical range described in other steps.
- the upper limit or lower limit described in a certain numerical range may be replaced with the values shown in the examples.
- process is not only an independent process, but even if it cannot be clearly distinguished from other processes, it is included in this term as long as the intended purpose of the process is achieved. .
- the weight average molecular weight (Mw) and number average molecular weight (Mn) are measured using TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all trade names manufactured by Tosoh Corporation). ), using THF (tetrahydrofuran) as an eluent, a differential refractometer as a detector, and polystyrene as a standard substance, a value converted using polystyrene as a standard substance measured by a gel permeation chromatography (GPC) analyzer.
- GPC gel permeation chromatography
- the molecular weight of a compound having a molecular weight distribution is the weight average molecular weight (Mw).
- Mw weight average molecular weight
- the hue is a value measured using a color difference meter (CR-221, manufactured by Minolta Co., Ltd.).
- (meth)acryl is a concept that includes both acryl and methacryl
- (meth)acryloxy group is a concept that includes both acryloxy and methacryloxy groups.
- alkali-soluble means that the solubility in 100 g of a 1% by mass aqueous solution of sodium carbonate at 22°C is 0.1 g or more.
- water-soluble means that the solubility in 100 g of water at pH 7.0 at a liquid temperature of 22°C is 0.1 g or more.
- water-soluble resin is intended a resin that satisfies the solubility conditions set forth above.
- the “solid content” of the composition means a component that forms a composition layer formed using the composition, and when the composition contains a solvent (organic solvent, water, etc.), the solvent means all ingredients except In addition, as long as it is a component that forms a composition layer, a liquid component is also regarded as a solid content.
- a solvent organic solvent, water, etc.
- a feature of the laminate of the present invention is that it uses an organic film exhibiting a predetermined moisture permeability.
- the present inventors discovered for the first time that corrosion of a metal pattern consisting of a plurality of metal structures that function as a metamaterial occurs, and by using an organic film with a predetermined moisture permeability to suppress the corrosion, , found that corrosion of metal patterns can be suppressed.
- a first embodiment of the laminate of the present invention will be described with reference to the drawings.
- a laminate 10A shown in FIG. 1 has a dielectric film 12, a metal pattern 14, and an organic film 16 in this order.
- the metal pattern 14 is composed of a plurality of metal structures 18 .
- the plurality of metal structures 18 forming the metal pattern 14 can function as a resonator for electromagnetic waves in the terahertz band.
- Each member constituting the laminate will be described in detail below.
- a known dielectric film can be used as the dielectric film.
- the dielectric film is preferably an insulator that does not conduct electricity with respect to a DC voltage.
- the material constituting the dielectric film is not particularly limited, but a resin is preferable from the viewpoint of handleability and the like. In other words, the dielectric resin film is preferable as the dielectric film.
- 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), and cycloolefin polymers.
- polyolefins such as (COP) and cycloolefin copolymers (COC), vinyl resins, polycarbonates (PC), polyamides, polyimides, acrylic resins, and triacetyl cellulose (TAC).
- the cycloolefin polymer includes cycloolefin polymers described in paragraphs 0052 to 0071 of Japanese Patent No. 4991170.
- the thickness of the dielectric film is not particularly limited, it is preferably 5 to 100 ⁇ m, more preferably 10 to 80 ⁇ m, even more preferably 15 to 50 ⁇ m. When the thickness of the dielectric film is 5 ⁇ m or more, the handleability is excellent. In addition, it is preferable that the variation of the thickness of the dielectric film in the in-plane direction is within 1 ⁇ m.
- the transmittance of the dielectric film to terahertz waves is not particularly limited, it is preferably 75% or higher, more preferably 85% or higher, and even more preferably 95% or higher.
- the dielectric film may have a single layer structure or a multilayer structure.
- the metal pattern serves as a resonator for electromagnetic waves in the terahertz band (electromagnetic waves with a frequency of 0.1 to 10 THz (wavelength of 30 to 3000 ⁇ m)). More specifically, the metal pattern is composed of a plurality of metal structures, and the metal structures serve as resonators for electromagnetic waves in the terahertz band.
- the shape and size of the metal structure are not particularly limited, but when a terahertz-band electromagnetic wave is incident on the laminate, an electric charge is generated within the metal structure or between adjacent metal structures due to the interaction of the incident electromagnetic wave with an electric field or a magnetic field. It is preferable that the size is equal to or less than the wavelength of the incident electromagnetic wave, and has a shape that induces a dielectric or magnetic response change due to bias or current generation.
- Such metal patterns can function as so-called metamaterials.
- the shape of the metal structure is not particularly limited, and may be C-shaped, U-shaped, double ring-shaped, V-shaped, L-shaped, lattice-shaped, spiral-shaped, square-shaped, circular-shaped, cross-shaped, or the like. More specifically, for example, FIG. 2 exemplifies a mode in which a plurality of C-shaped metal structures 18A are arranged on the dielectric film 12 .
- the type of metal that constitutes the metal structure is not particularly limited, and is preferably gold, silver, platinum, copper, aluminum, or an alloy containing one or more of these, more preferably silver or copper.
- the size of the metal structure is not particularly limited as long as it resonates with electromagnetic waves in the terahertz band, but the maximum length of the metal structure is preferably 1 to 3000 ⁇ m, more preferably 5 to 1000 ⁇ m.
- the maximum length of the metal structure is the longest length when a straight line is drawn from one end to the other end of the metal structure.
- the arrangement position of the metal structure on the dielectric film is not particularly limited as long as the arrangement resonates with electromagnetic waves in the terahertz band. Further, when applying the laminate as a sheet-type collimating lens for electromagnetic waves in the terahertz band, in the in-plane direction of the dielectric film, the refractive index difference is 2 times or more for the electromagnetic waves in the terahertz band. It is preferred to arrange the metal structures such that a modulus distribution occurs. Further, the metal structure is arranged on the dielectric film so as to form a periodic structure in which the phase shift amount of the terahertz band electromagnetic wave continuously increases or decreases from the center of the laminate toward the outer region. You may When arranging the metal structures in this manner, the metal structures may be arranged in three or more concentrically arranged regions from the center of the laminate. At that time, the variation width of the diameter of each concentric circle is preferably 10 to 200 ⁇ m.
- FIG. 1 shows a mode in which the metal pattern is arranged only on one surface side of the dielectric film
- the present invention is not limited to this mode, and the metal pattern is arranged on both sides of the dielectric film. good too.
- the organic film has a role of preventing corrosion of the metal pattern as described above.
- An organic film is disposed on the metal pattern so as to cover the metal pattern.
- the organic film is a film having a moisture permeability (water vapor permeability) of 3000 g/(m 2 ⁇ 24 hr) or less in an environment of 40° C. temperature and 90% relative humidity.
- the moisture permeability is preferably 2000 g/(m 2 ⁇ 24 hr) or less, and 1000 g/( m 2 ⁇ 24 hr) or less is more preferable.
- the method for measuring the moisture permeability is as follows. A measurement sample in which five layers of organic films are laminated is prepared, and the measurement conditions are a temperature of 40 ° C. and a relative humidity of 90%. , to measure moisture permeability. The obtained measured value is multiplied by 5 to calculate the moisture permeability per layer. The above operation is performed on five measurement samples to obtain the values of water vapor permeability per five layers, and these numerical values are arithmetically averaged to obtain the water vapor permeability of the present invention.
- a transfer film containing a curable composition layer that can be an organic film is used and cured.
- a method of laminating the organic film five times and curing the resulting laminate to prepare a measurement sample in which five layers of organic films are laminated is exemplified.
- the thickness of the organic film is not particularly limited, and is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less in terms of not impairing electromagnetic wave transmission characteristics. Although the lower limit is not particularly limited, it is often 0.5 ⁇ m or more.
- the material contained in the organic film is not particularly limited, it preferably contains a polymer.
- polymers include saturated or unsaturated polyester resins, (meth)acrylic resins, acrylic urethane resins, polyester acrylate resins, polyurethane acrylate resins, epoxy acrylate resins, urethane resins, epoxy resins, vinyl resins, polycarbonate resins, and cellulose resins. , acetal resins, polyethylene resins, polystyrene resins, polyamide resins, polyimide resins, melamine resins, phenolic resins, and silicone resins.
- Examples of the polymer that may be contained in the organic film include a binder polymer that may be contained in the curable composition layer described later, and a polymer of a polymerizable compound that will be described in detail later. Described in When the organic film is formed using a curable composition layer described later, if the polymer contained in the curable composition layer contains a reactive group, the reactant of the polymer is contained in the organic film. Become.
- the polymer contained in the organic film may or may not have an acid group, but when the polymer has an acid group, the acid value of the polymer is not particularly limited, and is preferably 1000 mgKOH/g or less, and 200 mgKOH/g or less. is more preferred, and 20 mgKOH/g or less is even more preferred.
- the lower limit is not particularly limited, and is often greater than 0 mgKOH/g.
- the acid value of the polymer is a value measured according to the method described in JIS K0070:1992.
- the polymer content is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 30 to 70% by mass, relative to the total mass of the organic film.
- the organic film preferably contains a heterocyclic compound.
- a heterocyclic compound By including the heterocyclic compound in the organic film, corrosion of the metal pattern is further prevented.
- the heterocyclic compound that may be contained in the organic film include heterocyclic compounds that may be contained in the curable composition layer described later, and details thereof will be described later.
- the organic film may contain a single heterocyclic compound, or may contain two or more heterocyclic compounds.
- the content of the heterocyclic compound is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, relative to the total mass of the organic film.
- the organic film may contain components other than the above-described polymers and heterocyclic compounds (for example, surfactants, etc.).
- the laminate may include other structures than dielectric films, metal patterns, and organic films. Further, a metal pattern and an organic film may be repeatedly laminated on the organic film.
- the method for manufacturing the laminate described above is not particularly limited, and it can be manufactured by a known method.
- a dielectric film and a metal patterned film containing a metal pattern that serves as a resonator for electromagnetic waves in the terahertz band disposed on at least one surface side of the dielectric film (hereinafter simply referred to as "metal patterned film A”.)
- method of laminating a predetermined organic film on the metal pattern a curable composition is applied on the film A with the metal pattern, and if necessary, a curing treatment is performed to form the organic film.
- a method using a transfer film comprising a curable composition layer containing a temporary support and predetermined components.
- a film A with a metal pattern and a transfer film containing a temporary support and a curable composition layer are laminated to form a dielectric film, a metal pattern, a curable composition layer, and Step 1A of forming a precursor film having a temporary support in this order, and Step 2A of subjecting the curable composition layer to a curing treatment to obtain the above-described organic film, wherein Step 1A and Step 2A are combined.
- Step 2A a method further comprising a step 3A of peeling off the temporary support is preferable.
- the method using the transfer film will be described in detail below. The structure of the transfer film itself will be described later in detail.
- a dielectric film and a metal-patterned film A containing a metal pattern that serves as a resonator for electromagnetic waves in the terahertz band disposed on at least one surface side of the dielectric film are used. be done.
- the configuration of the metal pattern contained in the metal patterned film A is the same as the configuration of the metal pattern in the laminate described above.
- the method for producing the metal patterned film A is not particularly limited, and a metal layer is formed on a dielectric film, a predetermined resist pattern is arranged on the metal layer, and a metal layer not covered with the resist pattern is formed.
- a film with a metal pattern can be produced by removing by etching and peeling off the resist pattern.
- Step 1A a metal patterned film A and a transfer film containing a temporary support and a curable composition layer are laminated to form a dielectric film, a metal pattern, a curable composition layer, and a temporary support. It is the process of forming the precursor film which has in this order.
- the exposed curable composition layer on the temporary support of the transfer film is brought into contact with the film A with the metal pattern and bonded together.
- the curable composition layer and the temporary support are arranged on the film A with the metal pattern.
- the metal pattern and the surface of the curable composition layer are pressure-bonded so that they are in contact with each other.
- transfer methods and lamination methods can be used.
- a known laminator such as a vacuum laminator and an autocut laminator can be used for bonding.
- Step 2A is a step of curing the curable composition layer to obtain an organic film.
- the curing treatment is appropriately selected depending on the curable composition used, heat treatment is selected when the curable composition is a thermosetting composition, and the curable composition is a photocurable composition. In the case of , exposure processing is mentioned. Also, the exposure treatment and the heat treatment may be performed sequentially or simultaneously.
- the conditions for the heat treatment are not particularly limited, and the heating temperature is preferably 100 to 200°C, more preferably 110 to 180°C, and even more preferably 120 to 170°C.
- the heating time is preferably 0.05 to 5 hours, more preferably 0.08 to 3 hours, even more preferably 0.1 to 1 hour.
- the exposure process may be in the form of patternwise exposure.
- the light source for exposure can be appropriately selected and used as long as it can irradiate at least light in a wavelength range capable of curing the curable composition (for example, 365 nm or 405 nm).
- the dominant wavelength of exposure light for exposure is preferably 365 nm. Note that the dominant wavelength is the wavelength with the highest intensity.
- Examples of light sources include various lasers, light emitting diodes (LEDs), ultrahigh pressure mercury lamps, high pressure mercury lamps, and metal halide lamps.
- the exposure amount is preferably 5-200 mJ/cm 2 , more preferably 10-200 mJ/cm 2 .
- Step 3A is a step of peeling off the temporary support between Step 1A and Step 2A or after Step 2A.
- the peeling method is not particularly limited, and a mechanism similar to the cover film peeling mechanism described in paragraphs [0161] to [0162] of JP-A-2010-072589 can be used.
- a development step may be carried out when the pattern exposure is performed in the curing step.
- the development step is a step of developing the exposed curable composition layer to form a pattern.
- Development of the curable composition layer can be performed using a developer.
- a developer an alkaline aqueous solution is preferred.
- Alkaline compounds that can be contained in the alkaline aqueous solution include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).
- Development methods include, for example, puddle development, shower development, spin development, and dip development.
- Examples of the developer preferably used in the present disclosure include the developer described in paragraph [0194] of International Publication No. WO 2015/093271. /093271, paragraph [0195].
- the pattern (cured film of the curable composition layer) formed by the above procedure is preferably achromatic.
- the a * value of the pattern is preferably ⁇ 1.0 to 1.0
- the b * value of the pattern is ⁇ 1.0 to 1.0. .0 is preferred.
- the pattern obtained by the developing step may be exposed (post-exposure step) and/or heated (post-baking step).
- post-exposure step a post-exposure step and a post-bake step are included, post-baking is preferably performed after post-exposure.
- the transfer film has a temporary support and a curable composition layer disposed on the temporary support. By curing this curable composition layer, the above-described organic film is formed. Below, first, the configuration of the transfer film will be described in detail.
- the temporary support is a member that supports the curable composition layer, which will be described later, and is finally removed by a peeling treatment.
- the temporary support is preferably a film, more preferably a resin film.
- a film that is flexible and does not undergo significant deformation, shrinkage, or elongation under pressure or under pressure and heat can be used.
- Such films include polyethylene terephthalate films (eg, biaxially oriented polyethylene terephthalate films), cellulose triacetate films, polystyrene films, polyimide films, and polycarbonate films.
- a biaxially stretched polyethylene terephthalate film is preferable as the temporary support.
- the film used as the temporary support does not have deformation such as wrinkles, scratches, or the like.
- the temporary support preferably has high transparency because it can be exposed through the temporary support, and the transmittance at 365 nm is preferably 60% or more, more preferably 70% or more. From the viewpoint of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, it is preferable that the haze of the temporary support is small. 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. From the viewpoint of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, it is preferable that the number of fine particles, foreign matters and defects contained in the temporary support is small.
- the number of fine particles, foreign substances, and defects with a diameter of 1 ⁇ m or more is preferably 50/10 mm 2 or less, more preferably 10/10 mm 2 or less, still more preferably 3/10 mm 2 or less, and particularly preferably 0/10 mm 2 . .
- the thickness of the temporary support is not particularly limited, it is preferably 5 to 200 ⁇ m, more preferably 10 to 150 ⁇ m, still more preferably 10 to 50 ⁇ m from the viewpoint of ease of handling and versatility.
- a layer containing fine particles may be provided on the surface of the temporary support in order to impart handleability.
- the lubricant layer may be provided on one side or both sides of the temporary support.
- the particles contained in the lubricant layer can have a diameter of 0.05 to 0.8 ⁇ m.
- the film thickness of the lubricant layer can be 0.05 to 1.0 ⁇ m.
- Examples of the temporary support include a biaxially stretched polyethylene terephthalate film with a thickness of 16 ⁇ m, a biaxially stretched polyethylene terephthalate film with a thickness of 12 ⁇ m, and a biaxially stretched polyethylene terephthalate film with a thickness of 9 ⁇ m.
- Preferred forms of the temporary support include, for example, paragraphs [0017] to [0018] of JP-A-2014-085643, paragraphs [0019] to [0026] of JP-A-2016-027363, International Publication No. 2012/ No. 081680, paragraphs [0041] to [0057], and WO 2018/179370, paragraphs [0029] to [0040], the contents of these publications are incorporated herein.
- the transfer film has a curable composition layer. After the curable composition layer is transferred onto the metal pattern, the above organic film can be formed by performing a curing treatment.
- the curable composition layer may be a thermosetting composition layer or a photocurable composition layer. The components contained in the curable composition layer are described in detail below.
- the curable composition layer may contain a binder polymer.
- a binder polymer is a (meth)acrylic resin because of its excellent alkali developability and film formability.
- the (meth)acrylic resin means a resin having a structural unit derived from a (meth)acrylic compound.
- the content of structural units derived from the (meth)acrylic compound is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more, based on all the structural units of the (meth)acrylic resin. .
- the (meth)acrylic resin may be composed only of structural units derived from the (meth)acrylic compound, or may have structural units derived from polymerizable monomers other than the (meth)acrylic compound. . That is, the upper limit of the content of structural units derived from the (meth)acrylic compound is 100% by mass or less with respect to all structural units of the (meth)acrylic resin.
- (Meth)acrylic compounds include, for example, (meth)acrylic acid, (meth)acrylic acid esters, (meth)acrylamides, and (meth)acrylonitrile.
- (meth)acrylic acid esters include (meth)acrylic acid alkyl ester, (meth)acrylic acid tetrahydrofurfuryl ester, (meth)acrylic acid dimethylaminoethyl ester, (meth)acrylic acid diethylaminoethyl ester, (meth) ) acrylic acid glycidyl ester, (meth)acrylic acid benzyl ester, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate, ( Meth)acrylic acid alkyl esters are preferred.
- (Meth)acrylamides include, for example, acrylamides such as diacetone acrylamide.
- the alkyl group of the (meth)acrylic acid alkyl ester may be linear or branched. Specific examples include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, ( meth)heptyl acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, and (meth)acrylic Examples thereof include (meth)acrylic acid alkyl esters having an alkyl group having 1 to 12 carbon atoms such as dodecyl acid.
- an alkyl (meth)acrylic acid ester having an alkyl group having 1 to 4 carbon atoms is preferable, and methyl (meth)acrylate or ethyl (meth)acrylate is more preferable.
- the (meth)acrylic resin may have a structural unit other than the structural unit derived from the (meth)acrylic compound.
- the polymerizable monomer forming the structural unit is not particularly limited as long as it is a compound other than the (meth)acrylic compound copolymerizable with the (meth)acrylic compound.
- Examples include styrene, vinyl toluene, and ⁇ - Styrene compounds optionally having a substituent at the ⁇ -position or aromatic ring such as methylstyrene, vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether, maleic acid, maleic anhydride, monomethyl maleate, maleic acid Maleic acid monoesters such as monoethyl and monoisopropyl maleate, fumaric acid, cinnamic acid, ⁇ -cyanocinnamic acid, itaconic acid, and crotonic acid. These polymerizable monomers may be used singly or in combination of two or more.
- the (meth)acrylic resin preferably has a constitutional unit having an acid group from the viewpoint of improving alkali developability.
- Acid groups include, for example, carboxy groups, sulfo groups, phosphoric acid groups, and phosphonic acid groups.
- the (meth)acrylic resin more preferably has a structural unit having a carboxy group, and more preferably has a structural unit derived from the above (meth)acrylic acid.
- the content of the structural unit having an acid group (preferably a structural unit derived from (meth)acrylic acid) in the (meth)acrylic resin is excellent in developability, relative to the total mass of the (meth)acrylic resin, 10 mass % or more is preferable.
