CN110317357B - Photosensitive film laminate, cured product thereof, and electronic component - Google Patents

Photosensitive film laminate, cured product thereof, and electronic component Download PDF

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Publication number
CN110317357B
CN110317357B CN201910243227.1A CN201910243227A CN110317357B CN 110317357 B CN110317357 B CN 110317357B CN 201910243227 A CN201910243227 A CN 201910243227A CN 110317357 B CN110317357 B CN 110317357B
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photosensitive film
photosensitive
film
film laminate
laminate
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CN110317357A (en
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荒井康昭
舟越千弘
佐藤和也
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Taiyo Holdings Co Ltd
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Taiyo Ink Mfg Co Ltd
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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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin 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
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/03—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers with respect to the orientation of features
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • H—ELECTRICITY
    • H03—ELECTRONIC CIRCUITRY
    • H03H—IMPEDANCE NETWORKS, e.g. RESONANT CIRCUITS; RESONATORS
    • H03H3/00—Apparatus or processes specially adapted for the manufacture of impedance networks, resonating circuits, resonators
    • H03H3/007—Apparatus or processes specially adapted for the manufacture of impedance networks, resonating circuits, resonators for the manufacture of electromechanical resonators or networks
    • H03H3/08—Apparatus or processes specially adapted for the manufacture of impedance networks, resonating circuits, resonators for the manufacture of electromechanical resonators or networks for the manufacture of resonators or networks using surface acoustic waves
    • H—ELECTRICITY
    • H03—ELECTRONIC CIRCUITRY
    • H03H—IMPEDANCE NETWORKS, e.g. RESONANT CIRCUITS; RESONATORS
    • H03H9/00—Networks comprising electromechanical or electro-acoustic devices; Electromechanical resonators
    • H03H9/02—Details
    • H03H9/05—Holders; Supports
    • H03H9/058—Holders; Supports for surface acoustic wave devices
    • H03H9/0585—Holders; Supports for surface acoustic wave devices consisting of an adhesive layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/538—Roughness
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

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  • Physics & Mathematics (AREA)
  • Acoustics & Sound (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Materials For Photolithography (AREA)
  • Laminated Bodies (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)

Abstract

Provided are a photosensitive film laminate suitable for the formation of a hollow structure, a cured product thereof, and an electronic component, wherein peeling of a plating layer or the like in a portion close to the hollow structure can be suppressed in an electronic component having a hollow structure such as a SAW filter. A photosensitive film laminate comprising a support film, a photosensitive film formed from a photosensitive composition, and a protective film in this order, wherein the protective film is peeled from the photosensitive film laminate to expose the surface of the photosensitive film, the arithmetic average surface roughness of the surface of the photosensitive film after leaving the photosensitive film laminate in an environment of 23 ℃ and 42% relative humidity for 1 minute is Ra1, the protective film is peeled from the photosensitive film laminate to expose the surface of the photosensitive film, and the arithmetic average surface roughness of the surface of the photosensitive film after leaving the photosensitive film laminate in an environment of 23 ℃ and 42% relative humidity for 180 minutes is Ra2, wherein the following formula is satisfied: ra1 is more than or equal to 0.10 mu m and more than or equal to 0.40, and Ra2/Ra1 is less than 1.00.

Description

Photosensitive film laminate, cured product thereof, and electronic component
Technical Field
The present invention relates to a photosensitive film laminate, and more particularly, to a photosensitive film laminate which can be suitably used for forming a hollow structure in an electronic component having the hollow structure, a cured product thereof, and an electronic component.
Background
In recent years, electronic devices are increasingly required to be miniaturized and have high functionality, and electronic components used therein are also required to be further miniaturized, thinned, and have multiple functions. Among them, development of fine electronic components such as image sensors represented by CMOS and CCD sensors, gyro sensors using MEMS (Micro Electro Mechanical Systems) technology in which Mechanical elements and electronic circuit elements are integrated on one substrate by semiconductor microfabrication technology, and packages of elements exhibiting specific electric functions by forming an electrode pattern or a fine structure on a surface of a single crystal wafer represented by a Surface Acoustic Wave (SAW) filter have been attracting attention. In these fine electronic components, the following structures are formed: in order to prevent the active surface (movable portion) of the sensor element from coming into contact with other objects and to form a hollow structure in order to protect the sensor element from moisture, dust, and the like, a sensor and the like are disposed therein.
Conventionally, the electronic component is formed into a hollow structure by processing and bonding inorganic materials. However, in order to reduce the production cost and further reduce the size, a method of forming a hollow structure using a photosensitive resin or the like instead of an inorganic material has been studied, and for example, the following proposals have been made: a permanent resist is laminated, and a wall portion (wall surface) and a lid portion are formed by a photolithography technique to form a hollow structure (for example, WO 2009/151050).
Disclosure of Invention
The electronic component having a hollow structure such as the SAW filter is manufactured as a package structure having external terminals or external electrodes electrically connected to wiring electrodes of the piezoelectric substrate for mounting on a mounting substrate. At this time, the inner conductor is formed by plating or the like in the wall portion or the portion close to the lid portion forming the hollow structure in order to obtain connection reliability with the external wiring. In addition, in order to protect the element and improve the operability, the hollow structure or the proximity portion is resin-sealed by transfer molding or the like.
However, in the case of forming a hollow structure using a permanent resist, it was confirmed that: when the internal conductor is formed in the proximity portion, peeling of the plating layer or the like occurs, or the sealing material peels off from the surface of the wall portion or the lid portion of the hollow structure.
Accordingly, an object of the present invention is to provide a photosensitive film laminate suitable for formation of a hollow structure, which can suppress peeling of a plating layer or the like in an adjacent portion of the hollow structure in an electronic component having a hollow structure such as a SAW filter. Another object of the present invention is to provide a cured product formed using the photosensitive film laminate, and an electronic component having a hollow structure.