- the upper limit is not particularly limited, it is preferably 50% by mass or less, more preferably 40% by mass or less, from the viewpoint of excellent alkali resistance.
- the (meth)acrylic resin more preferably has structural units derived from the (meth)acrylic acid alkyl ester described above.
- the content of structural units derived from (meth)acrylic acid alkyl ester in the (meth)acrylic resin is 1 to 90% by mass is preferable, 1 to 50% by mass is more preferable, and 1 to 30% by mass is even more preferable.
- the (meth)acrylic resin a resin having both a structural unit derived from (meth)acrylic acid and a structural unit derived from a (meth)acrylic acid alkyl ester is preferable, and a structural unit derived from (meth)acrylic acid and A resin composed only of structural units derived from a (meth)acrylic acid alkyl ester is more preferable.
- an acrylic resin having a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from ethyl acrylate is also preferable.
- the (meth)acrylic resin may have at least one selected from the group consisting of a structural unit derived from methacrylic acid and a structural unit derived from a methacrylic acid alkyl ester, from the viewpoint that the effects of the present invention are more excellent.
- it has both a structural unit derived from methacrylic acid and a structural unit derived from a methacrylic acid alkyl ester.
- the total content of structural units derived from methacrylic acid and structural units derived from methacrylic acid alkyl esters in the (meth)acrylic resin is 40% by mass or more is preferable, and 60% by mass or more is more preferable.
- the upper limit is not particularly limited, and may be 100% by mass or less, preferably 80% by mass or less.
- the (meth)acrylic resin has at least one selected from the group consisting of structural units derived from methacrylic acid and structural units derived from methacrylic acid alkyl esters, and acrylic acid It is also preferable to have at least one selected from the group consisting of structural units derived from and structural units derived from acrylic acid alkyl esters. From the point of view that the effect of the present invention is more excellent, the total content of the structural units derived from methacrylic acid and the structural units derived from the methacrylic acid alkyl ester is is preferably 60/40 to 80/20 in mass ratio with respect to the total content of
- the (meth)acrylic resin preferably has an ester group at its terminal from the viewpoint of excellent developability of the curable composition layer after transfer.
- the terminal portion of the (meth)acrylic resin is composed of a site derived from the polymerization initiator used in the synthesis.
- a (meth)acrylic resin having an ester group at its terminal can be synthesized by using a polymerization initiator that generates a radical having an ester group.
- the binder polymer is preferably a binder polymer having an acid value of 60 mgKOH/g or more, for example, from the viewpoint of developability.
- the binder polymer is, for example, a resin having a carboxy group with an acid value of 60 mgKOH/g or more (so-called carboxy group-containing resin) because it thermally crosslinks with a cross-linking component by heating and easily forms a strong film. More preferably, it is a (meth)acrylic resin having a carboxy group with an acid value of 60 mgKOH/g or more (so-called carboxy group-containing (meth)acrylic resin).
- the binder polymer is a resin having a carboxyl group
- a thermally crosslinkable compound such as a blocked isocyanate compound and thermally crosslinking
- the three-dimensional crosslinking density can be increased.
- the carboxy group of the resin having a carboxy group is dehydrated and hydrophobized, the wet heat resistance can be improved.
- the carboxy group-containing (meth)acrylic resin having an acid value of 60 mgKOH/g or more is not particularly limited as long as it satisfies the acid value conditions described above, and can be appropriately selected from known (meth)acrylic resins.
- a carboxy group-containing acrylic resin having an acid value of 60 mgKOH/g or more paragraphs [0033] to [0052] of JP-A-2010-237589
- carboxy group-containing acrylic resins having an acid value of 60 mgKOH/g or more can be preferably used.
- the binder polymer is a styrene-acrylic copolymer.
- the styrene-acrylic copolymer refers to a resin having a structural unit derived from a styrene compound and a structural unit derived from a (meth)acrylic compound, and a structural unit derived from the styrene compound.
- the total content of structural units derived from the (meth)acrylic compound is preferably 30% by mass or more, more preferably 50% by mass or more, based on all the structural units of the copolymer.
- the content of structural units derived from a styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 5 to 80% by mass, based on all the structural units of the copolymer. Further, the content of the structural unit derived from the (meth)acrylic compound is preferably 5% by mass or more, more preferably 10% by mass or more, and 20 to 95% by mass, based on the total structural units of the copolymer. is more preferred.
- the binder polymer preferably has an aromatic ring structure, and more preferably has a structural unit having an aromatic ring structure, from the viewpoint that the effects of the present invention are more excellent.
- Monomers that form structural units having an aromatic ring structure include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid , styrene dimers, and styrene trimers).
- a monomer having an aralkyl group or styrene is preferable.
- Aralkyl groups include substituted or unsubstituted phenylalkyl groups (excluding benzyl groups), substituted or unsubstituted benzyl groups, and the like, with substituted or unsubstituted benzyl groups being preferred.
- Examples of monomers having a phenylalkyl group include phenylethyl (meth)acrylate.
- Examples of monomers having a benzyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate; vinyl monomers having a benzyl group, such as vinylbenzyl chloride, and vinyl benzyl alcohol and the like. Among them, benzyl (meth)acrylate is preferred.
- the binder polymer more preferably has a structural unit (a structural unit derived from styrene) represented by the following formula (S), from the viewpoint that the effect of the present invention is more excellent.
- the content of the structural unit having an aromatic ring structure is 5 to 90 mass with respect to all structural units of the binder polymer, from the viewpoint that the effects of the present invention are more excellent. %, more preferably 10 to 70% by mass, even more preferably 20 to 60% by mass. Further, the content of structural units having an aromatic ring structure in the binder polymer is preferably 5 to 70 mol%, preferably 10 to 60 mol%, based on the total structural units of the binder polymer, from the viewpoint that the effects of the present invention are more excellent. is more preferred, and 20 to 60 mol % is even more preferred.
- the content of the structural unit represented by the above formula (S) in the binder polymer is preferably 5 to 70 mol%, based on the total structural units of the binder polymer, from the viewpoint that the effect of the present invention is more excellent, and 10 ⁇ 60 mol% is more preferred, 20 to 60 mol% is even more preferred, and 20 to 50 mol% is particularly preferred.
- the above-mentioned "structural unit” shall be synonymous with the "monomer unit”.
- the above-mentioned "monomer unit” may be modified after polymerization by a polymer reaction or the like. The same applies to the following.
- the binder polymer preferably has an aliphatic hydrocarbon ring structure from the viewpoint that the effects of the present invention are more excellent. That is, the binder polymer preferably has structural units having an aliphatic hydrocarbon ring structure.
- the aliphatic hydrocarbon ring structure may be monocyclic or polycyclic.
- the binder polymer more preferably has a ring structure in which two or more aliphatic hydrocarbon rings are condensed.
- rings constituting the aliphatic hydrocarbon ring structure in the constituent unit having the aliphatic hydrocarbon ring structure include tricyclodecane ring, cyclohexane ring, cyclopentane ring, norbornane ring, and isoboron ring. Among them, a ring obtained by condensing two or more aliphatic hydrocarbon rings is preferable, and a tetrahydrodicyclopentadiene ring (tricyclo[5.2.1.0 2,6 ]decane ring) is more preferred.
- Monomers that form structural units having an aliphatic hydrocarbon ring structure include dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate.
- the binder polymer preferably has a structural unit represented by the following formula (Cy) from the viewpoint of more excellent effects of the present invention. It is more preferable to have a structural unit represented by Cy).
- RM represents a hydrogen atom or a methyl group
- R Cy represents a monovalent group having an aliphatic hydrocarbon ring structure
- RM in formula (Cy) is preferably a methyl group.
- R Cy in the formula (Cy) is preferably a monovalent group having an aliphatic hydrocarbon ring structure with 5 to 20 carbon atoms from the viewpoint of better effects of the present invention, and an aliphatic A monovalent group having an aliphatic hydrocarbon ring structure is more preferred, and a monovalent group having an aliphatic hydrocarbon ring structure having 8 to 14 carbon atoms is even more preferred.
- the aliphatic hydrocarbon ring structure in R Cy of formula (Cy) is a cyclopentane ring structure, a cyclohexane ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornane ring structure, or An isoboron ring structure is preferred, a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure is more preferred, and a tetrahydrodicyclopentadiene ring structure is even more preferred.
- the aliphatic hydrocarbon ring structure in R Cy of formula (Cy) is preferably a ring structure in which two or more aliphatic hydrocarbon rings are condensed from the viewpoint of more excellent effects of the present invention. It is more preferable to have a ring structure in which up to four aliphatic hydrocarbon rings are condensed.
- the binder polymer may have one type of structural unit having an aliphatic hydrocarbon ring structure, or may have two or more types.
- the content of the structural unit having an aliphatic hydrocarbon ring structure is based on all the structural units of the binder polymer from the viewpoint that the effects of the present invention are more excellent. 5 to 90% by mass is preferable, 10 to 80% by mass is more preferable, and 20 to 70% by mass is even more preferable.
- the content of the structural unit having an aliphatic hydrocarbon ring structure in the binder polymer is preferably 5 to 70 mol%, based on the total structural units of the binder polymer, from the viewpoint that the effect of the present invention is more excellent, and 10 to 60 mol % is more preferred, and 20 to 50 mol % is even more preferred.
- the content of the structural unit represented by the above formula (Cy) in the binder polymer is preferably 5 to 70 mol% with respect to the total structural units of the binder polymer, from the viewpoint that the effect of the present invention is more excellent, and 10 ⁇ 60 mol% is more preferred, and 20 to 50 mol% is even more preferred.
- the total content of structural units having an aromatic ring structure and structural units having an aliphatic hydrocarbon ring structure is from the viewpoint that the effects of the invention are more excellent, it is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 40 to 75% by mass, based on the total structural units of the binder polymer.
- the total content of structural units having an aromatic ring structure and structural units having an aliphatic hydrocarbon ring structure in the binder polymer is 10 with respect to all structural units of the binder polymer, from the viewpoint that the effects of the present invention are more excellent.
- the total content of the structural units represented by the formula (S) and the structural units represented by the formula (Cy) in the binder polymer is the total structural units of the binder polymer from the viewpoint that the effects of the present invention are more excellent. is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and even more preferably 40 to 60 mol%.
- the molar amount nS of the structural unit represented by the formula (S) and the molar amount nCy of the structural unit represented by the formula (Cy) in the binder polymer are determined by the following formula from the viewpoint that the effect of the present invention is more excellent.
- the binder polymer preferably has a constitutional unit having an acid group from the viewpoint that the effects of the present invention are more excellent.
- the acid group include a carboxy group, a sulfo group, a phosphonic acid group, and a phosphoric acid group, with the carboxy group being preferred.
- the structural unit having an acid group a structural unit derived from (meth)acrylic acid shown below is preferable, and a structural unit derived from methacrylic acid is more preferable.
- the binder polymer may have one type of structural unit having an acid group, or may have two or more types.
- the content of the structural unit having an acid group is 5 to 50% by mass based on the total structural units of the binder polymer from the viewpoint that the effects of the present invention are more excellent.
- the content of the structural unit having an acid group in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 50 mol%, based on the total structural units of the binder polymer, from the viewpoint that the effects of the present invention are more excellent. More preferably, 20 to 40 mol % is even more preferable.
- the content of structural units derived from (meth)acrylic acid in the binder polymer is preferably 5 to 70 mol%, preferably 10 to 50, based on the total structural units of the binder polymer, from the viewpoint that the effects of the present invention are more excellent.
- mol % is more preferred, and 20 to 40 mol % is even more preferred.
- the binder polymer preferably has a reactive group, and more preferably has a structural unit having a reactive group, from the viewpoint that the effects of the present invention are more excellent.
- a reactive group a radically polymerizable group is preferred, and an ethylenically unsaturated group is more preferred.
- the binder polymer preferably has a structural unit having an ethylenically unsaturated group in its side chain. That is, a binder polymer having an ethylenically unsaturated group in a side chain is preferable as the binder polymer.
- main chain refers to the relatively longest bond chain in the molecule of the polymer compound that constitutes the resin
- side chain refers to an atomic group branched from the main chain. show.
- the ethylenically unsaturated group is more preferably an allyl group or a (meth)acryloxy group. Examples of structural units having a reactive group include, but are not limited to, those shown below.
- the binder polymer may have one type of structural unit having a reactive group, or may have two or more types.
- the content of the structural unit having a reactive group is 5 to 70 mass with respect to all structural units of the binder polymer, from the viewpoint that the effect of the present invention is more excellent. %, more preferably 10 to 50% by mass, even more preferably 20 to 40% by mass.
- the content of the structural unit having a reactive group in the binder polymer is preferably 5 to 70 mol%, preferably 10 to 60 mol%, based on the total structural units of the binder polymer, from the viewpoint that the effect of the present invention is more excellent. is more preferred, and 20 to 50 mol % is even more preferred.
- ком ⁇ онентs such as hydroxyl groups, carboxyl groups, primary amino groups, secondary amino groups, acetoacetyl groups, and sulfo groups may be added to epoxy compounds and blocked isocyanate groups. compounds, isocyanate compounds, vinylsulfone compounds, aldehyde compounds, methylol compounds, and carboxylic acid anhydrides.
- glycidyl (meth)acrylate is added to a part of the carboxy group of the resulting polymer by polymer reaction.
- the polymerization reaction is preferably carried out under temperature conditions of 70 to 100°C, more preferably under temperature conditions of 80 to 90°C.
- an azo initiator is preferable, and for example, V-601 (trade name) or V-65 (trade name) manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. is more preferable.
- the above polymer reaction is preferably carried out under temperature conditions of 80 to 110°C. In the polymer reaction, it is preferable to use a catalyst such as an ammonium salt.
- the binder polymer may be the polymer shown below.
- the content ratio (a to d) of each structural unit shown below, the weight average molecular weight Mw, and the like can be appropriately changed depending on the purpose.
- each of a to d in the binder polymer is preferably a: 20 to 60 wt%, b: 10 to 50 wt%, c: 5.0 to 25 wt%, and d: 10 to 50 wt%.
- each of a to d in the binder polymer is preferably a: 20 to 60 wt%, b: 10 to 50 wt%, c: 5.0 to 25 wt%, and d: 10 to 50 wt%.
- each of a to d in the binder polymer is preferably a: 30 to 65 wt%, b: 1.0 to 20 wt%, c: 5.0 to 25 wt%, and d: 10 to 50 wt%.
- each of a to d in the binder polymer is preferably a: 1.0 to 20 wt%, b: 20 to 60 wt%, c: 5.0 to 25 wt%, and d: 10 to 50 wt%.
- the binder polymer may also contain a polymer having a structural unit having a carboxylic anhydride structure (hereinafter also referred to as "polymer X").
- the carboxylic anhydride structure may be either a linear carboxylic anhydride structure or a cyclic carboxylic anhydride structure, but is preferably a cyclic carboxylic anhydride structure.
- the ring of the cyclic carboxylic anhydride structure is preferably a 5- to 7-membered ring, more preferably a 5- or 6-membered ring, and even more preferably a 5-membered ring.
- a structural unit having a carboxylic anhydride structure is a structural unit containing in the main chain a divalent group obtained by removing two hydrogen atoms from a compound represented by the following formula P-1, or a structural unit represented by the following formula P-1 It is preferably a structural unit in which a monovalent group obtained by removing one hydrogen atom from the represented compound is bonded to the main chain directly or via a divalent linking group.
- R A1a represents a substituent
- n 1a R A1a may be the same or different
- Examples of the substituent represented by RA1a include an alkyl group.
- Z 1a is preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, and still more preferably an alkylene group having 2 carbon atoms.
- n1a represents an integer of 0 or more.
- Z 1a represents an alkylene group having 2 to 4 carbon atoms
- n 1a is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, even more preferably 0.
- multiple R A1a may be the same or different.
- two or more RA1a groups may combine with each other to form a ring, but preferably do not combine with each other to form a ring.
- the structural unit having a carboxylic anhydride structure is preferably a structural unit derived from an unsaturated carboxylic anhydride, more preferably a structural unit derived from an unsaturated cyclic carboxylic anhydride, and an unsaturated aliphatic cyclic carboxylic acid anhydride.
- Structural units derived from acid anhydride are more preferred, structural units derived from maleic anhydride or itaconic anhydride are particularly preferred, and structural units derived from maleic anhydride are most preferred.
- Rx represents a hydrogen atom, a methyl group, a CH2OH group, or a CF3 group
- Me represents a methyl group
- the structural unit having a carboxylic anhydride structure in the polymer X may be of one type alone, or may be of two or more types.
- the total content of structural units having a carboxylic anhydride structure is preferably 0 to 60 mol%, more preferably 5 to 40 mol%, more preferably 10 to 35 mol%, relative to the total structural units of the polymer X. preferable.
- the organic film may contain only one type of polymer X, or may contain two or more types.
- the content of the polymer X is preferably 0.1 to 30% by mass, more preferably 0.2 to 20% by mass, more preferably 0.5% by mass, based on the total mass of the organic film. ⁇ 20% by mass is more preferable, and 1 to 20% by mass is even more preferable.
- a preferred embodiment of the binder polymer is a cycloolefin polymer.
- Cycloolefin polymers include the cycloolefin polymers that may be included in the dielectric film described above.
- the weight average molecular weight (Mw) of the binder polymer is preferably 5,000 or more, more preferably 10,000 or more, still more preferably 10,000 to 50,000, and 15,000, from the viewpoint of more excellent effects of the present invention. ⁇ 30,000 is particularly preferred. From the viewpoint of developability, the degree of dispersion of the binder polymer is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, still more preferably 1.0 to 4.0, and 1.0 to 3. .0 is particularly preferred.
- the binder polymer may or may not have an acid group, but when the binder polymer has an acid group, the acid value of the binder polymer is not particularly limited, and is preferably 1000 mgKOH/g or less, more preferably 200 mgKOH/g or less. Preferably, 20 mgKOH/g or less is more preferable. When the polymer has acid groups, the lower limit is not particularly limited, and is often greater than 0 mgKOH/g.
- the acid value of the binder polymer is a value measured according to the method described in JIS K0070:1992.
- the curable composition layer may contain a single binder polymer, or may contain two or more binder polymers.
- the content of the binder polymer is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, based on the total mass of the curable composition layer, and 30 to 70%. % by mass is more preferred.
- the curable composition layer may contain a curable compound.
- a curable compound a compound that is cured by light or heat is preferred.
- Compounds that cure with light or heat include compounds having an ethylenically unsaturated double bond, compounds having a conjugated diene moiety, compounds having a maleimide moiety, en-thiol compounds that cure by a thiol reaction, epoxy compounds, and acids. and a compound having a cross-linking group by the action of A compound having an ethylenically unsaturated double bond is preferred from the viewpoint of curability.
- a compound having an acryloyl group in the molecule is more preferable as the curable compound in terms of curability and compatibility with the alkali-soluble resin.
- the compound having an ethylenically unsaturated double bond for example, a compound obtained by adding (meth)acrylic acid to one end of a polyalkylene oxide, or adding (meth)acrylic acid to one end and adding the other Examples thereof include those whose terminals are alkyl ether or allyl ether.
- Examples of such a compound include phenoxyhexaethylene glycol mono(meth)acrylate which is a (meth)acrylate of a compound obtained by adding polyethylene glycol to a phenyl group, or polypropylene glycol obtained by adding an average of 2 mol of propylene oxide and an average of 7 mol.
- 4-Normal nonylphenoxyheptaethylene glycol dipropylene glycol (meth) acrylate which is a (meth) acrylate of a compound obtained by adding polyethylene glycol to which ethylene oxide is added to nonylphenol, average 1 mol of propylene oxide added polypropylene glycol and average 4-Normal nonylphenoxypentaethylene glycol monopropylene glycol (meth)acrylate which is a (meth)acrylate of a compound obtained by adding polyethylene glycol to which 5 mol of ethylene oxide is added to nonylphenol.
- M-114 4-Normal nonylphenoxyoctaethylene glycol (meth)acrylate (M-114, manufactured by Toagosei Co., Ltd.), which is an acrylate of a compound obtained by adding polyethylene glycol to which an average of 8 mol of ethylene oxide is added to nonylphenol, may also be mentioned.
- the compound having an ethylenically unsaturated double bond includes, for example, a compound having (meth)acryloyl groups at both ends of an alkylene oxide chain, or an alkylene oxide chain in which an ethylene oxide chain and a propylene oxide chain are randomly or block-bonded. Also includes compounds having (meth)acryloyl groups at both ends. 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.