As a method of forming the hollow structure by using a resin, a hollow structure can be formed by laminating a plurality of photosensitive films, forming a wall portion in advance by exposure and development, placing another photosensitive film on the upper end of the wall portion, forming a lid portion by exposure and development so as to form a predetermined shape, and thermally curing the photosensitive resin. The present inventors have conducted intensive studies on the above problems, and as a result, have found that: when the hollow structure is formed using the photosensitive film as described above, the developer used in the developing step slightly remains on the wall portion or the lid portion constituting the hollow structure, and the developer seeps out from the interface, thereby suppressing adhesion to the plating layer or the like and facilitating peeling. As a result of further studies, it has been found that, in a photosensitive film laminate provided with a protective film, when the photosensitive film laminate is used for forming a hollow structure, the surface morphology of the photosensitive film laminate, which has been exposed by peeling off the protective film, is changed to a specific range with time, it is possible to suppress the inhibition of adhesion to a plating layer or the like, and to manufacture an electronic component having a high-quality hollow structure.
The present invention is as follows.
[1] A photosensitive film laminate comprising a support film, a photosensitive film formed from a photosensitive composition, and a protective film in this order,
the protective film was peeled off from the photosensitive film laminate to expose the surface of the photosensitive film, and the arithmetic average surface roughness of the surface of the photosensitive film after leaving the laminate in an environment of 23 ℃ and a relative humidity of 42% for 1 minute was Ra1,
the protective film was peeled off from the photosensitive film laminate to expose the surface of the photosensitive film, the arithmetic average surface roughness of the surface of the photosensitive film after leaving the photosensitive film laminate in an environment of 23 ℃ and a relative humidity of 42% for 180 minutes was Ra2,
at this time, the following equation is satisfied:
ra1 is more than or equal to 0.10 mu m and more than or equal to 0.40, and Ra2/Ra1 is less than 1.00.
[2] The photosensitive film laminate according to [1],
peeling the protective film from the photosensitive film laminate to expose the surface of the photosensitive film, wherein Ry1 represents the maximum height of the surface of the photosensitive film after the photosensitive film laminate is left for 1 minute in an environment of 23 ℃ and 42% relative humidity,
peeling the protective film from the photosensitive film laminate to expose the surface of the photosensitive film, setting Ry2 as the maximum height of the surface of the photosensitive film after leaving the photosensitive film laminate in an environment of 23 ℃ and 42% relative humidity for 180 minutes,
at this time, the following equation is satisfied:
ry1 is more than or equal to 1.00 mu m, Ry2/Ry1 is more than or equal to 0.30 and less than 1.00.
[3] The photosensitive film laminate according to [1], wherein the photosensitive composition comprises a photocurable compound.
[4] The photosensitive film laminate according to [1], wherein the photosensitive composition further comprises a photopolymerization initiator.
[5] The photosensitive film laminate according to [1], which is used for forming a lid or a wall constituting the hollow structure in an electronic component having the hollow structure.
[6] A cured product obtained by curing the photosensitive film of the photosensitive film laminate according to any one of [1] to [5 ].
[7] An electronic component, which is characterized by having the cured product of [6 ].
[8] The electronic component according to [7], which has a hollow structure comprising a wall portion and a lid portion, wherein either one or both of the wall portion and the lid portion is composed of the cured product.
According to the present invention, it is possible to provide a photosensitive film laminate suitable for forming a hollow structure, which can suppress peeling of a plating layer or the like in an adjacent portion of the hollow structure in an electronic component having the hollow structure. Further, according to another embodiment of the present invention, a cured product and an electronic component formed using the photosensitive film laminate can be provided.
Drawings
Fig. 1 is a schematic cross-sectional view showing the steps of manufacturing the test substrates manufactured in examples 4 and 5.
Fig. 2 is a schematic cross-sectional view showing a manufacturing step of the test substrates manufactured in example 4 and example 5.
Fig. 3 is a schematic cross-sectional view showing a manufacturing step of the test substrates manufactured in example 4 and example 5.
Fig. 4 is a schematic cross-sectional view showing a manufacturing step of the test substrates manufactured in example 4 and example 5.
Detailed Description
< photosensitive film laminate >
The photosensitive film laminate of the present invention comprises a support film, a photosensitive film formed from a photosensitive composition, and a protective film in this order. Hereinafter, each constituent element constituting the photosensitive film laminate of the present invention will be described. In the present specification, unless otherwise specified, the numerical range represented by the symbols "to" means a range including the upper limit and the lower limit thereof (i.e., a range from the lower limit thereof to the upper limit thereof).
[ supporting film ]
The support film constituting the photosensitive film laminate of the present invention supports the photosensitive film, and any known support film capable of achieving the above function can be used without any particular limitation, and for example, films made of thermoplastic resins such as polyester films of polyethylene terephthalate, polyethylene naphthalate and the like, polyimide films, polyamide-imide films, polypropylene films, polystyrene films and the like can be suitably used. In the case of using the above thermoplastic resin film, a filler may be added to the resin (mixing treatment) at the time of film formation, a matte coating treatment (coating treatment) may be performed, a spray treatment such as a sandblasting treatment may be performed on the film surface, or a treatment such as a hairline treatment or chemical etching may be performed. Among these, polyester films can be suitably used in view of heat resistance, mechanical strength, handling properties, and the like. The support film may be a single layer or may be stacked in 2 or more layers.
For the purpose of improving strength, a film stretched in a uniaxial direction or a biaxial direction is preferably used as the thermoplastic resin film.
For the purpose of improving strength, a film stretched in a uniaxial direction or a biaxial direction is preferably used as the thermoplastic resin film.
The thickness of the support film is not particularly limited, and is generally in the range of 10 μm to 3,000 μm depending on the application.
[ photosensitive film ]
The photosensitive film constituting the photosensitive film laminate of the present invention is formed from a photosensitive composition. That is, the photosensitive composition containing each component described later is applied to one surface of the support film and dried, whereby the support film can be formed. The photosensitive film is formed into a predetermined shape by exposure and development, and then the photosensitive composition is cured to obtain a cured product. Therefore, in a state where the protective film is peeled off from the photosensitive film laminate and the surface of the photosensitive film is exposed, the photosensitive composition is in an uncured state, and thus the surface morphology of the photosensitive film changes with time. In the present invention, it was found that there is a certain relationship between the change of the surface morphology of the photosensitive film with time and the peeling of the plating layer or the like, and by forming a photosensitive film laminate satisfying the following conditions, it is possible to realize an electronic component having a high-quality hollow structure by forming the hollow structure of the electronic component using the photosensitive film laminate, while suppressing the inhibition of adhesion to the plating layer or the like.
In the present invention, the protective film is peeled off from the photosensitive film laminate to expose the surface of the photosensitive film, the arithmetic average surface roughness of the surface of the photosensitive film after leaving the photosensitive film laminate in an environment of 23 ℃ and 42% relative humidity for 1 minute is Ra1,
the protective film was peeled off from the photosensitive film laminate to expose the surface of the photosensitive film, the arithmetic average surface roughness of the surface of the photosensitive film after leaving the photosensitive film laminate in an environment of 23 ℃ and a relative humidity of 42% for 180 minutes was Ra2,
at this time, the following equation is satisfied:
ra1 is 0.10 μm or more and 0.40. ltoreq. Ra2/Ra1<1.00, which is important.
When the photosensitive film has an uneven surface with a predetermined arithmetic mean surface roughness when the protective film is peeled off, the uneven surface tends to gradually become flat, and the surface morphology changes with time. In the present invention, by focusing on the change in the surface morphology with time, the use of a photosensitive film which remains in a specific change in the surface morphology can suppress peeling of a plating layer or the like in the vicinity of the hollow structure.
In the present invention, the surface of the photosensitive film in contact with the protective film after the protective film is peeled has an arithmetic average surface roughness Ra1 of 0.10 μm or more, preferably 0.15 μm or more, and more preferably 0.20 μm or more. When the upper limit is set, the particle size is preferably 1.00 μm or less, more preferably 0.80 μm or less, and still more preferably 0.60 μm or less. It should be noted that Ra1 is defined as: the protective film was peeled off to expose the surface of the photosensitive film, and the film was left to stand at 23 ℃ and a relative humidity of 42% for 1 minute.
In addition, from the viewpoint of further suppressing peeling of the plating layer or the like, the maximum height Ry1 of the photosensitive film on the surface in contact with the protective film after the protective film is peeled off is preferably 1.00 or more, more preferably 1.20 μm or more, and further preferably 1.40 μm or more. When the upper limit is set, the thickness is preferably 5.00 μm or less, more preferably 4.00 μm or less, and still more preferably 3.00 μm or less. It should be noted that Ry1 is defined as: the protective film was peeled off to expose the surface of the photosensitive film, and the film was left to stand at 23 ℃ and a relative humidity of 42% for 1 minute.
The change in shape of the photosensitive film surface with time was evaluated by the ratio of the arithmetic mean surface roughness after a predetermined time had elapsed to the arithmetic mean surface roughness immediately after the protective film was peeled (i.e., Ra 1). In the present invention, peeling of a plating layer or the like in a proximal portion of a hollow structure can be suppressed by a photosensitive film laminate in which a protective film is peeled from the photosensitive film laminate to expose a photosensitive film surface, and the arithmetic average surface roughness of the photosensitive film on the surface in contact with the protective film after being left for 180 minutes in an environment of 23 ℃ and 42% relative humidity is Ra2, and when Ra2/Ra1<1.00 is satisfied 0.40 or more. The reason is not confirmed, but is considered as follows. Namely, it is presumed that: in the photosensitive film laminate provided with the protective film, the surface morphology having a certain roughness after the surface of the photosensitive film is exposed by peeling off the protective film slowly changes over time, and if the ratio of the change is constant, the degree of adhesion to the substrate is more appropriate in the case of the wall material, and the degree of adhesion to the wall material is more appropriate in the case of the lid material, and the residual developing solution used in the development can be prevented from entering the periphery of the hollow structure, and as a result, peeling off of the plating layer and the like due to the residual developing solution can be suppressed. However, this is merely an assumption and is not necessarily limited thereto. In the present invention, the place where the photosensitive film is left for 180 minutes with the protective film peeled off and the surface of the photosensitive film exposed is under a yellow light.
From the viewpoint of further suppressing peeling due to a moderate shape change, the shape change with time of the photosensitive film surface preferably satisfies 0.50. ltoreq. Ra2/Ra 1. ltoreq.0.95, and more preferably satisfies 0.60. ltoreq. Ra2/Ra 1. ltoreq.0.90.
Further, peeling of the plating layer or the like can be further suppressed in a photosensitive film laminate which satisfies 0.30. ltoreq. Ry2/Ry1<1.00 when Ry2 is the maximum height of the photosensitive film on the surface which is in contact with the protective film after the protective film is peeled from the photosensitive film laminate to expose the surface of the photosensitive film and left to stand in an environment of 23 ℃ and 42% relative humidity for 180 minutes. In the present invention, the place where the photosensitive film was left for 180 minutes with the protective film peeled off to expose the surface of the photosensitive film was placed under a yellow lamp.
From the viewpoint of further suppressing peeling due to an appropriate shape change, the shape change of the photosensitive film surface with time is preferably 0.35. ltoreq. Ry2/Ry 1. ltoreq.0.80, more preferably 0.40. ltoreq. Ry2/Ry 1. ltoreq.0.70.
The arithmetic surface roughness Ra ″ and the maximum height Ry ″ of the surface of the photosensitive film in contact with the support film are also preferably within the same range or at the same rate as the arithmetic surface roughness Ra and the maximum height Ry ″ of the surface of the photosensitive film in contact with the protective film. In particular, it is effective in the case of a photosensitive film laminate comprising a support film and a photosensitive film formed from a photosensitive composition in this order without a protective film. In this case, the support film is preferably made of the same material and thickness as those of the protective film described later.