- Examples include acrylates, nonaethylene glycol di(meth)acrylate, decaethylene glycol di(meth)acrylate, and compounds having (meth)acryloyl groups at both ends of 12 moles of ethylene oxide chain. Furthermore, a polyalkylene oxide di(meth)acrylate compound containing at least an ethylene oxide group and a propylene oxide group in the compound is preferable from the viewpoint of resolution, flexibility and plating resistance. From the same point of view, the molecular weight of the compound is preferably 600 to 1,500, more preferably 900 to 1,300, and still more preferably 1,000 to 1,200.
- the polyalkylene oxide di(meth)acrylate compound containing at least an ethylene oxide group and a propylene oxide group in the compound is, for example, polypropylene glycol to which an average of 12 mol of propylene oxide is added and an average of 3 mol of ethylene oxide is further added to each end of the polypropylene glycol.
- Dimethacrylates of glycols and dimethacrylates of glycols obtained by adding an average of 18 mols of propylene oxide to polypropylene glycol and further adding an average of 15 mols of ethylene oxide to both ends of the glycol are exemplified.
- a compound obtained by modifying bisphenol A with alkylene oxide and having (meth)acryloyl groups at both ends is also preferable.
- Alkylene oxide modifications include ethylene oxide modifications, propylene oxide modifications, butylene oxide modifications, pentylene oxide modifications, and hexylene oxide modifications.
- a compound obtained by modifying bisphenol A with ethylene oxide and having (meth)acryloyl groups at both terminals is preferable.
- Examples of such compounds include 2,2-bis(4-((meth)acryloxydiethoxy)phenyl)propane (NK Ester BPE-200 manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis (4-((meth)acryloxytriethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxytetraethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxy) oxypentaethoxy)phenyl)propane (NK Ester BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-((meth)acryloxyhexaethoxy)phenyl)propane, 2,2-bis( 4-((meth)acryloxyheptaethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxyoctaethoxy)phenyl)propane, 2,2-bis(4-((meth)acryl
- a compound having more than two (meth)acryloyl groups in one molecule has 3 moles or more of a group to which an alkylene oxide group can be added in the molecule as a central skeleton, and an ethylene oxide group and propylene oxide or butylene It is obtained by adding an alkylene oxide group such as an oxide to form an alcohol (meth)acrylate.
- Compounds that can serve as the central skeleton include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and isocyanurate rings.
- urethane compounds are also included.
- hexamethylene diisocyanate, tolylene diisocyanate or a diisocyanate compound e.g., 2,2,4-trimethylhexamethylene diisocyanate
- a compound having a hydroxyl group and a (meth)acrylic group in one molecule such as 2-hydroxypropyl Urethane compounds with acrylates and oligopropylene glycol monomethacrylates
- 2-hydroxypropyl Urethane compounds with acrylates and oligopropylene glycol monomethacrylates can be mentioned.
- there is a reaction product of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate manufactured by NOF Corporation, Blenmer PP1000).
- Di- or tri(meth)acrylates of isocyanuric acid esters modified with polypropylene glycol or polycaprolactone are also included.
- Urethane oligomers obtained by reacting a terminal of a urethane compound obtained as a polyadduct of diisocyanate and polyol with a compound having an ethylenically unsaturated double bond and a hydroxyl group are also included.
- Examples of compounds having a conjugated diene moiety include non-volatile compounds obtained by introducing substituents into butadiene, isoprene, etc., polyacetylene and its derivatives, and polyphenylacetylene.
- Compounds having a maleimide moiety include polymer compounds having a maleimide group in the side chain, compounds having two or more maleimide groups in the molecule, and compounds having a (meth)acryloyl group and a maleimide group in the molecule. .
- Thiol compounds that cure by en-thiol reaction include pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis(3-mercaptobutyrate), and 1,3,5-tris(3-mercaptobutyloxyethyl)- Examples include compounds having an aliphatic thiol group such as 1,3,5-triazine-2,4,6(1H,3H,5H)-trione.
- epoxy compounds include epoxy-modified novolak resins, epoxy-modified cresol novolak resins, epoxy-modified bisphenol A, bisphenol A modified with ethylene oxide or propylene oxide and further epoxy-modified, and dicyclopentadiene.
- Epoxy resins having a skeleton and alicyclic epoxy compounds are included. Among them, a compound having at least one glycidyl ether bond and at least one dicyclopentadienyl group in one molecule is preferable.
- Cyclic epoxy compounds have at least one cycloaliphatic epoxy group.
- the alicyclic epoxy group refers to a monovalent substituent having a condensed ring of an epoxy ring and a saturated hydrocarbon ring, preferably a monovalent substituent having a condensed ring of an epoxy ring and a cycloalkane ring.
- Commercially available products that can be suitably used as alicyclic epoxy compounds include Celoxide (registered trademark) 2000, Celoxide 2021P, Celoxide 3000, Celoxide 8000, Cychromer (registered trademark) M100, Epolead GT301, and Epolead available from Daicel Chemical Industries, Ltd.
- Examples include GT401, 4-vinylcyclohexene dioxide manufactured by Sigma-Aldrich, D-limonene oxide manufactured by Nippon Terpene Chemical Co., Ltd., and Sansocizer (registered trademark) E-PS manufactured by Shin Nippon Rika. These can be used individually by 1 type or in combination of 2 or more types.
- Compounds having groups that crosslink by the action of acids include amino compounds such as melamine resins, urea resins, guanamine resins, glycoluril-formaldehyde resins, succinylamide-formaldehyde resins, and ethylene urea-formaldehyde resins.
- amino compounds such as melamine resins, urea resins, guanamine resins, glycoluril-formaldehyde resins, succinylamide-formaldehyde resins, and ethylene urea-formaldehyde resins.
- alkoxymethylated amino resins such as alkoxymethylated melamine resins and alkoxymethylated urea resins are preferred.
- Alkoxymethylated amino resins are, for example, a condensate obtained by reacting melamine or urea with formalin in a boiling aqueous solution, with lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, and isopropyl alcohol. It can be prepared by reacting to form an ether and then precipitating out by cooling the reaction mixture.
- alkoxymethylated amino resins include methoxymethylated melamine resin, ethoxymethylated melamine resin, propoxymethylated melamine resin, butoxymethylated melamine resin, methoxymethylated urea resin, ethoxymethylated urea resin, propoxymethylated Urea resins and butoxymethylated urea resins are included.
- Alkoxymethylated amino resins can be used alone or in combination of two or more. Methoxymethylated melamine resins, ethoxymethylated melamine resins, propoxymethylated melamine resins or butoxymethylated melamine resins are preferred.
- melamine resins include melamine, methylolmelamine, etherified methylolmelamine, benzoguanamine, methylolbenzoguanamine, etherified methylolbenzoguanamine, and condensates thereof.
- etherified methylolmelamine is preferable because of its good chemical resistance.
- a mixture of etherified methylolmelamine and its condensate is commercially available as Nikalac MW-30 (trade name) manufactured by Sanwa Chemical Co., Ltd.
- Combinations of polyvalent isocyanates and polyols can also be used as thermosetting compounds.
- a urethane bond is formed by the reaction between the isocyanate group and the hydroxyl group of the polyol, and a urethane polymer is produced as a binder.
- Polyvalent isocyanates include phenylene-1,3-diisocyanate, phenylene-1,4-diisocyanate, 1-methoxyphenylene-2,4-diisocyanate, and 1-methylphenylene-2,4-diisocyanate.
- diisocyanates for example, 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-tris(methyl isocyanate), 3,5-dimethylcyclohexane-1,3,5-tris(methyl isocyanate), 1,3,5-trimethylcyclohexane-1,3, 5-tris (methyl isocyanate), dicyclohexylmethane-2,4,2-triisocyanate,
- Polyols (compounds having two or more functional alcoholic hydroxyl groups) include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,4-butanediol, polytetramethylene glycol, glycerin, and trimethylol. Propane and pentaerythritol.
- the binder precursor more preferably contains a reaction accelerator that accelerates the thermosetting reaction between the polyisocyanate and the polyol.
- a reaction accelerator By adding a reaction accelerator, the reaction between isocyanate and hydroxyl groups is accelerated, making it possible to produce good urethane polymers even at low temperatures.
- reaction accelerators include tetraalkylammonium salts, cyclic amidines such as diazabicycloundecene (DBU) and diazabicyclononene (DBN) and salts thereof, 1,4-diazabicyclo[2.2.2]octane ( DABCO) and other nitrogen atom-containing heteroaromatic compounds such as pyridines, imidazoles and their salts, alkyltin compounds and their salts, alkylzinc compounds and their salts, zirconium compounds, titanium compounds, alkylaluminums, In addition, boric acids are preferred.
- cyclic amidines such as diazabicycloundecene (DBU) and diazabicyclononene (DBN) and salts thereof, 1,4-diazabicyclo[2.2.2]octane ( DABCO) and other nitrogen atom-containing heteroaromatic compounds
- pyridines imidazoles and their salts
- Thermosetting resins that are cyclized and cured with a base such as polyimide precursor resins, polyamideimide precursor resins, and polybenzoxazole precursor resins, can also be used.
- the curable composition layer may contain a single curable compound, or may contain two or more curable compounds.
- the content of the curable compound is preferably 10% by mass or more, more preferably 25% by mass or more, relative to the total mass of the curable composition layer.
- the upper limit is not particularly limited, it is preferably 70% by mass or less, more preferably 60% by mass or less.
- the curable composition layer may contain an epoxy curing agent.
- epoxy curing agents acid anhydride curing agents, polyamine curing agents, catalyst curing agents, and polycarboxylic acid curing agents are preferred.
- Acid anhydride curing agents include maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrotrimellitic anhydride, phthalic anhydride, and trimellitic anhydride. and styrene-maleic anhydride copolymers.
- polyamine curing agents examples include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dicyandiamide, polyamidoamine (polyamide resin), ketimine compounds, isophoronediamine, m-xylenediamine, m-phenylenediamine, 1,3-bis(amino methyl)cyclohexane, N-aminoethylpiperazine, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, and diaminodiphenylsulfone.
- Catalytic curing agents include tertiary amine compounds and imidazole compounds.
- Polycarboxylic acid curing agents include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, hexachlorendomethylenetetrahydro Phthalic anhydride and methyl-3,6-endomethylenetetrahydrophthalic anhydride are included.
- the content of the curing agent is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, based on the total mass of the curable composition layer. .
- the curable composition layer may contain a polymerization initiator.
- a polymerization initiator it is preferable to use a suitable polymerization initiator according to the type of the curable compound, and a photo- or thermal polymerization initiator is more preferable.
- a photopolymerization initiator is a compound that can be decomposed by exposure to generate initiating species such as radicals and acids, and the initiating species can initiate and accelerate the polymerization reaction of a polymerizable compound.
- the polymerization form may be radical polymerization, cationic polymerization, or anionic polymerization. If at least a part of the components of the polymerization initiator, or impurities or decomposed substances that contain highly nucleophilic substances are contained in the polymerization initiator, they will adsorb to the surface of the phosphor and weaken the reaction rate of the epoxide. It may affect the luminous efficiency of the phosphor contained in the dispersion composition. Therefore, it is preferable that the content of highly nucleophilic components, particularly primary amines and secondary amines, be small in the polymerization initiator.
- photopolymerization initiators include quinones, aromatic ketones, acetophenones, acylphosphine oxides, benzoin or benzoin ethers, dialkylketals, thioxanthones, dialkylaminobenzoic acid esters, oxime esters, and acridines. , hexaarylbiimidazole, pyrazoline derivatives, N-arylamino acids or their ester compounds, and halogen compounds.
- the 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-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2 , 3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone.
- Aromatic ketones include benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], 4,4'-bis(diethylamino)benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone. .
- Acetophenones include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecyl Phenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenylketone, 2-benzyl-2- Dimethylamino-1-(4-morpholinophenyl)-butanone-1 and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1.
- Commercially available products include Irgacure-907, Irgacure-369 and Irgacure-379 manufactured by Ciba Specialty Chemicals.
- Acylphosphine oxides include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phosphine oxide, and bis(2,6-dimethoxybenzoyl)-2 , 4,4-trimethyl-pentyl phosphone oxide.
- Commercially available products include Lucirin TPO manufactured by BASF and Irgacure-819 manufactured by Ciba Specialty Chemicals.
- Benzoin or benzoin ethers include benzoin, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, and ethylbenzoin.
- Dialkyl ketals include benzyl dimethyl ketal and benzyl diethyl ketal.
- Thioxanthones include 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.
- Dialkylaminobenzoic acid esters include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, and 2-ethylhexyl-4-(dimethylamino)benzoate.
- Oxime esters include 1-phenyl-1,2-propanedione-2-O-benzoyloxime and 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime.
- Commercially available products include CGI-325, Irgacure OXE01 and Irgacure OXE02 manufactured by Ciba Specialty Chemicals.
- a photocationic polymerization initiator can also be used as the photopolymerization initiator.
- the photocationic polymerization initiator for example, paragraphs [0019] to [0024] of Japanese Patent No. 4675719 can be referred to.
- Preferred photocationic polymerization initiators include iodonium salt compounds, sulfonium salt compounds, pyridinium salt compounds, and phosphonium salt compounds. Among them, an iodonium salt compound or a sulfonium salt compound is preferable from the viewpoint of excellent thermal stability.
- An iodonium salt compound is a salt formed by a cation moiety containing I + in the structure and an anion moiety having an arbitrary structure, having three or more electron-donating groups, and at least one of these electron-donating groups More preferred are diaryliodonium salts, one of which is an alkoxy group. By introducing an alkoxy group, which is an electron-donating group, into the diaryliodonium salt in this way, decomposition due to water or nucleophiles over time and electron transfer due to heat can be suppressed, thereby improving stability. can be expected.
- Usable cationic photopolymerization initiators include, for example, the following commercially available products, or a combination of two or more of them: CPI-110P (photocationic polymerization initiator C below), CPI-101A, manufactured by San-Apro Co., Ltd. CPI-110P, CPI-200K, Wako Pure Chemical Industries, Ltd. WPI-113, WPI-116, WPI-124, WPI-169, WPI-170, Rhodia PI-2074, BASF Corporation ) manufactured by Irgacure (registered trademark)-250, Irgacure-270, and Irgacure-290 (photo cationic polymerization initiator D below).
- CPI-110P photocationic polymerization initiator C below
- CPI-101A manufactured by San-Apro Co., Ltd.
- CPI-200K CPI-200K
- Thermal polymerization initiators include onium salt compounds such as iodonium salts, sulfonium salts and phosphonium salts, boron trifluoride and Lewis acid compounds (e.g., zinc halide, tin halide, aluminum halide and halogen iron oxide, etc.) with tertiary amines or nitrogen atom-containing heteroaromatics, imidazoles, cyclic amidines, and salts of these with organic acids.
- onium salt compounds such as iodonium salts, sulfonium salts and phosphonium salts, boron trifluoride and Lewis acid compounds (e.g., zinc halide, tin halide, aluminum halide and halogen iron oxide, etc.) with tertiary amines or nitrogen atom-containing heteroaromatics, imidazoles, cyclic amidines, and salts of these with organic acids.
- Lewis acid compounds e.g., zinc halide,
- the curable composition layer may contain a single polymerization initiator, or may contain two or more polymerization initiators.
- the content of the polymerization initiator is preferably 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the total mass of the curable composition layer. more preferred.
- the curable composition layer may contain a heterocyclic compound.
- the heterocyclic ring contained in the heterocyclic compound may be either monocyclic or polycyclic heterocyclic ring.
- a nitrogen atom, an oxygen atom, and a sulfur atom are mentioned as a heteroatom which a heterocyclic compound has.
- the heterocyclic compound preferably has at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably has a nitrogen atom.
- heterocyclic compounds examples include triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, benzoxazole compounds, and pyrimidine compounds (e.g., iso nicotinamide).
- the heterocyclic compound is at least one selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzimidazole compounds, and benzoxazole compounds.
- At least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, and benzoxazole compounds is more preferred.
- heterocyclic compound Preferred specific examples of the heterocyclic compound are shown below.
- triazole compounds and benzotriazole compounds include the following compounds.
- the following compounds can be exemplified as thiadiazole compounds.
- triazine compounds include the following compounds.
- the following compounds can be exemplified as rhodanine compounds.
- the following compounds can be exemplified as thiazole compounds.
- the following compounds can be exemplified as benzimidazole compounds.
- the curable composition layer may contain a single heterocyclic compound, or may contain two or more heterocyclic compounds.
- the content of the heterocyclic compound is preferably 0.01 to 20% by mass, based on the total mass of the curable composition layer, and 0.1 to 10% by mass. more preferred.
- the curable composition layer may contain blocked isocyanate.
- a blocked isocyanate compound refers to "a compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) with a blocking agent”.
- the dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 to 160°C, more preferably 130 to 150°C.
- the dissociation temperature of the blocked isocyanate means "the temperature of the endothermic peak associated with the deprotection reaction of the blocked isocyanate as measured by DSC (Differential Scanning Calorimetry) analysis using a differential scanning calorimeter".
- DSC Different Scanning Calorimetry
- a differential scanning calorimeter for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be suitably used. However, the differential scanning calorimeter is not limited to this.
- the blocking agent having a dissociation temperature of 100 to 160° C. is preferably at least one selected from oxime compounds from the viewpoint of storage stability.
- the blocked isocyanate compound preferably has an isocyanurate structure from the viewpoints of, for example, improving the brittleness of the film and improving the adhesion to the transferred material.
- a blocked isocyanate compound having an isocyanurate structure is obtained, for example, by isocyanurating hexamethylene diisocyanate and protecting it.
- a compound having an oxime structure using an oxime compound as a blocking agent tends to have a dissociation temperature within a preferred range and produces less development residue than compounds having no oxime structure. It is preferable because it is easy to
- the blocked isocyanate compound may have a polymerizable group.
- the polymerizable group is not particularly limited, and any known polymerizable group can be used, and a radically polymerizable group is preferred.
- Polymerizable groups include ethylenically unsaturated groups such as (meth)acryloxy groups, (meth)acrylamide groups, and styryl groups, and groups having epoxy groups such as glycidyl groups. Among them, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth)acryloxy group, and still more preferably an acryloxy group.
- a commercial item can be used as a block isocyanate compound.
- blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (manufactured by Showa Denko KK), block type Duranate series (eg, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals).
- the compound of the following structure can also be used as a blocked isocyanate compound.
- the curable composition layer may contain a single blocked isocyanate, or may contain two or more blocked isocyanates.
- the content of the blocked isocyanate in the curable composition layer is preferably 1 to 50% by mass, preferably 5 to 30% by mass, based on the total mass of the curable composition layer. % is more preferred.
- the curable composition layer may contain an aliphatic thiol compound.
- the curable composition layer contains an aliphatic thiol compound, the en-thiol reaction between the aliphatic thiol compound and a radically polymerizable compound having an ethylenically unsaturated group cure shrinkage of the film formed. is suppressed and the stress is relieved.
- aliphatic thiol compound a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (that is, a bifunctional or higher aliphatic thiol compound) is preferable.
- the aliphatic thiol compound is preferably a polyfunctional aliphatic thiol compound, for example, from the viewpoint of adhesion of the formed pattern (especially adhesion after exposure).
- polyfunctional aliphatic thiol compound means an aliphatic compound having two or more thiol groups (also referred to as “mercapto groups”) in the molecule.
- a low-molecular-weight compound having a molecular weight of 100 or more is preferable as the polyfunctional aliphatic thiol compound.
- the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, still more preferably 150 to 1,000.
- the number of functional groups of the polyfunctional aliphatic thiol compound is, for example, preferably 2 to 10 functional, more preferably 2 to 8 functional, and even more preferably 2 to 6 functional, from the viewpoint of adhesion of the pattern to be formed.
- polyfunctional aliphatic thiol compounds include trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolethane tris(3-mercaptobutyrate ), tris [(3-mercaptopropionyloxy) ethyl] isocyanurate, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate pionate), dipentaerythritol hexakis(3-mercaptopropionat
- polyfunctional aliphatic thiol compounds include trimethylolpropane tris (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, and 1,3,5-tris At least one compound selected from the group consisting of (3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione is preferred.
- Examples of monofunctional aliphatic thiol compounds include 1-octanethiol, 1-dodecanethiol, ⁇ -mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n- Octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.