In the present invention, the "arithmetic average surface roughness Ra" and the "maximum height Ry" are values measured by a measuring apparatus according to JIS B0601-1994. Hereinafter, a specific measurement method will be described. The arithmetic average surface roughness Ra and the maximum height Ry can be measured using a shape measuring laser microscope (for example, VK-X100 manufactured by KEYENCE K.K.). After a main body (control unit) of a shape measurement laser microscope (same VK-X100) and a VK observation application (VK-H1 VX manufactured by KEYENCE K.K.) were started, a sample (photosensitive film) to be measured was placed on an X-y stage. The focal length and brightness were roughly adjusted in an image observation mode of a VK observation application (same VK-H1VX) by rotating a lens converter of a microscope unit (VK-X110 manufactured by KEYENCE K.K.) and selecting an objective lens with a magnification of 10 times. The x-y stage is operated to adjust the desired measurement portion of the sample surface to the center of the screen. The objective lens having the magnification of 10 times was changed to the magnification of 50 times, and the surface of the sample was focused by the autofocus function in the image observation mode of the VK observation application (same VK-H1 VX). By selecting a simple mode of a shape measurement tab of a VK observation application (same VK-H1VX), and pressing a measurement start button, the surface shape of the sample is measured, and a surface image file can be obtained. The VK analysis application (VK-H1 XA manufactured by KEYENCE corporation) was started, and the resulting surface image file was displayed and then subjected to tilt correction. The measurement range (lateral direction) for observation in the measurement of the surface shape of the sample was 270 μm. A line roughness window is displayed, and after JIS B0601-1994 is selected in a parameter setting area, a horizontal line is selected from a measuring line button, the horizontal line is displayed at an arbitrary position in a surface image, and an OK button is pressed, thereby obtaining numerical values of arithmetic average surface roughness Ra and maximum height Ry. Further, horizontal lines are displayed at different four places within the surface image, and numerical values of each arithmetic average surface roughness Ra and the maximum height Ry are obtained. The average of the obtained 5 values was calculated as the arithmetic average surface roughness Ra and the maximum height Ry of the sample surface. In the measurement of the arithmetic average surface roughness Ra and the maximum height Ry, a photosensitive film in a state before a curing step by exposure or the like is used as a measurement sample. In the case where the protective film is laminated as the laminated body in the present invention, the measurement sample is used in a state where the protective film is peeled off before being laminated on the substrate. In this case, the "arithmetic average surface roughness Ra" and the "maximum height Ry" of the sample surface were measured immediately after (1 minute) and 180 minutes after the protective film was peeled off to expose the photosensitive film. The measurement environment in the present invention is a temperature of 23 ℃ and a relative humidity of 42%.
In order to make the surface morphology of the photosensitive film within the above-mentioned range of the specific arithmetic average surface roughness Ra and the maximum height Ry, a known conventional method can be applied, and in view of easiness of forming the surface morphology, a photosensitive film can be formed using a protective film in which the arithmetic average surface roughness Ra and the maximum height Ry are adjusted in the protective film described later. Further, the roughness of the surface of the photosensitive film may be adjusted by attaching a protective film having a specific arithmetic average surface roughness Ra and a maximum height Ry, peeling the protective film, and then attaching another protective film having a different arithmetic average surface roughness Ra and a different maximum height Ry to the surface of the photosensitive film.
The change with time in the surface morphology of the photosensitive film after the protective film is peeled off can be adjusted by the type or amount of the component contained in the photosensitive composition before curing constituting the photosensitive film. For example, it can be adjusted by compounding materials different in solubility parameter (SP value), using a material having an appropriate glass transition temperature (Tg) or weight average molecular weight, or using a filler as appropriate, but is not limited thereto. In the present invention, the composition of the photosensitive composition for forming the photosensitive film is not particularly limited, and the photosensitive composition may include a photocurable compound, a photopolymerization initiator, a thermal crosslinking material, an inorganic filler, and the like. Hereinafter, each component constituting the photosensitive composition will be described.
[ Photocurable Compound ]
The photosensitive composition used in the photosensitive film laminate of the present invention contains a component that is cured by irradiation with ionizing radiation such as ultraviolet rays, and examples thereof include photocurable compounds. The photocurable compound is a compound having an ethylenically unsaturated double bond, and includes all of resins, oligomers, and monomers. Examples of such photocurable compounds include alkyl (meth) acrylates such as 2-ethylhexyl (meth) acrylate and cyclohexyl (meth) acrylate; hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; mono (meth) acrylates or di (meth) acrylates of alkylene oxide derivatives such as ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol; polyhydric (meth) acrylates such as polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, and trishydroxyethyl isocyanurate, or ethylene oxide or propylene oxide adducts thereof; (meth) acrylic acid esters of ethylene oxide or propylene oxide adducts of phenols such as phenoxyethyl (meth) acrylate and polyethoxy di (meth) acrylate of bisphenol A; (meth) acrylic acid esters of glycidyl ethers such as glycerol diglycidyl ether, trimethylolpropane triglycidyl ether and triglycidyl isocyanurate; and melamine (meth) acrylate, and the like. In the present specification, the term (meth) acrylate is a general term referring to acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.
In addition to the above, urethane monomers and urethane oligomers such as (meth) acrylate compounds having an amide bond and (meth) acrylate compounds having a urethane bond may be used.
The photocurable compound may be a carboxyl group-containing photosensitive resin obtained by reacting an unsaturated carboxylic acid such as acrylic acid or methacrylic acid with an epoxy resin, a phenol resin, or the like. Such a carboxyl group-containing photosensitive resin is preferably polymerizable or crosslinkable by light irradiation to be cured, and further preferably contains a carboxyl group, because the resin is not only solvent-developable but also alkali-developable. Particularly, it is preferable that the developer is weakly alkaline, specifically, has a pH of 7.0 to 12.0, since the developer has excellent developability.
Specific examples of the carboxyl group-containing photosensitive resin include the following compounds (which may be either an oligomer or a polymer).
There may be mentioned:
(1) a carboxyl group-containing photosensitive resin obtained by reacting a polyfunctional (solid) epoxy resin having 2 or more functional groups with (meth) acrylic acid to add a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride to a hydroxyl group present in a side chain;
(2) a carboxyl group-containing photosensitive resin obtained by reacting a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of a 2-functional (solid) epoxy resin with (meth) acrylic acid using epichlorohydrin and adding a dibasic acid anhydride to the resulting hydroxyl group;
(3) a carboxyl group-containing photosensitive resin obtained by reacting an epoxy compound having 2 or more epoxy groups in 1 molecule with a compound having at least 1 alcoholic hydroxyl group and 1 phenolic hydroxyl group in 1 molecule and an unsaturated group-containing monocarboxylic acid such as (meth) acrylic acid, and reacting the alcoholic hydroxyl group of the reaction product obtained with a polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, adipic anhydride or the like;
(4) a carboxyl group-containing photosensitive resin obtained by reacting a compound having 2 or more phenolic hydroxyl groups in 1 molecule, such as bisphenol a, bisphenol F, bisphenol S, novolak-type phenol resins, polyparahydroxystyrene, condensates of naphthol and aldehydes, and condensates of dihydroxynaphthalene and aldehydes, with an alkylene oxide such as ethylene oxide or propylene oxide, reacting the resulting reaction product with an unsaturated group-containing monocarboxylic acid such as (meth) acrylic acid, and reacting the resulting reaction product with a polybasic acid anhydride;
(5) a carboxyl group-containing photosensitive resin obtained by reacting a compound having 2 or more phenolic hydroxyl groups in 1 molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, reacting the obtained reaction product with an unsaturated group-containing monocarboxylic acid, and reacting the obtained reaction product with a polybasic acid anhydride;
(6) a terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with the terminal of a urethane resin obtained by a polyaddition reaction of a diisocyanate compound such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate, or an aromatic diisocyanate with a diol compound such as a polycarbonate polyol, a polyether polyol, a polyester polyol, a polyolefin polyol, an acrylic polyol, a bisphenol a alkylene oxide adduct diol, or a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group;
(7) a carboxyl group-containing photosensitive urethane resin in which a compound having 1 hydroxyl group and 1 or more (meth) acryloyl groups in a molecule, such as hydroxyalkyl (meth) acrylate, is added to the synthesis of a carboxyl group-containing urethane resin by a polyaddition reaction of a carboxyl group-containing diol compound, such as diisocyanate, dimethylolpropionic acid, dimethylolbutyric acid, and the diol compound, thereby causing (meth) acryloyl group at the end;
(8) a carboxyl group-containing photosensitive urethane resin in which a terminal is (meth) acrylated by adding a compound having 1 isocyanate group and 1 or more (meth) acryloyl groups in a molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate, to the synthesis of a carboxyl group-containing urethane resin by a polyaddition reaction of diisocyanate, carboxyl group-containing diol compound, and diol compound;
(9) a carboxyl group-containing photosensitive resin obtained by reacting a polyfunctional oxetane resin with a dicarboxylic acid such as adipic acid, phthalic acid or hexahydrophthalic acid to add a dibasic acid anhydride to the primary hydroxyl group formed and further adding a compound having 1 epoxy group and 1 or more (meth) acryloyl groups in 1 molecule such as glycidyl (meth) acrylate or α -methylglycidyl (meth) acrylate to the carboxyl group-containing polyester resin;
(10) a carboxyl group-containing photosensitive resin obtained by adding a compound having a cyclic ether group and a (meth) acryloyl group in 1 molecule to any one of the carboxyl group-containing photosensitive resins (1) to (9);
(11) a carboxyl group-containing photosensitive resin obtained by reacting a carboxyl group-containing resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth) acrylic acid with an unsaturated group-containing compound such as styrene, α -methylstyrene, a lower alkyl (meth) acrylate, or isobutylene with a compound having a cyclic ether group and a (meth) acryloyl group in one molecule such as 3, 4-epoxycyclohexyl methacrylate; and so on. Here, the term (meth) acrylate is a general term for acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions below.
The weight average molecular weight of the photocurable compound varies depending on the resin skeleton, and is preferably 2,000 to 200,000. By setting the weight average molecular weight to 2,000 or more, the nonstick property and the resolution can be improved. Further, the change in state of the coating film surface with time becomes moderate, and the adhesion to the substrate can be further improved. Further, the weight average molecular weight is 200,000 or less, whereby the developability and storage stability can be improved. The weight average molecular weight is more preferably 4,000 to 150,000, and still more preferably 5,000 to 100,000. The weight average molecular weight can be measured by a Gel Permeation Chromatography (GPC) method (polystyrene standard).
When the composition further contains a thermal crosslinking material described later, the mixing amount of the photocurable compound is preferably 50 to 90 parts by mass, based on 100 parts by mass of the total amount of the photocurable compound and the thermal crosslinking material in terms of solid content. When the mixing amount of the photocurable compound is within the above range, a hollow structure having further strength can be formed. In addition, the change in state of the coating film surface with time becomes moderate, and adhesion to the substrate can be further improved.
[ thermally crosslinkable Material ]
By adding the thermal crosslinking material, the heat resistance of the photosensitive film can be expected to be improved. The thermal crosslinking material can be used alone in 1 kind or more than 2 kinds in combination. As the thermally crosslinkable material, any known thermally crosslinkable material can be used. For example, known thermosetting components such as amino resins such as melamine resin, benzoguanamine resin, melamine derivative, benzoguanamine derivative, isocyanate compounds, blocked isocyanate compounds, cyclic carbonate compounds, epoxy compounds, oxetane compounds, episulfide resins, bismaleimide, carbodiimide resins, melamine resins, urea resins, polyimide resins, phenol novolac, cresol novolac, and the like can be used. Among these, epoxy resins, melamine resins, and urea resins are preferable, and epoxy resins are more preferable, from the viewpoint of adhesion between a cured product of the photosensitive composition and a substrate.
When the composition further contains the photocurable compound, the mixing amount of the photocurable compound and the thermal crosslinking material is preferably 10 to 40 parts by mass, based on 100 parts by mass of the total amount of the photocurable compound and the thermal crosslinking material in terms of solid content. By setting the mixing amount of the thermal crosslinking material to the above range, a hollow structure having more strength can be formed. In addition, when the mixing amount of the thermal crosslinking material is 40 parts by mass or less, the ratio of the photocurable compound is increased, and thus the resolution is further improved.