- the curable composition layer may contain a single aliphatic thiol compound, or may contain two or more aliphatic thiol compounds.
- the content of the aliphatic thiol compound is preferably 5% by mass or more, more preferably 5 to 50% by mass, with respect to the total mass of the curable composition layer. , more preferably 5 to 30% by mass, particularly preferably 8 to 20% by mass.
- the curable composition layer may contain a surfactant.
- surfactants include surfactants described in paragraph [0017] of Japanese Patent No. 4502784 and paragraphs [0060] to [0071] of JP-A-2009-237362.
- a fluorine-based surfactant or a silicon-based surfactant is preferable.
- fluorosurfactants include MEGAFACE F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, and F-144. , F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F -558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, EXP. MFS-578, EXP.
- an acrylic compound that has a molecular structure with a functional group containing a fluorine atom and in which the portion of the functional group containing the fluorine atom is cleaved and the fluorine atom volatilizes when heat is applied can also be suitably used.
- fluorine-based surfactants include Megafac DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Megafac and DS-21.
- the fluorosurfactant it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.
- a block polymer can also be used as the fluorosurfactant.
- the fluorine-based surfactant has a structural unit derived from a (meth)acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups).
- a fluorine-containing polymer compound containing a structural unit derived from a (meth)acrylate compound can also be preferably used.
- a fluoropolymer having an ethylenically unsaturated bond-containing group in a side chain can also be used.
- Megafac RS-101, RS-102, RS-718K, RS-72-K manufactured by DIC Corporation
- DIC Corporation Megafac RS-101, RS-102, RS-718K, RS-72-K (manufactured by DIC Corporation) and the like.
- fluorine-based surfactants from the viewpoint of improving environmental suitability, compounds having linear perfluoroalkyl groups having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), are used.
- PFOA perfluorooctanoic acid
- PFOS perfluorooctane sulfonic acid
- Surfactants derived from alternative materials are preferred.
- Hydrocarbon surfactants include glycerol, trimethylolpropane, trimethylolethane, their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether , polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, and the like.
- Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, HYDROPALAT WE 3323 (manufactured by BASF), Solsperse 20000 (manufactured by BASF) Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), Pionin D-1105, D-6112, D-6112-W, D -6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), Olphine E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.) and the like.
- silicone-based surfactants include straight-chain polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups are introduced into side chains and terminals.
- silicone-based surfactants include EXP. S-309-2, EXP. S-315, EXP. S-503-2, EXP. S-505-2 (manufactured by DIC Corporation), DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 ( Above, Dow Corning Toray Co., Ltd.) and 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-105, KP-106 ,
- the curable composition layer may contain a single surfactant, or may contain two or more surfactants.
- the content of the surfactant is preferably 0.01 to 3% by mass, preferably 0.05 to 1% by mass, based on the total mass of the curable composition layer. is more preferred, and 0.1 to 0.8% by mass is even more preferred.
- the curable composition layer may contain a hydrogen donating compound.
- the hydrogen-donating compound has actions such as further improving the sensitivity of the photopolymerization initiator to actinic rays and suppressing inhibition of polymerization of the polymerizable compound by oxygen.
- amines such as M.I. R. "Journal of Polymer Society" by Sander et al., Vol. JP-A-60-084305, JP-A-62-018537, JP-A-64-033104, and Research Disclosure 33825.
- hydrogen donating compounds include triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, and p-methylthiodimethylaniline.
- the hydrogen-donating compound includes amino acid compounds (N-phenylglycine, etc.), organometallic compounds (tributyltin acetate, etc.) described in JP-B-48-042965, and hydrogen described in JP-B-55-034414. Also included are donors and sulfur compounds (such as trithiane) described in JP-A-6-308727.
- the curable composition layer may contain a single hydrogen donating compound, or may contain two or more hydrogen donating compounds.
- the content of the hydrogen-donating compound is in the total mass of the curable composition layer, from the viewpoint of improving the curing rate due to the balance between the polymerization growth rate and the chain transfer.
- 0.01 to 10% by mass is preferable, 0.03 to 5% by mass is more preferable, and 0.05 to 3% by mass is even more preferable.
- the curable composition layer may contain components other than the components described above (hereinafter also referred to as “other components”).
- Other ingredients include, for example, particles (eg, metal oxide particles) and colorants.
- other components include, for example, the thermal polymerization inhibitor described in paragraph [0018] of Japanese Patent No. 4502784, and other components described in paragraphs [0058] to [0071] of JP-A-2000-310706. Additives of are also included.
- the curable composition layer may contain particles for the purpose of adjusting refractive index, light transmittance, and the like.
- Particles include, for example, metal oxide particles.
- Metals in metal oxide particles also include semimetals such as B, Si, Ge, As, Sb, and Te.
- the average primary particle diameter of the particles is, for example, preferably 1 to 200 nm, more preferably 3 to 80 nm, from the viewpoint of pattern transparency.
- the average primary particle diameter of particles is calculated by measuring the particle diameters of 200 arbitrary particles using an electron microscope and arithmetically averaging the measurement results. When the shape of the particles is not spherical, the longest side is taken as the particle diameter.
- the curable composition layer may contain a single type of particles, or may contain two or more types of particles. When the curable composition layer contains particles, it may contain only one type of particles having different metal types, sizes, etc., or may contain two or more types.
- the curable composition layer does not contain particles, or the content of particles is preferably more than 0% by mass and 35% by mass or less with respect to the total mass of the curable composition layer, and contains particles. or the content of the particles is more than 0% by mass and 10% by mass or less with respect to the total mass of the curable composition layer, and the particles are not included, or the content of the particles is more than 0% by mass and 5% by mass or less with respect to the total mass of the curable composition layer, and does not contain particles, or the content of particles is the total mass of the curable composition layer It is particularly preferred that it is more than 0% by mass and not more than 1% by mass, and most preferably does not contain particles.
- the curable composition layer may contain a trace amount of coloring agents (eg, pigments and dyes), it is preferred that the curable composition layer does not substantially contain coloring agents, for example, from the viewpoint of transparency.
- the content of the colorant is preferably less than 1% by mass, more preferably less than 0.1% by mass, relative to the total mass of the curable composition layer.
- the curable composition layer may contain a certain amount of impurities.
- impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens and ions thereof.
- halide ions, sodium ions, and potassium ions are likely to be mixed as impurities, so the following contents are preferable.
- the content of impurities in the curable composition layer is preferably 80 ppm or less, more preferably 10 ppm or less, and even more preferably 2 ppm or less on a mass basis.
- the content of impurities in the curable composition layer can be 1 ppb or more, and can be 0.1 ppm or more on a mass basis.
- the amount of impurities can be made within the above range.
- Impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.
- ICP Inductively Coupled Plasma
- the content of compounds such as benzene, formaldehyde, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the curable composition layer is Less is preferred.
- 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, based on mass.
- the lower limit can be 10 ppb or more, and can be 100 ppb or more on a mass basis.
- the content of these compounds can be suppressed in the same manner as the metal impurities described above. Moreover, it can quantify by a well-known measuring method.
- the water content in the curable composition layer is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass, from the viewpoint of improving reliability and laminating properties.
- the upper limit of the thickness of the curable composition layer is preferably 20.0 ⁇ m or less, more preferably 15.0 ⁇ m or less, and even more preferably 12.0 ⁇ m or less, from the viewpoint of coatability.
- the lower limit of the thickness of the curable composition is preferably 0.05 ⁇ m or more.
- the thickness of the curable composition layer is calculated as an average value of arbitrary five points measured by cross-sectional observation with a scanning electron microscope (SEM).
- the curable composition layer is preferably achromatic.
- the a * value of the curable composition layer is preferably -1.0 to 1.0, and the b * value of the curable composition layer is preferably -1.0 to 1.0.
- the hue of the curable composition layer can be measured using a color difference meter (CR-221, manufactured by Minolta Co., Ltd.).
- a method for producing the transfer film is not particularly limited, and a known method can be used. Among them, in terms of excellent productivity, a method of applying a curable composition on a temporary support and performing a drying treatment as necessary to form a curable composition layer (hereinafter, this method is referred to as a "coating method ) is preferable.
- the curable composition used in the coating method includes components constituting the curable composition layer described above (e.g., polymerizable compound, polymer, heterocyclic compound, polymerization initiator, blocked isocyanate compound, etc.) and a solvent. preferably included.
- a solvent preferably included.
- an organic solvent is preferred. 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, and caprolactam.
- a mixed solvent of methyl ethyl ketone and propylene glycol monomethyl ether acetate or a mixed solvent of diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate is preferable.
- the curable composition may contain a single solvent, or may contain two or more solvents.
- the total solid content of the curable composition is preferably 5 to 80% by mass, more preferably 5 to 40% by mass, based on the total mass of the curable composition. 30 mass % is more preferable.
- the viscosity of the curable composition at 25° C. is preferably 1 to 50 mPa ⁇ s, more preferably 2 to 40 mPa ⁇ s, more preferably 3 to 30 mPa ⁇ s, from the viewpoint of coating properties. s is more preferred. Viscosity is measured using a viscometer.
- a viscometer for example, a viscometer manufactured by Toki Sangyo Co., Ltd. (trade name: VISCOMETER TV-22) can be suitably used.
- the viscometer is not limited to the viscometers described above.
- the surface tension of the curable composition at 25° C. is, for example, from the viewpoint of coatability, preferably 5 to 100 mN/m, more preferably 10 to 80 mN/m, and 15 to 40 mN. /m is more preferred.
- Surface tension is measured using a surface tensiometer.
- a surface tensiometer manufactured by Kyowa Interface Science Co., Ltd. (trade name: Automatic Surface Tensiometer CBVP-Z) can be suitably used.
- the surface tension meter is not limited to the surface tension meter described above.
- Examples of methods for applying the curable composition include printing, spraying, roll coating, bar coating, curtain coating, spin coating, and die coating (that is, slit coating).
- Drying methods include, for example, natural drying, heat drying, and vacuum drying. The methods described above can be applied singly or in combination. In the present disclosure, “drying” means removing at least part of the solvent contained in the composition.
- a transfer film when a transfer film has a protective film, a transfer film can be manufactured by bonding a protective film together to a curable composition layer.
- a method for laminating the protective film to the curable composition layer is not particularly limited, and includes known methods.
- Apparatuses for bonding the protective film to the curable composition layer include known laminators such as a vacuum laminator and an autocut laminator.
- the laminator is equipped with any heatable roller, such as a rubber roller, and can be applied with pressure and heat.
- the laminate 20 shown in FIG. 3 includes a dielectric film 22, a first metal pattern 24 arranged on one surface side of the dielectric film 22, and a first organic film 26 arranged on the first metal pattern 24. , a second metal pattern 28 arranged on the other surface side of the dielectric film 22 , and a first organic film 30 arranged on the first metal pattern 28 .
- the first metal pattern 24 is composed of a plurality of first metal structures 32 and the second metal pattern 28 is composed of a plurality of second metal structures 34 .
- the first metal pattern 24 and the second metal pattern 28 form a resonator for electromagnetic waves in the terahertz band. More specifically, resonance occurs between the first metal structure 32 in the first metal pattern 24 and the second metal structure 34 in the second metal pattern 28 with respect to the electromagnetic waves in the terahertz band.
- Metal structure 32 and second metal structure 34 can function as one resonator.
- the dielectric film included in the second embodiment and the dielectric film included in the first embodiment are the same member, and the description thereof is omitted. Further, the first organic film and the second organic film included in the second embodiment and the organic film included in the first embodiment are the same members, and the description thereof is omitted.
- the first metal structure included in the first metal pattern and the second metal structure constituting the second metal pattern included in the second embodiment are described in the first embodiment.
- Various characteristics described in the metal structure constituting the metal pattern included in the embodiments can be mentioned. From the viewpoint of resonance with respect to electromagnetic waves in the terahertz band, when the laminate is viewed from above, the first metal structure included in the first metal pattern and the second metal structure included in the second metal pattern are separated. , are preferably arranged so as to at least partially overlap. Further, when the laminate is viewed in plan, the first metal structure included in the first metal pattern and the second metal structure included in the second metal pattern may be arranged so as not to overlap. However, the deviation is preferably 20 ⁇ m or less.
- the manufacturing method of the second embodiment of the laminate is not particularly limited, but a dielectric film, a first metal pattern composed of a plurality of first metal structures arranged on one surface side of the dielectric film, a second metal pattern composed of a plurality of second metal structures arranged on the other surface side of the dielectric film, wherein the first metal pattern and the second metal pattern serve as a resonator for electromagnetic waves in the terahertz band; Constituting a metal patterned film (hereinafter also simply referred to as "metal patterned film B”) and a transfer film containing a temporary support and a curable composition layer, and a temporary support, curable Step 1B of forming a precursor film having a composition layer, a first metal pattern, a dielectric film, a second metal pattern, a curable composition layer, and a temporary support in this order; A method comprising Step 2B of applying a curing treatment to obtain an organic film, and Step 3B of peeling off the temporary support between Steps
- a film B with a metal pattern is used.
- the configuration of the metal pattern contained in the film B with the metal pattern is the same as the configuration of the metal pattern in the laminate described above.
- the method for producing the metal patterned film B is not particularly limited. By etching away the layer and peeling off the resist pattern, a film B with a metal pattern can be produced.
- Step 1B a film B with a metal pattern and a transfer film containing a temporary support and a curable composition layer are laminated to form a temporary support, a curable composition layer, a first metal pattern, a dielectric film, It is a step of forming a precursor film having a second metal pattern, a curable composition layer, and a temporary support in this order. In this step, two transfer films are prepared, and the transfer films are laminated on both sides of the film B with the metal pattern.
- the bonding method includes the method described in step 1A.
- Step 2B is a step of curing the curable composition layer to obtain an organic film.
- the first organic film is formed on the first metal pattern
- the second organic film is formed on the second metal pattern.
- the hardening treatment method includes the method described in step 2A.
- Step 3B is a step of peeling off the temporary support between Step 1B and Step 2B or after Step 2B.
- the peeling method is not particularly limited, and a mechanism similar to the cover film peeling mechanism described in paragraphs [0161] to [0162] of JP-A-2010-072589 can be used.
- the laminate of the present invention can be applied to various uses.
- the optical element of the present invention includes the laminate described above.
- Optical elements include planar lenses, diffraction gratings, wavelength filters, polarizers, and sensors.
- the size of the laminate is not particularly limited, and an optimum size is appropriately selected according to the intended use.
- the area of the laminate is preferably 1 cm 2 or more, more preferably 5 cm 2 or more.
- the weight average molecular weight of the resin is the weight average molecular weight determined by gel permeation chromatography (GPC) in terms of polystyrene. Moreover, the theoretical acid value was used for the acid value.
- a COP film was produced by the method described in Japanese Patent No. 4991170.
- the thickness of the COP film was 50 ⁇ m.
- the film cut into a size of 10 cm is placed inside the sputtering film forming apparatus, and after the pressure inside the apparatus is reduced, argon gas is introduced, and Cu is used as the target. was used to perform sputtering.
- a copper layer having a thickness of 50 nm was formed on both sides, one side at a time.
- the photosensitive transfer member (negative transfer material 1) disclosed in JP-A-2020-204757 was unwound, and the cover film was peeled off from the photosensitive transfer member.
- the photosensitive transfer member and the COP film on which the copper layer was arranged were laminated together so that the photosensitive resin layer and the copper layer exposed by peeling off the cover film were in contact with each other to obtain a laminate.
- This bonding step was performed under conditions of a roll temperature of 100° C., a linear pressure of 1.0 MPa, and a linear velocity of 4.0 m/min.
- a photomask 40 shown in FIG. 4 has a plurality of rectangular openings 42 arranged at equal intervals in the width direction and the length direction.
- the opening 42 has a length L of 313 ⁇ m and a width W of 54 ⁇ m.
- the distance D1 between the openings in the length direction of the openings was 94 ⁇ m, and the distance D2 between the openings in the width direction of the openings was 86 ⁇ m.
- the laminate was subjected to shower development for 30 seconds using a 1.0% sodium carbonate aqueous solution at a liquid temperature of 25° C., and a resist was applied onto the copper layer. formed a pattern. Then, the resulting laminate was etched with a copper etchant (Cu-02: manufactured by Kanto Kagaku Co., Ltd.) at 23° C. for 30 seconds, and the resist pattern was removed using propylene glycol monomethyl ether acetate. , a metal patterned film 1 having copper patterns patterned on the front and back was obtained. The transmission characteristics of the resulting metal patterned film 1 were measured using terahertz time domain spectroscopy (THz-TDS).
- THz-TDS terahertz time domain spectroscopy
- the sample was fixed in an aperture of ⁇ 10 mm (NA ⁇ 1/6) and irradiated with a terahertz beam under an environment of 25°C temperature and 20% humidity.
- the polarization direction and the long axis direction of the pattern were matched.
- a steep trough (dent) and phase reversal of the transmittance were observed near 320 GHz, suggesting that the metal patterns arranged on both sides of the COP film resonated.
- Metal patterned film 2 was prepared according to the same procedure as (Metal patterned film 1) above, except that a COP film with silver layers on both sides was used instead of a COP film with copper layers on both sides. manufactured.
- the transmission characteristics of the metal patterns arranged on both sides of the COP film in the metal patterned film 2 obtained were measured in the same manner as in the case of the metal patterned film 1, and resonance occurred with respect to electromagnetic waves in the terahertz band. I confirmed that A COP film having silver layers on both sides was produced by the following method.
- conductive metal nano ink DryCureAg-J (10% by weight aqueous solution of silver nanoparticles) manufactured by C-INK Co., Ltd. was applied to both sides of the COP film, and then heated to 120 ° C. for 60 minutes to obtain a silver layer.
- ⁇ St styrene
- MAA-GMA structural unit obtained by adding glycidyl methacrylate to a structural unit derived from methacrylic acid
- MAA methacrylic acid
- DCPMA dicyclopentanyl methacrylate
- MAA-GMA methyl methacrylate
- Curable compositions A-1 to A-6 having compositions shown in Table 3 below were prepared.
- the numerical value of each component represents the content (solid content mass) of each component, methyl ethyl ketone and 1-methoxy-2-propyl acetate were added as appropriate, and the content of methyl ethyl ketone in the solvent was 60% by mass, and the solid content was 60% by mass.
- a curable composition was prepared so that the concentration was 25% by mass.
- a curable composition B-1 having the composition shown in Table 5 below was prepared.
- a curable composition B-2 having the composition shown in Table 5 below was prepared.
- the curable composition B-2 was a two-pack set consisting of A and B liquids.
- the protective film of each transfer film of Examples and Comparative Examples was peeled off, and the surface of the exposed curable composition layer was brought into contact with the metal pattern of the film with a metal pattern so that the curable composition layer covered the metal pattern. to form a laminate in which the curable composition layer and the temporary support are arranged on the film with a metal pattern.
- the above lamination was performed using a vacuum laminator manufactured by MCK 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.
- the distance between the exposure mask surface and the temporary support was set to 125 ⁇ m, and the temporary support was interposed.
- the entire surface was exposed with an exposure amount of 100 mJ/cm 2 (i-line), and a heating (post-baking) treatment was performed at 150° C. for 60 minutes to use as a measurement sample.
- the obtained evaluation sample was allowed to stand at a temperature of 40° C. and a relative humidity of 90% for 24 hours, and then the moisture permeability was determined under the same conditions (temperature of 40° C. and a relative humidity of 90%) by the method described in JIS Z 0208.
- the obtained water vapor permeability value was multiplied by 5 to obtain the water vapor permeability per one layer of the organic film.
- the above operation was performed on five measurement samples to determine the water vapor transmission rate per five layers, and these numerical values were arithmetically averaged to obtain the water vapor transmission rate (WVTR) of the present invention.
- the obtained water vapor transmission rate (WVTR) was evaluated according to the latter evaluation criteria.
- an evaluation sample was prepared by performing only a heat treatment at 145° C. for 30 minutes without performing the exposure treatment.
- WVTR is 1000 g/(m 2 24 hr) or less
- the "film” column represents the type of film with metal pattern, "1” represents film 1 with metal pattern, and “2” represents film 2 with metal pattern.
- the “heterocyclic compound” column indicates whether or not the organic film contains a heterocyclic compound. It means that it does not contain a ring compound.