When an epoxy resin or the like is used as the thermal crosslinking material, a curing agent for curing the epoxy resin may be further contained. Examples of the curing agent include amines, imidazoles, polyfunctional phenols, acid anhydrides, isocyanates, and polymers containing these functional groups, and two or more of these may be used as necessary.
[ photopolymerization initiator ]
Specific examples of the photopolymerization initiator include: bis (2, 6-dichlorobenzoyl) phenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -2, 5-dimethylphenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -1-naphthylphosphine oxide, bisacylphosphine oxides such as bis- (2, 6-dimethoxybenzoyl) phenylphosphine oxide, bis- (2, 6-dimethoxybenzoyl) -2,4, 4-trimethylpentylphosphine oxide, bis- (2, 6-dimethoxybenzoyl) -2, 5-dimethylphenylphosphine oxide, and bis- (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide; monoacyl phosphine oxides such as 2, 6-dimethoxybenzoyldiphenylphosphine oxide, 2, 6-dichlorobenzoyldiphenylphosphine oxide, methyl 2,4, 6-trimethylbenzoylphenylphosphinate, 2-methylbenzoyldiphenylphosphine oxide, isopropyl pivaloylphenylphosphine oxide and 2,4, 6-trimethylbenzoyldiphenylphosphine oxide; hydroxybenzophenones such as ethyl phenyl (2,4, 6-trimethylbenzoyl) phosphinate, 1-hydroxy-cyclohexylphenyl ketone, 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] phenyl } -2-methyl-propan-1-one, and 2-hydroxy-2-methyl-1-phenylpropan-1-one; benzoins such as benzoin, benzil, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, and benzoin n-butyl ether; benzoin alkyl ethers; benzophenones such as benzophenone, p-methylbenzophenone, michelione, methylbenzophenone, 4 '-dichlorobenzophenone, and 4, 4' -bis (diethylamino) benzophenone; acetophenones such as acetophenone, 2-dimethoxy-2-phenylacetophenone, 2-diethoxy-2-phenylacetophenone, 1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl) -1- [4- (4-morpholino) phenyl ] -1-butanone, and N, N-dimethylaminoacetophenone; thioxanthones such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, 2-chlorothioxanthone and 2, 4-diisopropylthioxanthone; anthraquinones such as anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone; ketals such as acetophenone dimethyl ketal and benzoin dimethyl ether; benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2- (dimethylamino) ethyl benzoate, and ethyl p-dimethylbenzoate; oxime esters such as 1, 2-octanedione, 1- [4- (phenylthio) -,2- (O-benzoyloxime) ], ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (O-acetyloxime) and the like; cyclopentadienyltitanates such as bis (. eta.5-2, 4-cyclopentadien-1-yl) -bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium and bis (cyclopentadien) -bis [2, 6-difluoro-3- (2- (1-pyrrol-1-yl) ethyl) phenyl ] titanium; phenyl disulfide 2-nitrofluorene, butyroin, anisoin ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide, and the like.
When the composition contains the above-mentioned photocurable compound, the amount of the photopolymerization initiator to be blended is preferably 0.1 to 10 parts by mass in terms of solid content per 100 parts by mass of the photocurable compound. By setting the mixing amount of the photopolymerization initiator to the above range, the resolution is further improved.
A photoinitiator aid or sensitizer may be used in combination with the photopolymerization initiator. Examples of the photo-initiation aid or sensitizer include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, xanthone compounds, and the like. These compounds may be used as a photopolymerization initiator, but are preferably used in combination with a photopolymerization initiator. In addition, the photoinitiator aid or sensitizer may be used singly or in combination of two or more.
These photopolymerization initiators, photoinitiator aids, and sensitizers absorb specific wavelengths, and thus, in some cases, the sensitivity is lowered, and they may function as ultraviolet absorbers. However, these reagents are not solely used for the purpose of improving the sensitivity of the composition. The optical film can absorb light of a specific wavelength as required, and can improve the photoreactivity of the surface and improve the accuracy of the shape during exposure and development.
[ Filler ]
By blending a filler in the photosensitive composition, the change with time of the surface morphology of the photosensitive film can be improved while improving the hardness, heat resistance, and the like of the coating film. As such a filler, a known inorganic or organic filler can be used, and an inorganic filler is preferable. Examples of the inorganic filler include metal hydroxides such as barium sulfate, silica, mica, hydrotalcite, talc, metal oxides, and aluminum hydroxide. Among these, silica and mica are preferable. Examples of the silica include spherical silica and amorphous silica.
If necessary, other resins than the above-mentioned ones, a thermal radical initiator, a polymerization inhibitor, an adhesion promoter, an organic solvent, and the like may be added to the photosensitive composition.
For example, by compounding another resin, heat resistance can be improved. Examples of the other resin include polyimide, polyoxazoles, and precursors thereof, novolak resins such as phenol novolak and cresol novolak, polyamideimide, polyamide, phenoxy resin, polyether sulfone, and the like. These may be used alone or in combination of two or more.
In addition, the polyimide resin may be made alkali-soluble. Specifically, the imide group has an alkali-soluble group such as a carboxyl group or an acid anhydride group. The alkali-soluble group can be introduced by a known and conventional method. For example, a resin obtained by reacting a carboxylic acid anhydride component with at least one of an amine component and an isocyanate component is mentioned. The imidization may be carried out by thermal imidization or chemical imidization, and they may be produced by using them in combination.
Further, by compounding a thermal radical initiator, the photocurable compound can be cured at a low temperature in a short time. Examples of the thermal radical initiator include peroxides and azo compounds.
Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, t-butyl catechol, phenothiazine, and the like. Examples of the adhesion promoter include silane coupling agents such as γ -glycidoxysilane, aminosilane, and γ -ureidosilane.
The photosensitive film can be formed by applying the photosensitive composition on one surface of the support film and drying the photosensitive composition. In consideration of the coatability of the photosensitive composition, the photosensitive composition may be diluted with an organic solvent to adjust the viscosity to an appropriate value, and coated on one surface of the support film with a uniform thickness by a comma coater, a knife coater, a lip coater, a bar coater, a squeeze coater, a reverse coater, a roll coater, a gravure coater, a spray coater, a bar coater, a roll coater, a comma coater, a slit die extrusion coater, a spin coater, or the like, and the organic solvent may be evaporated by drying, thereby obtaining a non-tacky coating film. The coating film thickness is not particularly limited, and is usually appropriately selected in the range of 0.5 to 500 μm in terms of the film thickness after drying. The thickness is preferably in the range of 1 to 300 μm in terms of the material used for forming the wall portion or the lid portion of the hollow structure.
The organic solvent to be used is not particularly limited, and examples thereof include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, it is: ketones such as Methyl Ethyl Ketone (MEK) and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol butyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha and solvent naphtha, and N-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide and γ -butyrolactone. Such organic solvents may be used alone in 1 kind, or may be used as a mixture of 2 or more kinds.
The organic solvent can be volatilized and dried by using a hot air circulation type drying furnace, an IR furnace, a hot plate, a convection heating furnace, or the like (a method of bringing hot air in a drying machine into convection contact with a heat source of an air heating system using steam and a method of spraying the hot air to a support through a nozzle). The conditions for the volatilization drying are appropriately selected from the range of 60 to 120 ℃ for 1 to 60 minutes.
[ protective film ]
The photosensitive film laminate of the present invention is provided with a protective film on the surface of the photosensitive film opposite to the support film for the purpose of preventing adhesion of dust and the like to the surface of the photosensitive film and improving the handling property, and further for the purpose of adjusting the arithmetic average surface roughness Ra of the surface of the photosensitive film.
As the protective film, for example, a polyester film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used, and a polypropylene film is particularly preferable. In addition, it is preferable to select a material having a smaller adhesive force between the protective film and the photosensitive film than between the protective film and the photosensitive film. In addition, when the photosensitive film laminate is used, the surface of the protective film in contact with the photosensitive film may be subjected to the release treatment in order to facilitate the peeling of the protective film.
The thickness of the protective film is not particularly limited, and is appropriately selected in the range of approximately 10 μm to 200 μm depending on the application.
In the present invention, it is preferable to use a protective film having an arithmetic average surface roughness Ra' of 0.10 μm or more on the surface of the protective film on the side in contact with the photosensitive film. Further, it is more preferable to use a protective film having an arithmetic average surface roughness Ry' of 1.00 μm or more on the surface of the protective film on the side in contact with the photosensitive film. By using the protective film having such a surface morphology, a photosensitive film having an arithmetic average surface roughness Ra of 0.10 μm or more and further a photosensitive film having an arithmetic average surface roughness Ry of 1.00 μm or more can be easily formed. The arithmetic average surface roughness Ra' of the protective film is more preferably 0.15 μm or more, and still more preferably 0.20 μm or more. When the upper limit is set, the thickness is preferably 1.00 μm or less, more preferably 0.80 μm or less, and still more preferably 0.60 μm or less.
The maximum height Ry' of the protective film on the surface side in contact with the photosensitive film is more preferably 1.20 μm or more, and still more preferably 1.40 μm or more. When the upper limit is set, the thickness is preferably 5.00 μm or less, more preferably 4.00 μm or less, and still more preferably 3.00 μm or less. Here, the portions of the arithmetic average surface roughness Ra 'and the maximum height Ry' and the specific measurement method thereof are explained in the above [ photosensitive film ]. The arithmetic average surface roughness Ra 'of the protective film and the arithmetic average surface roughness Ra of the photosensitive film, and the maximum height Ry' of the protective film and the maximum height Ry of the photosensitive film are not necessarily equal to each other, and the arithmetic average surface roughness Ra and the maximum height Ry of the photosensitive film can be adjusted to fall within the above specific ranges.
The method of adjusting the protective film having the arithmetic average surface roughness Ra 'and the maximum height Ry' is not particularly limited, and for example, when a filler is added to the resin of the protective film, the particle diameter or the amount of the filler added is adjusted, and the surface of the protective film can be made to have a predetermined form by performing sandblasting, texturing, matte coating, chemical etching, or the like.
[ cured product ]
A cured product is formed by using the photosensitive film laminate of the present invention. As an example of the cured product, a method of forming a hollow structure having a wall portion and a lid portion using the photosensitive film laminate of the present invention will be described.
[ method of Forming wall portion ]
First, a wall portion is formed using the photosensitive film laminate. Specifically, the desired wall portion can be formed through the following steps: a laminating step of peeling the protective film from the photosensitive film laminate and laminating the photosensitive film on an adherend such as a substrate; an exposure step of irradiating a predetermined portion of the photosensitive film with light through a mask to photocure the exposed portion; a developing step of removing a portion of the photosensitive film other than the portion subjected to photocuring by using a developing solution; and a main curing step of curing the photo-cured portion of the photosensitive film with light or heat to form a cured product. Hereinafter, each step will be described.
In the laminating step, the protective film is peeled off from the photosensitive film laminate, and the exposed photosensitive film surface side is laminated on the substrate. The lamination may be performed by bonding by thermocompression bonding or the like. Examples of the adherend substrate include a silicon wafer, a glass substrate, a ceramic substrate, an aluminum-based substrate, a stainless-steel substrate, a glass epoxy substrate, a polyester substrate, and a polyimide substrate. Examples of the thermocompression bonding method include thermocompression bonding, roll lamination, vacuum press bonding, diaphragm vacuum lamination, and the like. From the aspects of adhesion and embedding property with the substrate; and maintaining good resolution without curing the photosensitive composition during thermocompression bonding, the thermocompression bonding temperature is preferably 20 to 150 ℃, more preferably 35 to 100 ℃, and even more preferably 40 to 85 ℃. The lamination pressure is preferably 0.005MPa to 10MPa, more preferably 0.005MPa to 3 MPa.