- the “acid value” column represents whether the acid value of the polymer contained in the organic film is 20 mgKOH/g or less, “A” represents 20 mgKOH/g or less, and “B” represents 20 mgKOH. /g.
- the “thickness ( ⁇ m)” column represents the thickness ( ⁇ m) of the organic film.
- the laminate of the present invention exhibits desired effects. From the comparison between Examples 8 and 9, more excellent effects were obtained when the organic film contained a heterocyclic compound. From a comparison between Examples 8 and 10, when the acid value of the polymer contained in the organic film was 20 mgKOH/g or less, more excellent effects were obtained.
- Reference Signs List 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
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Abstract
Description
また、本発明は、積層体の製造方法を提供することも課題とする。
誘電体フィルムの少なくとも一方の表面側に配置された、テラヘルツ帯の電磁波に対して共振器となる、金属パターンと、
金属パターン上に配置された、温度40℃、相対湿度90%の環境下における透湿度が3000g/(m2・24hr)以下である有機膜と、を有する、積層体。
(2) 有機膜が、複素環化合物を含む、(1)に記載の積層体。
(3) 有機膜が、酸価が20mgKOH/g以下であるポリマーを含む、(1)又は(2)に記載の積層体。
(4) 有機膜が硬化性組成物を用いて形成され、
硬化性組成物がブロックイソシアネートを含む、(1)~(3)のいずれかに記載の積層体。
(5) 誘電体フィルムと、
誘電体フィルムの一方の表面側に配置された、複数の第1金属構造体から構成された第1金属パターンと、
第1金属パターン上に配置された、温度40℃、相対湿度90%の環境下における透湿度が3000g/(m2・24hr)以下である第1有機膜と、
誘電体フィルムの他方の表面側に配置された、複数の第2金属構造体から構成された第2金属パターンと、
第2金属パターン上に配置された、温度40℃、相対湿度90%の環境下における透湿度が3000g/(m2・24hr)以下である第2有機膜と、を有し、
第1金属パターンと第2金属パターンとが、テラヘルツ帯の電磁波に対して共振器を構成する、積層体。
(6) 積層体を平面視した際に、第1金属パターンに含まれる第1金属構造体と、第2金属パターンに含まれる第2金属構造体とが、少なくとも一部重複するように配置されている、(5)に記載の積層体。
(7) 第1有機膜及び第2有機膜が、複素環化合物を含む、(5)又は(6)に記載の積層体。
(8) 第1有機膜及び第2有機膜が、酸価が20mgKOH/g以下であるポリマーを含む、(5)~(7)のいずれかに記載の積層体。
(9) 第1有機膜及び第2有機膜が硬化性組成物を用いて形成され、
硬化性組成物がブロックイソシアネートを含む、(5)~(8)のいずれかに記載の積層体。
(10) (1)~(9)のいずれかに記載の積層体を含む、光学素子。
(11) 誘電体フィルム、及び、誘電体フィルムの少なくとも一方の表面側に配置された、テラヘルツ帯の電磁波に対して共振器となる金属パターンを含む金属パターン付きフィルムと、仮支持体及び硬化性組成物層を含む転写フィルムとを貼合して、誘電体フィルム、金属パターン、硬化性組成物層、及び、仮支持体をこの順で有する前駆体フィルムを形成する工程1Aと、
硬化性組成物層に硬化処理を施して、温度40℃、相対湿度90%の環境下における透湿度が3000g/(m2・24hr)以下である有機膜を得る工程2Aと、を、有し、
工程1Aと工程2Aとの間、又は、工程2Aの後に、仮支持体を剥離する工程を更に有する、積層体の製造方法。
(12) 有機膜が、複素環化合物を含む、(11)に記載の積層体の製造方法。
(13) 有機膜が、酸価が20mgKOH/g以下であるポリマーを含む、(11)又は(12)に記載の積層体の製造方法。
(14) 硬化性組成物層がブロックイソシアネートを含む、(11)~(13)のいずれかに記載の積層体の製造方法。
(15) 誘電体フィルムと、誘電体フィルムの一方の表面側に配置された、複数の第1金属構造体から構成された第1金属パターンと、誘電体フィルムの他方の表面側に配置された、複数の第2金属構造体から構成された第2金属パターンとを含み、第1金属パターンと第2金属パターンとがテラヘルツ帯の電磁波に対して共振器を構成する金属パターン付きフィルムと、仮支持体及び硬化性組成物層を含む転写フィルムとを貼合して、仮支持体、硬化性組成物層、第1金属パターン、誘電体フィルム、第2金属パターン、硬化性組成物層、及び、仮支持体をこの順で有する前駆体フィルムを形成する工程1Bと、
硬化性組成物層に硬化処理を施して、温度40℃、相対湿度90%の環境下における透湿度が3000g/(m2・24hr)以下である有機膜を得る工程2Bと、を、有し、
工程1Bと工程2Bとの間、又は、工程2Bの後に、仮支持体を剥離する工程3Bを更に有する、積層体の製造方法。
(16) 金属パターン付きフィルムを平面視した際に、第1金属パターンに含まれる第1金属構造体と、第2金属パターンに含まれる第2金属構造体とが、少なくとも一部重複するように配置されている、(15)に記載の積層体の製造方法。
(17) 有機膜が、複素環化合物を含む、(15)又は(16)に記載の積層体の製造方法。
(18) 有機膜が、酸価が20mgKOH/g以下であるポリマーを含む、(15)~(17)のいずれかに記載の積層体の製造方法。
(19) 硬化性組成物層がブロックイソシアネートを含む、(15)~(18)のいずれかに記載の積層体の製造方法。
また、本発明によれば、積層体の製造方法を提供することも課題とする。
以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされる場合があるが、本発明はそのような実施態様に制限されない。
本明細書において、「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。
本明細書において、段階的に記載されている数値範囲において、ある数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本明細書に記載されている数値範囲において、ある数値範囲で記載された上限値又は下限値は、実施例に示されている値に置き換えてもよい。
本明細書において、特段の断りがない限り、分子量分布がある化合物の分子量は、重量平均分子量(Mw)である。
本明細書において、特段の断りがない限り、色相は、色差計(CR-221、ミノルタ株式会社製)を用いて測定した値である。
本発明者らは、メタマテリアルとしての機能を生じさせる複数の金属構造体からなる金属パターンの腐食が生じることを初めて見出し、その腐食を抑制するために所定の透湿度の有機膜を用いることにより、金属パターンの腐食を抑制できることを見出している。
本発明の積層体の第1実施態様について図面を用いて説明する。
図1に示す積層体10Aは、誘電体フィルム12と、金属パターン14と、有機膜16とをこの順で有する。なお、図1においては、金属パターン14は、複数の金属構造体18から構成される。
後段で詳述するように、金属パターン14を構成する複数の金属構造体18は、テラヘルツ帯の電磁波に対して共振器として機能し得る。
以下、積層体を構成する各部材について詳述する。
誘電体フィルムとしては、公知の誘電体フィルムを用いることができる。
誘電体フィルムとしては、直流電圧に対して電気を通さない絶縁体であることが好ましい。
誘電体フィルムを構成する材料は特に制限されないが、取り扱い性等の点から、樹脂が好ましい。つまり、誘電体フィルムとしては、誘電体樹脂フィルムが好ましい。
誘電体樹脂フィルムを構成する樹脂としては、ポリエチレンテレフタレート(PET)及びポリエチレンナフタレート(PEN)等のポリエステル類、ポリエチレン(PE)、ポリプロピレン(PP)、ポリスチレン、エチレンビニルアセテート(EVA)、シクロオレフィンポリマー(COP)及びシクロオレフィンコポリマー(COC)等のポリオレフィン類、ビニル系樹脂、ポリカーボネート(PC)、ポリアミド、ポリイミド、アクリル樹脂、並びに、トリアセチルセルロース(TAC)が挙げられる。なかでも、シクロオレフィンポリマー、又は、シクロオレフィンコポリマーが好ましい。
誘電体フィルムの厚みが5μm以上であると取り扱い性に優れ、100μm以下であると金属パターンのメタマテリアルとしての機能がより発揮されやすい。
また、誘電体フィルムの厚みの面内方向のバラツキは、1μm以内であることが好ましい。
金属パターンは、テラヘルツ帯の電磁波(周波数が0.1~10THz(波長が30~3000μm)の電磁波)に対して共振器となる。より具体的には、金属パターンは複数の金属構造体からなり、金属構造体がテラヘルツ帯の電磁波に対して共振器となる。
金属構造体の形状やサイズは特に制限されないが、積層体にテラヘルツ帯の電磁波が入射すると、入射した電磁波の電界や磁界との相互作用によって、金属構造体内又は隣接する金属構造体間において電荷の偏りや電流が発生し、誘電的又は磁性的な応答変化を誘起するような形状で、入射する電磁波の波長のサイズ以下であることが好ましい。このような金属パターンは、いわゆるメタマテリアルとして機能し得る。
上記金属構造体の最大長さとは、金属構造体の一端から他端まで直線を引いた際に最も長くなる長さである。
また、積層体をテラヘルツ帯の電磁波に対するシート型コリメートレンズとして適用する際には、誘電体フィルムの面内方向において、テラヘルツ帯の電磁波に対して、2倍以上の屈折率差が生じるような屈折率分布が生じるように、金属構造体を配置することが好ましい。
また、積層体の中心から外側の領域にいくに従って、テラヘルツ帯の電磁波の位相シフト量が連続的に増大又は減少するような周期構造を形成するように、金属構造体を誘電体フィルム上に配置してもよい。このように金属構造体を配置する際には、積層体の中心から同心円状に配列された3つ以上の領域に分けて、金属構造体を配置してもよい。その際、各同心円状の直径の変化幅は、10~200μmであることが好ましい。
有機膜は、上述した金属パターンの腐食を防止するための役割を有する。有機膜は、金属パターンを覆うように、金属パターン上に配置される。
有機膜は、温度40℃、相対湿度90%の環境下における透湿度(水蒸気透過率)が3000g/(m2・24hr)以下である膜である。
上記透湿度は、金属パターンの腐食がより抑制される点(以下、単に「本発明の効果がより優れる点」ともいう。)で、2000g/(m2・24hr)以下が好ましく、1000g/(m2・24hr)以下がより好ましい。下限は特に制限されないが、150g/(m2・24hr)以上の場合が多く、250g/(m2・24hr)以上の場合がより多い。
上記透湿度の測定方法は、以下の通りである。
有機膜を5層積層させた測定サンプルを用意し、測定条件:温度40℃、相対湿度90%にて、測定サンプルを24時間静置した後、その測定条件にてJIS Z 0208記載の方法により、透湿度の測定を行う。得られた測定値を5倍にして、1層あたりの透湿度を算出する。
上記操作を5つの測定サンプルに対して実施して、5つの1層あたりの透湿度の値を求め、これらの数値を算術平均して、本発明の透湿度とする。
なお、上記有機膜を5層積層させた測定サンプルの作製方法としては、例えば、後述する実施例にて記載するように、有機膜となり得る硬化性組成物層を含む転写フィルムを用いて、硬化性組成物層を5回ラミネートして、得られた積層体に対して硬化処理を施して、有機膜が5層積層された測定サンプルを作製する方法が挙げられる。
ポリマーとしては、例えば、飽和又は不飽和のポリエステル樹脂、(メタ)アクリル樹脂、アクリルウレタン樹脂、ポリエステルアクリレート樹脂、ポリウレタンアクリレート樹脂、エポキシアクリレート樹脂、ウレタン樹脂、エポキシ樹脂、ビニル樹脂、ポリカーボネート樹脂、セルロース樹脂、アセタール樹脂、ポリエチレン樹脂、ポリスチレン樹脂、ポリアミド樹脂、ポリイミド樹脂、メラミン樹脂、フェノール樹脂、及び、シリコーン樹脂が挙げられる。
なお、有機膜が後述する硬化性組成物層を用いて形成される際に、硬化性組成物層に含まれるポリマーが反応性基を含む場合、ポリマーの反応物が有機膜に含まれることになる。
なお、ポリマーの酸価は、JIS K0070:1992に記載の方法に従って、測定される値である。
有機膜に含まれていてもよい複素環化合物としては、後述する硬化性組成物層に含まれていてもよい複素環化合物が挙げられ、詳細は後段で記載する。
有機膜は、1種単独の複素環化合物を含んでいてもよく、2種以上の複素環化合物を含んでいてもよい。
上記積層体は、誘電体フィルム、金属パターン、及び、有機膜以外の他の構成を含んでいてもよい。
また、有機膜上には、更に金属パターン及び有機膜が繰り返し積層されていてもよい。
上述した積層体の製造方法は特に制限されず、公知の方法により製造できる。
例えば、誘電体フィルム、及び、誘電体フィルムの少なくとも一方の表面側に配置された、テラヘルツ帯の電磁波に対して共振器となる金属パターンを含む金属パターン付きフィルム(以下、単に「金属パターン付きフィルムA」ともいう。)の金属パターン上に所定の有機膜を貼合する方法、金属パターン付きフィルムA上に硬化性組成物を塗布して、必要に応じて硬化処理を実施して、有機膜を形成する方法、並びに、仮支持体及び所定の成分を含む硬化性組成物層を含む転写フィルムを用いる方法が挙げられる。
転写フィルムを用いる方法としては、金属パターン付きフィルムAと、仮支持体及び硬化性組成物層を含む転写フィルムとを貼合して、誘電体フィルム、金属パターン、硬化性組成物層、及び、仮支持体をこの順で有する前駆体フィルムを形成する工程1Aと、硬化性組成物層に硬化処理を施して、上述した有機膜を得る工程2Aとを有し、工程1Aと工程2Aとの間、又は、工程2Aの後に、仮支持体を剥離する工程3Aを更に有する方法が好ましい。
以下、転写フィルムを用いる方法について詳述する。なお、転写フィルムの構成自体に関しては、後段で詳述する。
転写フィルムを用いる方法においては、誘電体フィルム、及び、誘電体フィルムの少なくとも一方の表面側に配置された、テラヘルツ帯の電磁波に対して共振器となる金属パターンを含む金属パターン付きフィルムAが用いられる。
金属パターン付きフィルムAに含まれる金属パターンの構成は、上述した積層体中の金属パターンの構成と同様である。
上記金属パターン付きフィルムAの製造方法は特に制限されず、誘電体フィルム上に金属層を形成して、金属層上に所定のレジストパターンを配置して、レジストパターンで覆われていない金属層をエッチング除去し、レジストパターンを剥離することにより、金属パターン付きフィルムを製造できる。
工程1Aは、金属パターン付きフィルムAと、仮支持体及び硬化性組成物層を含む転写フィルムとを貼合して、誘電体フィルム、金属パターン、硬化性組成物層、及び、仮支持体をこの順で有する前駆体フィルムを形成する工程である。
上記貼合においては、上記金属パターンと上記硬化性組成物層の表面と、が接触するように圧着させることが好ましい。
上記圧着の方法としては特に制限はなく、公知の転写方法、及び、ラミネート方法を用いることができる。なかでも、硬化性組成物層の表面を、金属パターンを有する誘電体フィルムに重ね、ロール等による加圧及び加熱することに行われることが好ましい。
貼り合せには、真空ラミネーター、及び、オートカットラミネーター等の公知のラミネーターを使用できる。
工程2Aは、硬化性組成物層に硬化処理を施して、有機膜を得る工程である。
硬化処理としては、使用される硬化性組成物に応じて適宜選択され、硬化性組成物が熱硬化性組成物である場合には加熱処理が選択され、硬化性組成物が光硬化性組成物である場合には露光処理が挙げられる。また、露光処理と加熱処理とを順次又は同時に実施してもよい。
加熱処理の条件は特に制限されず、加熱温度としては100~200℃が好ましく、110~180℃がより好ましく、120~170℃が更に好ましい。加熱時間としては、0.05~5時間が好ましく、0.08~3時間がより好ましく、0.1~1時間が更に好ましい。
露光の光源としては、少なくとも硬化性組成物を硬化し得る波長域の光(例えば、365nm又は405nm)を照射できるものであれば適宜選定して用いることができる。なかでも、露光の露光光の主波長は、365nmが好ましい。なお、主波長とは、最も強度が高い波長である。
露光量は、5~200mJ/cm2が好ましく、10~200mJ/cm2がより好ましい。
工程3Aは、工程1Aと工程2Aとの間、又は、工程2Aの後に、仮支持体を剥離する工程である。
剥離方法は特に制限されず、特開2010-072589号公報の段落[0161]~[0162]に記載されたカバーフィルム剥離機構と同様の機構を用いることができる。
硬化工程においてパターン露光がなされた際に、必要に応じて、現像工程を実施してもよい。現像工程は、露光された硬化性組成物層を現像して、パターンを形成する工程である。
上記硬化性組成物層の現像は、現像液を用いて行うことができる。
現像液として、アルカリ性水溶液が好ましい。アルカリ性水溶液に含まれ得るアルカリ性化合物としては、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、及び、コリン(2-ヒドロキシエチルトリメチルアンモニウムヒドロキシド)が挙げられる。
ポスト露光工程及びポストベーク工程の両方を含む場合、ポスト露光の後、ポストベークを実施することが好ましい。
転写フィルムは、仮支持体と、仮支持体上に配置された硬化性組成物層とを有する。この硬化性組成物層を硬化させることにより、上述した有機膜が形成される。
以下では、まず、転写フィルムの構成について詳述する。
仮支持体は、後述する硬化性組成物層を支持する部材であり、最終的には剥離処理により除去される。
仮支持体は、フィルムであることが好ましく、樹脂フィルムであることがより好ましい。仮支持体としては、可撓性を有し、かつ、加圧下、又は、加圧及び加熱下において、著しい変形、収縮、又は伸びを生じないフィルムを用いることができる。
このようなフィルムとして、ポリエチレンテレフタレートフィルム(例えば、2軸延伸ポリエチレンテレフタレートフィルム)、トリ酢酸セルロースフィルム、ポリスチレンフィルム、ポリイミドフィルム、及び、ポリカーボネートフィルムが挙げられる。
これらの中でも、仮支持体としては、2軸延伸ポリエチレンテレフタレートフィルムが好ましい。
また、仮支持体として使用するフィルムには、シワ等の変形、及び、傷等がないことが好ましい。
仮支持体を介するパターン露光時のパターン形成性、及び、仮支持体の透明性の点から、仮支持体のヘイズは小さい方が好ましい。具体的には、仮支持体のヘイズ値が、2%以下が好ましく、0.5%以下がより好ましく、0.1%以下が更に好ましい。
仮支持体を介するパターン露光時のパターン形成性、及び、仮支持体の透明性の点から、仮支持体に含まれる微粒子、異物及び欠陥の数は少ない方が好ましい。直径1μm以上の微粒子、異物及び欠陥の数は、50個/10mm2以下が好ましく、10個/10mm2以下がより好ましく、3個/10mm2以下が更に好ましく、0個/10mm2が特に好ましい。
転写フィルムは、硬化性組成物層を有する。硬化性組成物層を金属パターン上に転写した後、硬化処理を行うことにより、上述した有機膜を形成できる。
硬化性組成物層は、熱硬化性組成物層であってもよいし、光硬化性組成物層であってもよい。
以下、硬化性組成物層に含まれる成分について詳述する。
硬化性組成物層は、バインダーポリマーを含んでいてもよい。
バインダーポリマーの好適態様の一つとして、アルカリ現像性及びフィルム形成性に優れる点で、(メタ)アクリル樹脂が挙げられる。
なお、本明細書において、(メタ)アクリル樹脂とは、(メタ)アクリル化合物に由来する構成単位を有する樹脂を意味する。(メタ)アクリル化合物に由来する構成単位の含有量は、(メタ)アクリル樹脂の全構成単位に対して、50質量%以上が好ましく、70質量%以上がより好ましく、90質量%以上が更に好ましい。
(メタ)アクリル樹脂は、(メタ)アクリル化合物に由来する構成単位のみで構成されていてもよく、(メタ)アクリル化合物以外の重合性単量体に由来する構成単位を有していてもよい。すなわち、(メタ)アクリル化合物に由来する構成単位の含有量の上限は、(メタ)アクリル樹脂の全構成単位に対して、100質量%以下である。
(メタ)アクリル酸エステルとしては、例えば、(メタ)アクリル酸アルキルエステル、(メタ)アクリル酸テトラヒドロフルフリルエステル、(メタ)アクリル酸ジメチルアミノエチルエステル、(メタ)アクリル酸ジエチルアミノエチルエステル、(メタ)アクリル酸グリシジルエステル、(メタ)アクリル酸ベンジルエステル、2,2,2-トリフルオロエチル(メタ)アクリレート、及び、2,2,3,3-テトラフルオロプロピル(メタ)アクリレートが挙げられ、(メタ)アクリル酸アルキルエステルが好ましい。
(メタ)アクリルアミドとしては、例えば、ジアセトンアクリルアミド等のアクリルアミドが挙げられる。
(メタ)アクリル酸エステルとしては、炭素数1~4のアルキル基を有する(メタ)アクリル酸アルキルエステルが好ましく、(メタ)アクリル酸メチル又は(メタ)アクリル酸エチルがより好ましい。
上記構成単位を形成する重合性単量体としては、(メタ)アクリル化合物と共重合可能な(メタ)アクリル化合物以外の化合物であれば特に制限されず、例えば、スチレン、ビニルトルエン、及び、α-メチルスチレン等のα位又は芳香族環に置換基を有してもよいスチレン化合物、アクリロニトリル及びビニル-n-ブチルエーテル等のビニルアルコールエステル、マレイン酸、マレイン酸無水物、マレイン酸モノメチル、マレイン酸モノエチル、及び、マレイン酸モノイソプロピル等のマレイン酸モノエステル、フマール酸、ケイ皮酸、α-シアノケイ皮酸、イタコン酸、並びに、クロトン酸が挙げられる。
これらの重合性単量体は、1種又は2種以上を組み合わせて用いてもよい。
なかでも、(メタ)アクリル樹脂は、カルボキシ基を有する構成単位を有することがより好ましく、上記の(メタ)アクリル酸に由来する構成単位を有することが更に好ましい。
(メタ)アクリル酸アルキルエステルに由来する構成単位を有する場合、(メタ)アクリル樹脂における(メタ)アクリル酸アルキルエステルに由来する構成単位の含有量は、(メタ)アクリル樹脂の全構成単位に対して、1~90質量%が好ましく、1~50質量%がより好ましく、1~30質量%が更に好ましい。
また、(メタ)アクリル樹脂としては、メタクリル酸に由来する構成単位、メタクリル酸メチルに由来する構成単位、及び、アクリル酸エチルに由来する構成単位を有するアクリル樹脂も好ましい。
(メタ)アクリル樹脂におけるメタクリル酸に由来する構成単位及びメタクリル酸アルキルエステルに由来する構成単位の合計含有量は、本発明の効果がより優れる点から、(メタ)アクリル樹脂の全構成単位に対して、40質量%以上が好ましく、60質量%以上がより好ましい。上限は特に制限されず、100質量%以下であってもよく、80質量%以下が好ましい。
本発明の効果がより優れる点から、メタクリル酸に由来する構成単位及びメタクリル酸アルキルエステルに由来する構成単位の合計含有量は、アクリル酸に由来する構成単位及びアクリル酸アルキルエステルに由来する構成単位の合計含有量に対して、質量比で60/40~80/20が好ましい。
なお、(メタ)アクリル樹脂の末端部は、合成に用いた重合開始剤に由来する部位により構成される。末端にエステル基を有する(メタ)アクリル樹脂は、エステル基を有するラジカルを発生する重合開始剤を用いることにより合成できる。
バインダーポリマーは、例えば、現像性の点から、酸価60mgKOH/g以上のバインダーポリマーであることも好ましい。
また、バインダーポリマーは、例えば、加熱により架橋成分と熱架橋し、強固な膜を形成しやすいという点から、酸価60mgKOH/g以上のカルボキシ基を有する樹脂(いわゆる、カルボキシ基含有樹脂)であることがより好ましく、酸価60mgKOH/g以上のカルボキシ基を有する(メタ)アクリル樹脂(いわゆる、カルボキシ基含有(メタ)アクリル樹脂)であることが更に好ましい。
バインダーポリマーがカルボキシ基を有する樹脂であると、例えば、ブロックイソシアネート化合物等の熱架橋性化合物を添加して熱架橋することで、3次元架橋密度を高めることができる。また、カルボキシ基を有する樹脂のカルボキシ基が無水化され、疎水化すると、湿熱耐性が改善し得る。
例えば、特開2011-095716号公報の段落[0025]に記載のポリマーのうち、酸価60mgKOH/g以上のカルボキシ基含有アクリル樹脂、特開2010-237589号公報の段落[0033]~[0052]に記載のポリマーのうち、酸価60mgKOH/g以上のカルボキシ基含有アクリル樹脂等を好ましく使用できる。
なお、本明細書において、スチレン-アクリル共重合体とは、スチレン化合物に由来する構成単位と、(メタ)アクリル化合物に由来する構成単位とを有する樹脂を指し、上記スチレン化合物に由来する構成単位、及び、上記(メタ)アクリル化合物に由来する構成単位の合計含有量は、上記共重合体の全構成単位に対して、30質量%以上が好ましく、50質量%以上がより好ましい。
また、スチレン化合物に由来する構成単位の含有量は、上記共重合体の全構成単位に対して、1質量%以上が好ましく、5質量%以上がより好ましく、5~80質量%が更に好ましい。
また、上記(メタ)アクリル化合物に由来する構成単位の含有量は、上記共重合体の全構成単位に対して、5質量%以上が好ましく、10質量%以上がより好ましく、20~95質量%が更に好ましい。
芳香環構造を有する構成単位を形成するモノマーとしては、アラルキル基を有するモノマー、スチレン、及び重合可能なスチレン誘導体(例えば、メチルスチレン、ビニルトルエン、tert-ブトキシスチレン、アセトキシスチレン、4-ビニル安息香酸、スチレンダイマー、及びスチレントリマー等)が挙げられる。なかでも、アラルキル基を有するモノマー、又はスチレンが好ましい。アラルキル基としては、置換又は非置換のフェニルアルキル基(ベンジル基を除く)、及び置換又は非置換のベンジル基等が挙げられ、置換又は非置換のベンジル基が好ましい。
また、バインダーポリマーにおける芳香環構造を有する構成単位の含有量は、本発明の効果がより優れる点から、バインダーポリマーの全構成単位に対して、5~70モル%が好ましく、10~60モル%がより好ましく、20~60モル%が更に好ましい。
更に、バインダーポリマーにおける上記式(S)で表される構成単位の含有量は、本発明の効果がより優れる点から、バインダーポリマーの全構成単位に対して、5~70モル%が好ましく、10~60モル%がより好ましく、20~60モル%が更に好ましく、20~50モル%が特に好ましい。
なお、本明細書において、「構成単位」の含有量をモル比で規定する場合、上記「構成単位」は「モノマー単位」と同義であるものとする。また、本明細書において、上記「モノマー単位」は、高分子反応等により重合後に修飾されていてもよい。以下においても同様である。
なかでも、本発明の効果がより優れる点から、2環以上の脂肪族炭化水素環が縮環した環が好ましく、テトラヒドロジシクロペンタジエン環(トリシクロ[5.2.1.02,6]デカン環)がより好ましい。
脂肪族炭化水素環構造を有する構成単位を形成するモノマーとしては、ジシクロペンタニル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、及び、イソボルニル(メタ)アクリレートが挙げられる。
また、バインダーポリマーは、本発明の効果がより優れる点から、下記式(Cy)で表される構成単位を有することが好ましく、上記式(S)で表される構成単位、及び、下記式(Cy)で表される構成単位を有することがより好ましい。
式(Cy)におけるRCyは、本発明の効果がより優れる点から、炭素数5~20の脂肪族炭化水素環構造を有する一価の基であることが好ましく、炭素数6~16の脂肪族炭化水素環構造を有する一価の基であることがより好ましく、炭素数8~14の脂肪族炭化水素環構造を有する一価の基であることが更に好ましい。
また、式(Cy)のRCyにおける脂肪族炭化水素環構造は、本発明の効果がより優れる点から、シクロペンタン環構造、シクロヘキサン環構造、テトラヒドロジシクロペンタジエン環構造、ノルボルナン環構造、又は、イソボロン環構造であることが好ましく、シクロヘキサン環構造、又は、テトラヒドロジシクロペンタジエン環構造であることがより好ましく、テトラヒドロジシクロペンタジエン環構造であることが更に好ましい。
更に、式(Cy)のRCyにおける脂肪族炭化水素環構造は、本発明の効果がより優れる点から、2環以上の脂肪族炭化水素環が縮環した環構造であることが好ましく、2~4環の脂肪族炭化水素環が縮環した環構造であることがより好ましい。
更に、式(Cy)におけるRCyは、本発明の効果がより優れる点から、式(Cy)における-C(=O)O-の酸素原子と脂肪族炭化水素環構造とが直接結合する基、すなわち、脂肪族炭化水素環基であることが好ましく、シクロヘキシル基、又は、ジシクロペンタニル基であることがより好ましく、ジシクロペンタニル基であることが更に好ましい。
バインダーポリマーが脂肪族炭化水素環構造を有する構成単位を有する場合、脂肪族炭化水素環構造を有する構成単位の含有量は、本発明の効果がより優れる点から、バインダーポリマーの全構成単位に対して、5~90質量%が好ましく、10~80質量%がより好ましく、20~70質量%が更に好ましい。
また、バインダーポリマーにおける脂肪族炭化水素環構造を有する構成単位の含有量は、本発明の効果がより優れる点から、バインダーポリマーの全構成単位に対して、5~70モル%が好ましく、10~60モル%がより好ましく、20~50モル%が更に好ましい。
更に、バインダーポリマーにおける上記式(Cy)で表される構成単位の含有量は、本発明の効果がより優れる点から、バインダーポリマーの全構成単位に対して、5~70モル%が好ましく、10~60モル%がより好ましく、20~50モル%が更に好ましい。
また、バインダーポリマーにおける芳香環構造を有する構成単位及び脂肪族炭化水素環構造を有する構成単位の総含有量は、本発明の効果がより優れる点から、バインダーポリマーの全構成単位に対して、10~80モル%が好ましく、20~70モル%がより好ましく、40~60モル%が更に好ましい。
更に、バインダーポリマーにおける上記式(S)で表される構成単位及び上記式(Cy)で表される構成単位の総含有量は、本発明の効果がより優れる点から、バインダーポリマーの全構成単位に対して、10~80モル%が好ましく、20~70モル%がより好ましく、40~60モル%が更に好ましい。
また、バインダーポリマーにおける上記式(S)で表される構成単位のモル量nSと上記式(Cy)で表される構成単位のモル量nCyは、本発明の効果がより優れる点から、下記式(SCy)に示す関係を満たすことが好ましく、下記式(SCy-1)を満たすことがより好ましく、下記式(SCy-2)を満たすことが更に好ましい。
0.2≦nS/(nS+nCy)≦0.8 式(SCy)
0.30≦nS/(nS+nCy)≦0.75 式(SCy-1)
0.40≦nS/(nS+nCy)≦0.70 式(SCy-2)
上記酸基としては、カルボキシ基、スルホ基、ホスホン酸基、及び、リン酸基が挙げられ、カルボキシ基が好ましい。
上記酸基を有する構成単位としては、下記に示す、(メタ)アクリル酸由来の構成単位が好ましく、メタクリル酸由来の構成単位がより好ましい。
バインダーポリマーが酸基を有する構成単位を有する場合、酸基を有する構成単位の含有量は、本発明の効果がより優れる点から、バインダーポリマーの全構成単位に対して、5~50質量%が好ましく、5~40質量%がより好ましく、10~30質量%が更に好ましい。
また、バインダーポリマーにおける酸基を有する構成単位の含有量は、本発明の効果がより優れる点から、バインダーポリマーの全構成単位に対して、5~70モル%が好ましく、10~50モル%がより好ましく、20~40モル%が更に好ましい。
更に、バインダーポリマーにおける(メタ)アクリル酸由来の構成単位の含有量は、本発明の効果がより優れる点から、バインダーポリマーの全構成単位に対して、5~70モル%が好ましく、10~50モル%がより好ましく、20~40モル%が更に好ましい。
反応性基としては、ラジカル重合性基が好ましく、エチレン性不飽和基がより好ましい。また、バインダーポリマーがエチレン性不飽和基を有している場合、バインダーポリマーは、側鎖にエチレン性不飽和基を有する構成単位を有することが好ましい。つまり、バインダーポリマーとしては、側鎖にエチレン性不飽和基を有するバインダーポリマーが好ましい。
本明細書において、「主鎖」とは、樹脂を構成する高分子化合物の分子中で相対的に最も長い結合鎖を表し、「側鎖」とは、主鎖から枝分かれしている原子団を表す。
エチレン性不飽和基としては、アリル基又は(メタ)アクリロキシ基がより好ましい。
反応性基を有する構成単位の一例としては、下記に示すものが挙げられるが、これらに限定されない。
バインダーポリマーが反応性基を有する構成単位を有する場合、反応性基を有する構成単位の含有量は、本発明の効果がより優れる点から、バインダーポリマーの全構成単位に対して、5~70質量%が好ましく、10~50質量%がより好ましく、20~40質量%が更に好ましい。
また、バインダーポリマーにおける反応性基を有する構成単位の含有量は、本発明の効果がより優れる点から、バインダーポリマーの全構成単位に対して、5~70モル%が好ましく、10~60モル%がより好ましく、20~50モル%が更に好ましい。
反応性基をバインダーポリマーに導入する手段の好ましい例としては、カルボキシ基を有するポリマーを重合反応により合成した後、高分子反応により、得られたポリマーのカルボキシ基の一部にグリシジル(メタ)アクリレートを反応させて、(メタ)アクリロキシ基をポリマーに導入する手段が挙げられる。この手段により、側鎖に(メタ)アクリロキシ基を有するバインダーポリマーを得ることができる。
上記重合反応は、70~100℃の温度条件で行うことが好ましく、80~90℃の温度条件で行うことがより好ましい。上記重合反応に用いる重合開始剤としては、アゾ系開始剤が好ましく、例えば、富士フイルム和光純薬(株)製のV-601(商品名)又はV-65(商品名)がより好ましい。上記高分子反応は、80~110℃の温度条件で行うことが好ましい。上記高分子反応においては、アンモニウム塩等の触媒を用いることが好ましい。
カルボン酸無水物構造は、鎖状カルボン酸無水物構造、及び、環状カルボン酸無水物構造のいずれであってもよいが、環状カルボン酸無水物構造であることが好ましい。
環状カルボン酸無水物構造の環としては、5~7員環が好ましく、5員環又は6員環がより好ましく、5員環が更に好ましい。
Z1aとしては、炭素数2~4のアルキレン基が好ましく、炭素数2又は3のアルキレン基がより好ましく、炭素数2のアルキレン基が更に好ましい。
n1aは、0以上の整数を表す。Z1aが炭素数2~4のアルキレン基を表す場合、n1aは、0~4の整数であることが好ましく、0~2の整数であることがより好ましく、0であることが更に好ましい。
n1aが2以上の整数を表す場合、複数存在するRA1aは、同一でも異なっていてもよい。また、複数存在するRA1aは、互いに結合して環を形成してもよいが、互いに結合して環を形成していないことが好ましい。
有機膜が重合体Xを含む場合、重合体Xの含有量は、有機膜全質量に対して、0.1~30質量%が好ましく、0.2~20質量%がより好ましく、0.5~20質量%が更に好ましく、1~20質量%が更に好ましい。
シクロオレフィンポリマーとしては、上述した誘電体フィルムに含まれていてもよいシクロオレフィンポリマーが挙げられる。
バインダーポリマーの分散度は、現像性の点から、1.0~6.0が好ましく、1.0~5.0がより好ましく、1.0~4.0が更に好ましく、1.0~3.0が特に好ましい。
なお、バインダーポリマーの酸価は、JIS K0070:1992に記載の方法に従って、測定される値である。
また、硬化性組成物層は、硬化性化合物を含んでいてもよい。
硬化性化合物としては、光又は熱で硬化する化合物が好ましい。
光又は熱で硬化する化合物としては、エチレン性不飽和二重結合を有する化合物、共役ジエン部位を有する化合物、マレイミド部位を有する化合物、エン-チオール反応により硬化するチオール化合物、エポキシ化合物、及び、酸の作用により架橋する基を有する化合物が挙げられる。硬化性の点から、エチレン性不飽和二重結合を有する化合物が好ましい。硬化性の点、及び、アルカリ可溶性樹脂との相溶性の点から、硬化性化合物としては、分子内にアクリロイル基を有する化合物がより好ましい。
このような化合物としては、ポリエチレングリコールをフェニル基に付加した化合物の(メタ)アクリレートであるフェノキシヘキサエチレングリコールモノ(メタ)アクリレート、又は、平均2モルのプロピレンオキサイドを付加したポリプロピレングリコールと平均7モルのエチレンオキサイドを付加したポリエチレングリコールをノニルフェノールに付加した化合物の(メタ)アクリレートである4-ノルマルノニルフェノキシヘプタエチレングリコールジプロピレングリコール(メタ)アクリレート、平均1モルのプロピレンオキサイドを付加したポリプロピレングリコールと平均5モルのエチレンオキサイドを付加したポリエチレングリコールをノニルフェノールに付加した化合物の(メタ)アクリレートである4-ノルマルノニルフェノキシペンタエチレングリコールモノプロピレングリコール(メタ)アクリレートが挙げられる。平均8モルのエチレンオキサイドを付加したポリエチレングリコールをノニルフェノールに付加した化合物のアクリレートである4-ノルマルノニルフェノキシオクタエチレングリコール(メタ)アクリレート(東亞合成(株)製、M-114)も挙げられる。
このような化合物としては、テトラエチレングリコールジ(メタ)アクリレート、ペンタエチレングリコールジ(メタ)アクリレート、ヘキサエチレングリコールジ(メタ)アクリレート、ヘプタエチレングリコールジ(メタ)アクリレート、オクタエチレングリコールジ(メタ)アクリレート、ノナエチレングリコールジ(メタ)アクリレート、デカエチレングリコールジ(メタ)アクリレート、及び、12モルのエチレンオキシド鎖の両末端に(メタ)アクリロイル基を有する化合物が挙げられる。
さらに、化合物中に少なくともエチレンオキシド基とプロピレンオキシド基とを含むポリアルキレンオキシドジ(メタ)アクリレート化合物が解像性、柔軟性、耐めっき性の点から好ましい。同様の点から、上記化合物の分子量は、600~1500が好ましく、900~1300がより好ましく、1000~1200が更に好ましい。
化合物中に少なくともエチレンオキシド基とプロピレンオキシド基とを含むポリアルキレンオキシドジ(メタ)アクリレート化合物としては、例えば、平均12モルのプロピレンオキシドを付加したポリプロピレングリコールにエチレンオキシドをさらに両端にそれぞれ平均3モル付加したグリコールのジメタクリレート、及び、平均18モルのプロピレンオキシドを付加したポリプロピレングリコールにエチレンオキシドをさらに両端にそれぞれ平均15モル付加したグリコールのジメタクリレートが挙げられる。
アルキレンオキシド変性としては、エチレンオキシド変性、プロピレンオキシド変性、ブチレンオキシド変性、ペンチレンオキシド変性、及び、へキシレンオキシド変性が挙げられる。上記化合物としては、ビスフェノールAにエチレンオキシド変性し、両末端に(メタ)アクリロイル基を有する化合物が好ましい。このような化合物としては、例えば、2,2-ビス(4-((メタ)アクリロキシジエトキシ)フェニル)プロパン(新中村化学工業(株)製NKエステルBPE-200)、2,2-ビス(4-((メタ)アクリロキシトリエトキシ)フェニル)プロパン、2,2-ビス(4-((メタ)アクリロキシテトラエトキシ)フェニル)プロパン、2,2-ビス(4-((メタ)アクリロキシペンタエトキシ)フェニル)プロパン(新中村化学工業(株)製NKエステルBPE-500)、2,2-ビス(4-((メタ)アクリロキシヘキサエトキシ)フェニル)プロパン、2,2-ビス(4-((メタ)アクリロキシヘプタエトキシ)フェニル)プロパン、2,2-ビス(4-((メタ)アクリロキシオクタエトキシ)フェニル)プロパン、2,2-ビス(4-((メタ)アクリロキシノナエトキシ)フェニル)プロパン、2,2-ビス(4-((メタ)アクリロキシデカエトキシ)フェニル)プロパン、2,2-ビス(4-((メタ)アクリロキシウンデカエトキシ)フェニル)プロパン、2,2-ビス(4-((メタ)アクリロキシドデカエトキシ)フェニル)プロパン、2,2-ビス(4-((メタ)アクリロキシトリデカエトキシ)フェニル)プロパン、2,2-ビス(4-((メタ)アクリロキシテトラデカエトキシ)フェニル)プロパン、2,2-ビス(4-((メタ)アクリロキシペンタデカエトキシ)フェニル)プロパン、及び、2,2-ビス(4-((メタ)アクリロキシヘキサデカエトキシ)フェニル)プロパン等の2,2-ビス(4-((メタ)アクリロキシポリエトキシ)フェニル)プロパンが挙げられる。
例えば、1,6-ヘキサンジオールジ(メタ)アクリレート、1,4-シクロヘキサンジオールジ(メタ)アクリレート、2-ジ(p-ヒドロキシフェニル)プロパンジ(メタ)アクリレート、2,2-ビス[(4-(メタ)アクリロキシポリプロピレンオキシ)フェニル]プロパン、2,2-ビス[(4-(メタ)アクリロキシポリブチレンオキシ)フェニル]プロパン、グリセロールトリ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ポリオキシプロピルトリメチロールプロパントリ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、トリメチロールプロパントリグリシジルエーテルトリ(メタ)アクリレート、β-ヒドロキシプロピル-β’-(アクリロイルキシ)プロピルフタレート、ノニルフェノキシポリプロピレングリコール(メタ)アクリレート、ノニルフェノキシポリブチレングリコール(メタ)アクリレート、及び、ポリプロピレングリコールモノ(メタ)アクリレートが挙げられる。
さらに以下のようなウレタン化合物も挙げられる。例えば、ヘキサメチレンジイソシアネート、トリレンジイソシアネート又はジイソシアネート化合物(例えば、2,2,4-トリメチルヘキサメチレンジイソシアネート)と、一分子中にヒドロキシル基と(メタ)アクリル基を有する化合物、例えば、2-ヒドロキシプロピルアクリレート、オリゴプロピレングリコールモノメタクリレートとのウレタン化合物が挙げられる。具体的には、ヘキサメチレンジイソシアネートとオリゴプロピレングリコールモノメタクリレート(日本油脂(株)製、ブレンマーPP1000)との反応生成物がある。また、ポリプロピレングリコール又はポリカプロラクトンにより変性したイソシアヌル酸エステルのジ又はトリ(メタ)アクリレート等も挙げられる。また、例えばジイソシアネートとポリオールとの重付加物として得られるウレタン化合物の末端とエチレン性不飽和二重結合及びヒドロキシル基を有する化合物とを反応させて得られるウレタンオリゴマーも挙げられる。
マレイミド部位を有する化合物としては、側鎖にマレイミド基を有する高分子化合物、分子内にマレイミド基を2つ以上有する化合物、及び、(メタ)アクリロイル基とマレイミド基を分子内に有する化合物が挙げられる。
エン-チオール反応により硬化するチオール化合物としては、ペンタエリスリトールテトラキスチオプロピオネート、ペンタエリスリトールテトラキス(3-メルカプトブチレート)、及び、1,3,5-トリス(3-メルカブトブチルオキシエチル)-1,3,5-トリアジン-2,4,6(1H,3H,5H)-トリオン等の脂肪族チオール基を有する化合物が挙げられる。
環式エポキシ化合物は、少なくとも1つの脂環式エポキシ基を有する。ここで脂環式エポキシ基とは、エポキシ環と飽和炭化水素環との縮環を有する1価の置換基をいい、好ましくはエポキシ環とシクロアルカン環との縮環を有する1価の置換基である。
脂環式エポキシ化合物として好適に使用できる市販品としては、ダイセル化学工業(株)のセロキサイド(登録商標)2000、セロキサイド2021P、セロキサイド3000、セロキサイド8000、サイクロマー(登録商標)M100、エポリードGT301、エポリードGT401、シグマアルドリッチ社製の4-ビニルシクロヘキセンジオキシド、日本テルペン化学(株)のD-リモネンオキサイド、新日本理化(株)のサンソサイザー(登録商標)E-PSが挙げられる。
これらは、1種単独で、又は2種以上組み合わせて用いることができる。
アルコキシメチル化アミノ樹脂は、例えば、沸騰水溶液中でメラミン又は尿素をホルマリンと反応させて得た縮合物を、メチルアルコール、エチルアルコール、プロピルアルコール、ブチルアルコール、及び、イソプロピルアルコール等の低級アルコール類と反応させてエーテルを形成し、次いで反応液を冷却して析出させることで製造できる。
アルコキシメチル化アミノ樹脂としては、具体的にメトキシメチル化メラミン樹脂、エトキシメチル化メラミン樹脂、プロポキシメチル化メラミン樹脂、ブトキシメチル化メラミン樹脂、メトキシメチル化尿素樹脂、エトキシメチル化尿素樹脂、プロポキシメチル化尿素樹脂、及び、ブトキシメチル化尿素樹脂が挙げられる。
アルコキシメチル化アミノ樹脂は、単独又は2種以上を組み合わせて用いることができる。メトキシメチル化メラミン樹脂、エトキシメチル化メラミン樹脂、プロポキシメチル化メラミン樹脂又はブトキシメチル化メラミン樹脂が好適である。
メラミン樹脂の具体例としては、メラミン、メチロールメラミン、エーテル化メチロールメラミン、ベンゾグアナミン、メチロールベンゾグアナミン、エーテル化メチロールベンゾグアナミン、及びそれらの縮合物が挙げられる。中でも、耐薬品性が良好であることから、エーテル化メチロールメラミンが好ましい。エーテル化メチロールメラミン及びその縮合物の混合物は、三和ケミカル(株)製のニカラックMW-30(商品名)として市販されている。
多価イソシアネート(2官能以上のイソシアネート)としては、フェニレン-1,3-ジイソシアネート、フェニレン-1,4-ジイソシアネート、1-メトキシフェニレン-2,4-ジイソシアネート、1-メチルフェニレン-2,4-ジイソシアネート、2,4-トリレンジイソシアネート、2,6-トリレンジイソシアネート、1,3-キシリレンジイソシアネート、1,4-キシリレンジイソシアネート、ビフェニレン-4,4-ジイソシアネート、3,3-ジメトキシビフェニレン-4,4-ジイソシアネート、3,3-ジメチルビフェニレン-4,4-ジイソシアネート、ジフェニルメタン-2,4-ジイソシアネート、ジフェニルメタン-4,4-ジイソシアネート、3,3-ジメトキシジフェニルメタン-4,4-ジイソシアネート、3,3-ジメチルジフェニルメタン-4,4-ジイソシアネート、ナフチレン-1,5-ジイソシアネート、シクロブチレン-1,3-ジイソシアネート、シクロペンチレン-1,3-ジイソシアネート、シクロヘキシレン-1,3-ジイソシアネート、シクロヘキシレン-1,4-ジイソシアネート、1-メチルシクロヘキシレン-2,4-ジイソシアネート、1-メチルシクロヘキシレン-2,6-ジイソシアネート、1-イソシアネート-3,3,5-トリメチル-5-イソシアネートメチルシクロヘキサン、シクロヘキサン-1,3-ビス(メチルイソシアネート)、シクロヘキサン-1,4-ビス(メチルイソシアネート)、イソホロンジイソシアネート、ジシクロヘキシルメタン-2,4-ジイソシアネート、ジシクロヘキシルメタン-4,4-ジイソシアネート、エチレンジイソシアネート、テトラメチレン-1,4-ジイソシアネート、ヘキサメチレン-1,6-ジイソシアネート、ドデカメチレン-1,12-ジイソシアネート、又は、これらの有機ジイソシアネートの化学量論的過剰量と2官能性活性水素含有化合物との反応により得られる両末端イソシアネートプレポリマーが挙げられる。
硬化性組成物層がエポキシ化合物を含む場合、硬化性組成物層はエポキシ硬化剤を含んでいてもよい。
エポキシ硬化剤としては、酸無水物系硬化剤、ポリアミン系硬化剤、触媒型硬化剤、及び、ポリカルボン酸系硬化剤が好ましい。
ポリアミン系硬化剤としては、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ジシアンジアミド、ポリアミドアミン(ポリアミド樹脂)、ケチミン化合物、イソホロンジアミン、m-キシレンジアミン、m-フェニレンジアミン、1,3-ビス(アミノメチル)シクロヘキサン、N-アミノエチルピペラジン、4,4’-ジアミノジフェニルメタン、4,4’-ジアミノ-3,3’-ジエチルジフェニルメタン、及び、ジアミノジフェニルスルフォンが挙げられる。
触媒型硬化剤としては、3級アミン化合物及びイミダゾール化合物が挙げられる。
ポリカルボン酸系硬化剤としては、無水フタル酸、無水トリメリット酸、無水ピロメリット酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、3,6-エンドメチレンテトラヒドロ無水フタル酸、ヘキサクロルエンドメチレンテトラヒドロ無水フタル酸、及び、メチル-3,6-エンドメチレンテトラヒドロ無水フタル酸が挙げられる。
硬化性組成物層は、重合開始剤を含んでいてもよい。
重合開始剤として、硬化性化合物の種類に応じて好適な重合開始剤を用いることが好ましく、光又は熱重合開始剤がより好ましい。光重合開始剤は、露光により分解してラジカル、酸等の開始種を発生させることができる化合物であり、この開始種により重合性化合物の重合反応を開始、促進させることができる化合物である。
芳香族ケトン類としては、ベンゾフェノン、ミヒラーズケトン[4,4’-ビス(ジメチルアミノ)ベンゾフェノン]、4,4’-ビス(ジエチルアミノ)ベンゾフェノン、及び、4-メトキシ-4’-ジメチルアミノベンゾフェノンが挙げられる。
アセトフェノン類としては、2-ヒドロキシ-2-メチル-1-フェニルプロパン-1-オン、1-(4-イソプロピルフェニル)-2-ヒドロキシ-2-メチルプロパン-1-オン、1-(4-ドデシルフェニル)-2-ヒドロキシ-2-メチルプロパン-1-オン、4-(2-ヒドロキシエトキシ)-フェニル(2-ヒドロキシ-2-プロピル)ケトン、1-ヒドロキシシクロヘキシルフェニルケトン、2-ベンジル-2-ジメチルアミノ-1-(4-モルホリノフェニル)-ブタノン-1、及び、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルフォリノ-プロパノン-1が挙げられる。市販品としては、チバ・スペシャリティ・ケミカルズ社製のイルガキュア-907、イルガキュア-369、イルガキュア-379が挙げられる。
ベンゾイン又はベンゾインエーテル類としては、ベンゾイン、ベンゾインエチルエーテル、ベンゾインフェニルエーテル、メチルベンゾイン、及び、エチルベンゾインが挙げられる。
ジアルキルケタール類としては、ベンジルジメチルケタール、及び、ベンジルジエチルケタールが挙げられる。
チオキサントン類としては、2,4-ジエチルチオキサントン、2,4-ジイソプロピルチオキサントン、及び、2-クロルチオキサントンが挙げられる。
ジアルキルアミノ安息香酸エステル類としては、ジメチルアミノ安息香酸エチル、ジエチルアミノ安息香酸エチル、エチル-p-ジメチルアミノベンゾエート、及び、2-エチルヘキシル-4-(ジメチルアミノ)ベンゾエートが挙げられる。
好ましい光カチオン重合開始剤としては、ヨードニウム塩化合物、スルホニウム塩化合物、ピリジニウム塩化合物、及び、ホスホニウム塩化合物が挙げられる。中でも、熱安定性に優れる点から、ヨードニウム塩化合物、又は、スルホニウム塩化合物が好ましい。
ヨードニウム塩化合物とは、構造中にI+を含むカチオン部と任意の構造のアニオン部とにより形成される塩であって、電子供与性基を3つ以上有し、これら電子供与性基の少なくとも1つがアルコキシ基であるジアリールヨードニウム塩が更に好ましい。このようにジアリールヨードニウム塩に電子供与性基であるアルコキシ基を導入することで、経時での水や求核剤による分解や、熱による電子移動が抑制することができること等により、安定性の向上が期待できる。
硬化性組成物層は、複素環化合物を含んでいてもよい。
複素環化合物が有する複素環は、単環及び多環のいずれの複素環でもよい。
複素環化合物が有するヘテロ原子としては、窒素原子、酸素原子、及び、硫黄原子が挙げられる。複素環化合物は、窒素原子、酸素原子、及び、硫黄原子からなる群より選ばれる少なくとも1種の原子を有することが好ましく、窒素原子を有することがより好ましい。
上記の中でも、複素環化合物としては、トリアゾール化合物、ベンゾトリアゾール化合物、テトラゾール化合物、チアジアゾール化合物、トリアジン化合物、ローダニン化合物、チアゾール化合物、ベンゾイミダゾール化合物、及び、ベンゾオキサゾール化合物からなる群より選ばれる少なくとも1種の化合物が好ましく、トリアゾール化合物、ベンゾトリアゾール化合物、テトラゾール化合物、チアジアゾール化合物、チアゾール化合物、ベンゾチアゾール化合物、ベンゾイミダゾール化合物、及び、ベンゾオキサゾール化合物からなる群より選ばれる少なくとも1種の化合物がより好ましい。
硬化性組成物層は、ブロックイソシアネートを含んでいてもよい。
ブロックイソシアネート化合物とは、「イソシアネートのイソシアネート基をブロック剤で保護(いわゆる、マスク)した構造を有する化合物」を指す。
ブロックイソシアネートの解離温度とは、「示差走査熱量計を用いて、DSC(Differential scanning calorimetry)分析にて測定した場合における、ブロックイソシアネートの脱保護反応に伴う吸熱ピークの温度」を意味する。
示差走査熱量計としては、例えば、セイコーインスツルメンツ社製の示差走査熱量計(型式:DSC6200)を好適に使用できる。但し、示差走査熱量計は、これに限定されない。
これらのなかでも、解離温度が100~160℃であるブロック剤としては、例えば、保存安定性の点から、オキシム化合物から選ばれる少なくとも1種が好ましい。
イソシアヌレート構造を有するブロックイソシアネート化合物は、例えば、ヘキサメチレンジイソシアネートをイソシアヌレート化して保護することにより得られる。
イソシアヌレート構造を有するブロックイソシアネート化合物のなかでも、オキシム化合物をブロック剤として用いたオキシム構造を有する化合物が、オキシム構造を有さない化合物よりも解離温度を好ましい範囲にしやすく、且つ、現像残渣を少なくしやすいという点から好ましい。
重合性基としては、特に制限はなく、公知の重合性基を用いることができ、ラジカル重合性基が好ましい。
重合性基としては、(メタ)アクリロキシ基、(メタ)アクリルアミド基、及びスチリル基等のエチレン性不飽和基、並びに、グリシジル基等のエポキシ基を有する基が挙げられる。
なかでも、重合性基としては、エチレン性不飽和基が好ましく、(メタ)アクリロキシ基がより好ましく、アクリロキシ基が更に好ましい。
ブロックイソシアネート化合物の市販品の例としては、カレンズ(登録商標) AOI-BM、カレンズ(登録商標) MOI-BM、カレンズ(登録商標) MOI-BP等(以上、昭和電工社製)、ブロック型のデュラネートシリーズ(例えば、デュラネート(登録商標) TPA-B80E、デュラネート(登録商標) WT32-B75P等、旭化成ケミカルズ社製)が挙げられる。
また、ブロックイソシアネート化合物として、下記の構造の化合物を用いることもできる。
硬化性組成物層は、脂肪族チオール化合物を含んでいてもよい。
硬化性組成物層が脂肪族チオール化合物を含むことで、脂肪族チオール化合物がエチレン性不飽和基を有するラジカル重合性化合物との間でエン-チオール反応することで、形成される膜の硬化収縮が抑えられ、応力が緩和される。
硬化性組成物層は、界面活性剤を含んでいてもよい。
界面活性剤としては、例えば、特許第4502784号公報の段落[0017]、及び特開2009-237362号公報の段落[0060]~[0071]に記載の界面活性剤が挙げられる。
また、フッ素系界面活性剤としては、フッ素原子を含有する官能基を持つ分子構造を有し、熱を加えるとフッ素原子を含有する官能基の部分が切断されてフッ素原子が揮発するアクリル系化合物も好適に使用できる。このようなフッ素系界面活性剤としては、DIC(株)製のメガファック DSシリーズ(化学工業日報(2016年2月22日)、日経産業新聞(2016年2月23日))、例えばメガファック DS-21が挙げられる。
また、フッ素系界面活性剤としては、フッ素化アルキル基またはフッ素化アルキレンエーテル基を有するフッ素原子含有ビニルエーテル化合物と、親水性のビニルエーテル化合物との重合体を用いることも好ましい。
また、フッ素系界面活性剤としては、ブロックポリマーも使用できる。
また、フッ素系界面活性剤としては、フッ素原子を有する(メタ)アクリレート化合物に由来する構成単位と、アルキレンオキシ基(好ましくはエチレンオキシ基、プロピレンオキシ基)を2以上(好ましくは5以上)有する(メタ)アクリレート化合物に由来する構成単位と、を含む含フッ素高分子化合物も好ましく使用できる。
また、フッ素系界面活性剤としては、エチレン性不飽和結合含有基を側鎖に有する含フッ素重合体も使用できる。メガファック RS-101、RS-102、RS-718K、RS-72-K(以上、DIC株式会社製)等が挙げられる。
炭化水素系界面活性剤としては、グリセロール、トリメチロールプロパン、トリメチロールエタン並びにそれらのエトキシレート及びプロポキシレート(例えば、グリセロールプロポキシレート、グリセロールエトキシレート等)、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート、ソルビタン脂肪酸エステル、等が挙げられる。
具体例としては、プルロニック L10、L31、L61、L62、10R5、17R2、25R2、テトロニック 304、701、704、901、904、150R1、HYDROPALAT WE 3323(以上、BASF社製)、ソルスパース 20000(以上、日本ルーブリゾール(株)製)、NCW-101、NCW-1001、NCW-1002(以上、富士フイルム和光純薬(株)製)、パイオニン D-1105、D-6112、D-6112-W、D-6315(以上、竹本油脂(株)製)、オルフィンE1010、サーフィノール104、400、440(以上、日信化学工業(株)製)等が挙げられる。
硬化性組成物層は、水素供与性化合物を含んでいてもよい。
水素供与性化合物は、光重合開始剤の活性光線に対する感度を一層向上させる、酸素による重合性化合物の重合阻害を抑制する等の作用を有する。
硬化性組成物層は、既述の成分以外の成分(以下、「他の成分」ともいう。)を含んでいてもよい。他の成分としては、例えば、粒子(例えば、金属酸化物粒子)、及び、着色剤が挙げられる。
また、他の成分としては、例えば、特許第4502784号公報の段落[0018]に記載の熱重合防止剤、及び、特開2000-310706号公報の段落[0058]~[0071]に記載のその他の添加剤も挙げられる。
金属酸化物粒子における金属には、B、Si、Ge、As、Sb、及び、Te等の半金属も含まれる。
硬化性組成物層が着色剤を含む場合、着色剤の含有量は、硬化性組成物層の全質量に対して、1質量%未満が好ましく、0.1質量%未満がより好ましい。
硬化性組成物層は、所定量の不純物を含んでいてもよい。
不純物の具体例としては、ナトリウム、カリウム、マグネシウム、カルシウム、鉄、マンガン、銅、アルミニウム、チタン、クロム、コバルト、ニッケル、亜鉛、スズ、ハロゲン及びこれらのイオンが挙げられる。中でも、ハロゲン化物イオン、ナトリウムイオン、及び、カリウムイオンは不純物として混入し易いため、下記の含有量にすることが好ましい。
硬化性組成物層の厚みの上限値は、塗布性の点から、20.0μm以下が好ましく、15.0μm以下がより好ましく、12.0μm以下が更に好ましい。
硬化性組成物の厚みの下限値は、0.05μm以上が好ましくい。
硬化性組成物層の厚みは、走査型電子顕微鏡(SEM)による断面観察により測定した任意の5点の平均値として算出する。
硬化性組成物層は無彩色であることが好ましい。硬化性組成物層のa*値は、-1.0~1.0であることが好ましく、硬化性組成物層のb*値は、-1.0~1.0であることが好ましい。
硬化性組成物層の色相は、色差計(CR-221、ミノルタ株式会社製)を用いて測定できる。
転写フィルムの製造方法は特に制限されず、公知の方法を用いることができる。
なかでも、生産性に優れる点で、仮支持体上に硬化性組成物を塗布し、必要に応じて乾燥処理を施し、硬化性組成物層を形成する方法(以下、この方法を「塗布方法」ともいう。)が好ましい。
溶剤としては、有機溶剤が好ましい。有機溶剤としては、例えば、メチルエチルケトン、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート(別名:1-メトキシ-2-プロピルアセテート)、ジエチレングリコールエチルメチルエーテル、シクロヘキサノン、メチルイソブチルケトン、乳酸エチル、乳酸メチル、カプロラクタム、n-プロパノール、及び、2-プロパノールが挙げられる。溶剤としては、メチルエチルケトンと、プロピレングリコールモノメチルエーテルアセテートとの混合溶剤、又は、ジエチレングリコールエチルメチルエーテルとプロピレングリコールモノメチルエーテルアセテートとの混合溶剤が好ましい。
硬化性組成物は、1種単独の溶剤を含んでいてもよく、2種以上の溶剤を含んでいてもよい。
本開示において、「乾燥」とは、組成物に含まれる溶剤の少なくとも一部を除去することを意味する。
保護フィルムを硬化性組成物層に貼り合わせる方法は特に制限されず、公知の方法が挙げられる。
保護フィルムを硬化性組成物層に貼り合わせる装置としては、真空ラミネーター、及び、オートカットラミネーター等の公知のラミネーターが挙げられる。
ラミネーターはゴムローラー等の任意の加熱可能なローラーを備え、加圧及び加熱ができるものであることが好ましい。
本発明の積層体の第2実施態様について図面を用いて説明する。
図3に示す積層体20は、誘電体フィルム22と、誘電体フィルム22の一方の表面側に配置された第1金属パターン24と、第1金属パターン24上に配置された第1有機膜26と、誘電体フィルム22の他方の表面側に配置された第2金属パターン28と、第1金属パターン28上に配置された第1有機膜30とを有する。
図3に示すように、第1金属パターン24は複数の第1金属構造体32により構成され、第2金属パターン28は複数の第2金属構造体34により構成される。
積層体20においては、第1金属パターン24と第2金属パターン28とが、テラヘルツ帯の電磁波に対して共振器を構成する。より具体的には、第1金属パターン24中の第1金属構造体32及び第2金属パターン28中の第2金属構造体34の間で、テラヘルツ帯の電磁波に対して共振が起こり、第1金属構造体32及び第2金属構造体34が1つの共振器として機能し得る。
また、第2実施態様に含まれる第1有機膜及び第2有機膜と、第1実施態様に含まれる有機膜とは同じ部材であり、説明を省略する。
なお、テラヘルツ帯の電磁波に対する共振の点からは、積層体を平面視した際に、第1金属パターンに含まれる第1金属構造体と、第2金属パターンに含まれる第2金属構造体とが、少なくとも一部重複するように配置されていることが好ましい。
また、積層体を平面視した際に、第1金属パターンに含まれる第1金属構造体と、第2金属パターンに含まれる第2金属構造体とが、重複しないように配置されていてもよいが、そのズレは20μm以下が好ましい。
積層体の第2実施態様の製造方法は特に制限されないが、誘電体フィルムと、誘電体フィルムの一方の表面側に配置された複数の第1金属構造体から構成された第1金属パターンと、誘電体フィルムの他方の表面側に配置された複数の第2金属構造体から構成された第2金属パターンを含み、第1金属パターンと第2金属パターンとがテラヘルツ帯の電磁波に対して共振器を構成する金属パターン付きフィルム(以下、単に「金属パターン付きフィルムB」ともいう。)と、仮支持体及び硬化性組成物層を含む転写フィルムとを貼合して、仮支持体、硬化性組成物層、第1金属パターン、誘電体フィルム、第2金属パターン、硬化性組成物層、及び、仮支持体をこの順で有する前駆体フィルムを形成する工程1Bと、硬化性組成物層に硬化処理を施して、有機膜を得る工程2Bとを、有し、工程1Bと工程2Bとの間、又は、工程2Bの後に、仮支持体を剥離する工程3Bを有する方法が好ましい。
以下、上記製造方法について詳述する。
上記方法においては、金属パターン付きフィルムBが用いられる。
金属パターン付きフィルムBに含まれる金属パターンの構成は、上述した積層体中の金属パターンの構成と同様である。
上記金属パターン付きフィルムBの製造方法は特に制限されず、誘電体フィルムの両面上に金属層を形成して、金属層上に所定のレジストパターンを配置して、レジストパターンで覆われていない金属層をエッチング除去し、レジストパターンを剥離することにより、金属パターン付きフィルムBを製造できる。
工程1Bは、金属パターン付きフィルムBと、仮支持体及び硬化性組成物層を含む転写フィルムとを貼合して、仮支持体、硬化性組成物層、第1金属パターン、誘電体フィルム、第2金属パターン、硬化性組成物層、及び、仮支持体をこの順で有する前駆体フィルムを形成する工程である。
本工程は2枚の転写フィルムを用意して、金属パターン付きフィルムBの両面に転写フィルムを貼合する。
貼合方法は、上述した工程1Aで述べた方法が挙げられる。
工程2Bは、硬化性組成物層に硬化処理を施して、有機膜を得る工程である。
本工程を実施することにより、第1金属パターン上には第1有機膜が、第2金属パターン上には第2有機膜が形成される。
硬化処理の方法は、上述した工程2Aで述べた方法が挙げられる。
工程3Bは、工程1Bと工程2Bとの間、又は、工程2Bの後に、仮支持体を剥離する工程である。
剥離方法は特に制限されず、特開2010-072589号公報の段落[0161]~[0162]に記載されたカバーフィルム剥離機構と同様の機構を用いることができる。
本発明の積層体は、種々の用途に適用できる。特に、本発明の積層体は、光学素子に含まれるシート型部材として用いることが好ましい。つまり、本発明の光学素子は、上述した積層体を含む。
光学素子としては、平板レンズ、回折格子、波長フィルタ、偏光子、および、センサーが挙げられる。
また、以下の実施例において、樹脂の重量平均分子量は、ゲルパーミエーションクロマトグラフィ(GPC)によるポリスチレン換算で求めた重量平均分子量である。また、酸価は、理論酸価を用いた。
(金属パターン付きフィルム1)
特許第4991170号記載の方法で、COPフィルムを作製した。COPフィルムの厚みは、50μmであった。
次に、COPフィルムの表面を超音波洗浄(45kHz)した後、スパッタリング成膜装置内部に、10cmサイズに切り出したフィルムを載置し、装置内部を減圧した後にアルゴンガスを導入し、ターゲットにCuを用いてスパッタリングを実施した。片面ずつ順に、両面に厚さ50nmの銅層を形成した。
図4に示すフォトマスク40は、長方形の開口部42が幅方向及び長方向に等間隔に複数配置されている。開口部42の長さLは313μmであり、幅Wは54μmである。開口部の長さ方向の開口部間の距離D1は94μmであり、開口部の幅方向の開口部間の距離D2は86μmであった。
露光された積層体から両面の仮支持体を剥離した後、積層体に対して、液温25℃の1.0%炭酸ナトリウム水溶液を用いて30秒間のシャワー現像を行い、銅層上にレジストパターンを形成した。
次いで得られた積層体に対して銅エッチング液(Cu-02:関東化学(株)製)により23℃で30秒エッチングし、更に、プロピレングリコールモノメチルエーテルアセテートを用いてレジストパターンを剥離することで、銅パターンが表裏にパターンニングされた金属パターン付きフィルム1を得た。得られた金属パターン付きフィルム1の透過特性を、テラヘルツ時間領域分光法(THz-TDS)を用いて測定した。試料をΦ10mmのアパーチャーに固定(NA~1/6)し、温度25℃、湿度20%環境下でテラヘルツビームを照射した。偏波方向とパターンの長軸方向を一致させた。320GHz付近に透過率の急峻な谷(凹み)と位相反転が観測され、COPフィルムの両面に配置された金属パターンの共振が生じていることが示唆された。
両面に銅層が配置されたCOPフィルムの代わりに、両面に銀層が配置されたCOPフィルムを用いた以外は、上記(金属パターン付きフィルム1)と同様の手順に従って、金属パターン付きフィルム2を製造した。得られた金属パターン付きフィルム2中のCOPフィルムの両面に配置された金属パターンを、金属パターン付きフィルム1の場合と同様の方法で透過特性を測定し、テラヘルツ帯の電磁波に対して共振が生じていることを確認した。
なお、両面に銀層が配置されたCOPフィルムは、以下の方法によって製造した。
COPフィルムの表面を超音波洗浄(45kHz)した後、株式会社C-INK社製導電性金属ナノインクDryCureAg-J(銀ナノ粒子10質量%水溶液)を、COPフィルムの両面に塗布した後、120℃で60分間加熱し、銀層を得た。
表1に示す各化合物由来の構成単位を含む樹脂P-100及びP-101を用意した。
表1に、合成した各樹脂の構成単位の量(質量%)、重量平均分子量(Mw)、分散度、及び、酸価を示す。
表1中、各略称は以下の通りである。
・St:スチレン
・MAA-GMA:メタクリル酸由来の構成単位にグリシジルメタクリレートを付加してなる構成単位
・MAA:メタクリル酸
・DCPMA:メタクリル酸ジシクロペンタニル
・MMA:メタクリル酸メチル
なお、上記GMA-MAAで表される繰り返し単位は、以下の式で表される。
窒素気流下、ブタノンオキシム(出光興産社製)453gをメチルエチルケトン700gに溶解させた。これに氷冷下、1,3-ビス(イソシアナトメチル)シクロヘキサン(cis,trans異性体混合物、三井化学社製、タケネート600)500gを1時間かけて滴下し、滴下後更に1時間反応させた。その後40℃に昇温して1時間反応させた。1H-NMR(Nuclear Magnetic Resonance)及びHPLC(High Performance Liquid Chromatography)にて反応が完結したことを確認し、ブロックイソシアネート化合物Q-1(下記式参照)のメチルエチルケトン溶液を得た。
ブロックイソシアネート化合物Q-1の合成方法を参考にして、ブロックイソシアネート化合物Q-2~Q-4(下記式参照)のメチルエチルケトン溶液を得た。
下記表3に示す組成の硬化性組成物A-1~A-6を調製した。表3中、各成分の数値は各成分の含有量(固形分質量)を表し、メチルエチルケトン及び1-メトキシ-2-プロピルアセテートを適宜加え、溶剤のうちメチルエチルケトンの含有量が60質量%に、固形分濃度が25質量%になるよう、硬化性組成物を調製した。
なお、硬化性組成物B-2は、A液とB液との2液セットであった。
仮支持体であるルミラー16KS40(厚み16μm、東レ株式会社製、ポリエチレンテレフタレートフィルム)に、スリット状ノズルを用いて、硬化性組成物A-1~A-6及びB-1~B-2のいずれか1種を塗布し、次に、100℃の乾燥ゾーンで溶剤を揮発させることにより、仮支持体上に硬化性組成物層を形成した。硬化性組成物の塗布量は、表6に記載された有機膜の厚みになるように調節した。次に、硬化性組成物層上に保護フィルム(ルミラー16KS40(東レ株式会社製))を圧着し、実施例1~10及び比較例1で使用する各転写フィルムを作製した。
なお、上記ラミネートは、MCK社製真空ラミネーターを用いて、誘電体フィルムの温度40℃、ゴムローラー温度100℃、線圧3N/cm、搬送速度2m/分の条件で行った。
その後、145℃で30分間のポストベーク処理を行って、積層体を形成した。
ただし、組成物B-2を用いた際には、上記露光処理を実施せずに、145℃で30分間の加熱処理のみを実施した。
なお、比較例1では硬化性組成物層が形成されていないフィルムを用いて、上記処理を行っている。
(透湿度)
JIS Z 0208記載の方法により、各実施例及び比較例の有機膜が5層積層された測定サンプルの透湿度の測定を行った(測定条件:温度40℃、相対湿度90%で、24時間経過後)。
より具体的には、以下の方法にて透湿度を算出した。
まず、測定サンプルの作製は、以下の方法で行った。市販のテフロン(登録商標)メッシュ上に作製した各実施例及び比較例の転写フィルムを5回ラミネートした(透明フィルム基板の温度:40℃、ゴムローラー温度110℃、線圧3N/cm、搬送速度2m/分)。その後、超高圧水銀灯を有するプロキシミティー型露光機(日立ハイテク電子エンジニアリング(株)製)を用いて、露光マスク面と仮支持体との間の距離を125μmに設定し、仮支持体を介して露光量100mJ/cm2(i線)で全面露光し、さらに150℃60分間の加熱(ポストベーク)処理を行ったものを測定サンプルとして用いた。
得られた評価サンプルを温度40℃、相対湿度90%で、24時間静置後、同条件(温度40℃、相対湿度90%)にてJIS Z 0208記載の方法にて透湿度を求めた。得られた透湿度の値を5倍にして、有機膜1層あたりの透湿度を求めた。
上記操作を5つの測定サンプルに対して実施して、5つの1層あたりの透湿度の値を求め、これらの数値を算術平均して、本発明の透湿度(WVTR)とした。得られた透湿度(WVTR)を後段の評価基準に従って、評価した。
なお、組成物B-2を用いた際には、上記露光処理を実施せずに、145℃30分間の加熱処理のみを実施して、評価サンプルを作製した。
A:WVTRが、1000g/(m2・24hr)以下
B:WVTRが、1000g/(m2・24hr)超2000g/(m2・24hr)以下
C:WVTRが、2000g/(m2・24hr)超3000g/(m2・24hr)以下
D:WVTRが、3000g/(m2・24hr)超
各実施例及び比較例で得られた積層体の有機膜側の表面に濃度50g/Lの塩水を5cm3滴下し、50cm2に均一に広げた後、常温にて水分を揮発させ、HAST試験装置EHS-221MD(エスペック株式会社製)を用いて温度110℃、相対湿度85%環境下で32時間経過させた。その後、塩水をふき取って積層体中の金属パターンの表面状態を観察し、以下の評点にしたがって評価した。
A、B、Cであることが実用上必要なレベルである。
A:銅又は銀の変色や荒れが全くない。
B:銅又は銀の一部にうすく変色や荒れが見られる。
C:銅又は銀の全面にうすく変色や荒れが見られる。
D:銅又は銀の全面に顕著に変色や荒れが見られる。
表6中、「複素環化合物」欄は、有機膜に複素環化合物が含まれるか否かを表し、「有」は有機膜が複素環化合物を含むことを、「無」は有機膜が複素環化合物を含まないことを表す。
表6中、「酸価」欄は、有機膜に含まれるポリマーの酸価が20mgKOH/g以下であるかを表し、「A」は20mgKOH/g以下であることを表し、「B」は20mgKOH/g超であることを表す。
表6中、「厚み(μm)」欄は、有機膜の厚み(μm)を表す。
実施例8と9との比較より、有機膜が複素環化合物を含む場合、より優れた効果が得られた。
実施例8と10との比較より、有機膜に含まれるポリマーの酸価が20mgKOH/g以下の場合、より優れた効果が得られた。
12,22 誘電体フィルム
14 金属パターン
16 有機膜
18,18A 金属構造体
24 第1金属パターン
26 第1有機膜
28 第2金属パターン
30 第2有機膜
32 第1金属構造体
34 第2金属構造体
40 フォトマスク
42 開口部
Claims (19)
- 誘電体フィルムと、
前記誘電体フィルムの少なくとも一方の表面側に配置された、テラヘルツ帯の電磁波に対して共振器となる、金属パターンと、
前記金属パターン上に配置された、温度40℃、相対湿度90%の環境下における透湿度が3000g/(m2・24hr)以下である有機膜と、を有する、積層体。 - 前記有機膜が、複素環化合物を含む、請求項1に記載の積層体。
- 前記有機膜が、酸価が20mgKOH/g以下であるポリマーを含む、請求項1に記載の積層体。
- 前記有機膜が硬化性組成物を用いて形成され、
前記硬化性組成物がブロックイソシアネートを含む、請求項1に記載の積層体。 - 誘電体フィルムと、
前記誘電体フィルムの一方の表面側に配置された、複数の第1金属構造体から構成された第1金属パターンと、
前記第1金属パターン上に配置された、温度40℃、相対湿度90%の環境下における透湿度が3000g/(m2・24hr)以下である第1有機膜と、
前記誘電体フィルムの他方の表面側に配置された、複数の第2金属構造体から構成された第2金属パターンと、
前記第2金属パターン上に配置された、温度40℃、相対湿度90%の環境下における透湿度が3000g/(m2・24hr)以下である第2有機膜と、を有し、
前記第1金属パターンと前記第2金属パターンとが、テラヘルツ帯の電磁波に対して共振器を構成する、積層体。 - 前記積層体を平面視した際に、前記第1金属パターンに含まれる前記第1金属構造体と、前記第2金属パターンに含まれる前記第2金属構造体とが、少なくとも一部重複するように配置されている、請求項5に記載の積層体。
- 前記第1有機膜及び前記第2有機膜が、複素環化合物を含む、請求項5に記載の積層体。
- 前記第1有機膜及び前記第2有機膜が、酸価が20mgKOH/g以下であるポリマーを含む、請求項5に記載の積層体。
- 前記第1有機膜及び前記第2有機膜が硬化性組成物を用いて形成され、
前記硬化性組成物がブロックイソシアネートを含む、請求項5に記載の積層体。 - 請求項1~9のいずれか1項に記載の積層体を含む、光学素子。
- 誘電体フィルム、及び、前記誘電体フィルムの少なくとも一方の表面側に配置された、テラヘルツ帯の電磁波に対して共振器となる金属パターンを含む金属パターン付きフィルムと、仮支持体及び硬化性組成物層を含む転写フィルムとを貼合して、前記誘電体フィルム、前記金属パターン、前記硬化性組成物層、及び、前記仮支持体をこの順で有する前駆体フィルムを形成する工程1Aと、
前記硬化性組成物層に硬化処理を施して、温度40℃、相対湿度90%の環境下における透湿度が3000g/(m2・24hr)以下である有機膜を得る工程2Aと、を、有し、
前記工程1Aと前記工程2Aとの間、又は、前記工程2Aの後に、前記仮支持体を剥離する工程を更に有する、積層体の製造方法。 - 前記有機膜が、複素環化合物を含む、請求項11に記載の積層体の製造方法。
- 前記有機膜が、酸価が20mgKOH/g以下であるポリマーを含む、請求項11又は12に記載の積層体の製造方法。
- 前記硬化性組成物層がブロックイソシアネートを含む、請求項11又は12に記載の積層体の製造方法。
- 誘電体フィルムと、前記誘電体フィルムの一方の表面側に配置された、複数の第1金属構造体から構成された第1金属パターンと、前記誘電体フィルムの他方の表面側に配置された、複数の第2金属構造体から構成された第2金属パターンとを含み、前記第1金属パターンと前記第2金属パターンとがテラヘルツ帯の電磁波に対して共振器を構成する金属パターン付きフィルムと、仮支持体及び硬化性組成物層を含む転写フィルムとを貼合して、前記仮支持体、前記硬化性組成物層、前記第1金属パターン、前記誘電体フィルム、前記第2金属パターン、前記硬化性組成物層、及び、前記仮支持体をこの順で有する前駆体フィルムを形成する工程1Bと、
前記硬化性組成物層に硬化処理を施して、温度40℃、相対湿度90%の環境下における透湿度が3000g/(m2・24hr)以下である有機膜を得る工程2Bと、を、有し、
前記工程1Bと前記工程2Bとの間、又は、前記工程2Bの後に、前記仮支持体を剥離する工程3Bを更に有する、積層体の製造方法。 - 前記金属パターン付きフィルムを平面視した際に、前記第1金属パターンに含まれる前記第1金属構造体と、前記第2金属パターンに含まれる前記第2金属構造体とが、少なくとも一部重複するように配置されている、請求項15に記載の積層体の製造方法。
- 前記有機膜が、複素環化合物を含む、請求項15又は16に記載の積層体の製造方法。
- 前記有機膜が、酸価が20mgKOH/g以下であるポリマーを含む、請求項15又は16に記載の積層体の製造方法。
- 前記硬化性組成物層がブロックイソシアネートを含む、請求項15又は16に記載の積層体の製造方法。
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