Next, an exposure process is performed. The exposure includes negative type and positive type, and negative type is preferable. In the case of a negative type, a photosensitive film laminate laminated on a substrate is irradiated with light through a negative mask having a desired pattern for forming a wall shape, and the exposed portion of the photosensitive film is photocured. Here, the active light used for exposure may be ultraviolet light, visible light, electron beam, X-ray, or the like. Among these, ultraviolet rays and visible rays are particularly preferable. Preferably, the exposure is performed through a photomask by using a mask of i-ray (365nm), h-ray (405nm) or g-ray (436nm) from an ultrahigh-pressure mercury lamp. Further, a method of directly drawing on a photosensitive film without a mask by using a laser beam having a wavelength of 405nm may be mentioned. In this step, the support film constituting the photosensitive film laminate may be peeled off before exposure or after exposure. The support film may be peeled or not peeled before exposure, and may be subjected to a heat treatment at a temperature of 40 to 150 ℃ for 5 seconds to 60 minutes using a heating furnace or a hot plate. After exposure, the support film may be peeled or not peeled, and subjected to a heat treatment at a temperature of 40 to 150 ℃ for 5 seconds to 60 minutes using a heating furnace or a hot plate.
Next, the portions (unexposed portions) of the photosensitive film other than those subjected to photocuring were removed using an organic solvent-based or alkali aqueous solution-based developer, thereby forming a pattern of the wall portions.
As the developer, an organic solvent such as N-methylpyrrolidone, ethanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate, γ -butyrolactone, triethylene glycol dimethyl ether, methyl amyl ketone (2-heptanone), butyl acetate, or the like can be used. In addition, an aqueous alkaline solution such as sodium carbonate, sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, or tetramethylammonium hydroxide (TMAH) can be used. Among these, propylene glycol methyl ether acetate is preferably used in the case of solvent development from the viewpoint of development speed. On the other hand, in the case of alkali development, sodium carbonate, sodium hydroxide, or tetramethylammonium hydroxide (TMAH) is preferable.
Examples of the developing method include spraying a developing solution to the photosensitive film, dipping the photosensitive film in the developing solution, or applying ultrasonic waves while dipping the photosensitive film.
After development, water is preferably used as necessary; alcohols such as methanol, ethanol, and isopropanol; n-butyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether acetate, and the like. Examples of the rinsing method include spraying a developing solution onto the photosensitive film surface, dipping the photosensitive film surface in a developing solution, or applying ultrasonic waves while dipping the photosensitive film surface.
Subsequently, the photo-cured portion (exposed portion) of the photosensitive film is cured by light or heat, thereby forming the wall portion. When curing (cure) after development is carried out by heat, it is preferable to select a temperature and carry out the curing for 1 to 2 hours while raising the temperature stepwise. The temperature of the thermosetting is suitably selected within the range of 120 to 400 ℃ and the time of 60 to 120 minutes. The temperature may be fixed to a constant temperature or may be increased in stages. In curing, it is preferable to perform heat treatment in an inert gas such as nitrogen or argon. The final heating temperature is preferably 150 ℃ to 350 ℃. In addition, photocuring may be performed before or after thermal curing or instead of thermal curing.
The thickness of the photosensitive film for forming the wall portion is preferably 1 μm to 3,000. mu.m, more preferably 5 μm to 1,000. mu.m, still more preferably 10 μm to 500. mu.m, particularly preferably 20 μm to 200. mu.m, and most preferably 20 μm to 100. mu.m. When the thickness of the photosensitive film is 1 μm or more, the shape of the wall portion is easily maintained, and large deformation is less likely to occur even under high-temperature and high-pressure conditions during molding. When the thickness is 3,000 μm or less, it is difficult to suppress the light transmittance of the photosensitive film at the time of exposure. The thickness of the wall portion may be increased by repeating a lamination step of overlapping the photosensitive films. The final film thickness of the wall portion formed through the curing step is also preferably 1 μm to 3,000. mu.m, more preferably 5 μm to 500. mu.m, and still more preferably 10 μm to 200. mu.m.
[ formation of lid portion ]
The wall portion formed of a cured product of the photosensitive film formed by the above-described forming method has a sufficient film thickness, and a hollow structure can be formed by covering an upper end of the wall portion with a ceramic substrate, a Si substrate, a glass substrate, a metal substrate, or the like as a cover, or a cover portion can be formed using a photosensitive film laminate. Hereinafter, a method of forming a lid portion using the photosensitive film laminate will be described.
The photosensitive film laminate from which the protective film is peeled is laminated on the upper end of the wall portion formed as described above, and the photosensitive film cured by light is cured by exposure and optionally development to form a lid portion, whereby a hollow structure can be formed. When the lid portion is formed by using the photosensitive film laminate, it is not necessarily required to go through a development step, and for example, when a plurality of hollow structure devices are simultaneously manufactured at one time, the lid portion of the hollow structure device is exposed to light through a mask to a size corresponding to the size of the lid portion, and then the unexposed portion around the lid portion is developed, whereby the hollow structure devices can be divided into individual pieces.
The lamination, exposure, development and curing of the photosensitive film laminate can be performed in the same manner as the formation of the wall portion. Here, the adhesion at the time of lamination of the laminated body forming the wall portion and the lid portion may be performed by thermal compression. Examples of the thermocompression bonding method include a thermocompression bonding process, a roll lamination process, a vacuum press process, a diaphragm type vacuum lamination process, and the like, and among them, the roll lamination process is preferable. The thermocompression bonding temperature is preferably 20 ℃ or higher in terms of adhesion to an adherend and embeddability. In addition, the thermocompression bonding temperature is preferably 150 ℃ or lower in order to prevent the resolution of pattern formation in exposure and development from being deteriorated due to the progress of curing of the photosensitive resin component in thermocompression bonding. Namely, in terms of adhesion to the substrate and embeddability; and maintaining good resolution without curing the photosensitive composition during thermocompression bonding, the thermocompression bonding temperature is preferably 20 to 150 ℃, more preferably 35 to 100 ℃, and even more preferably 40 to 85 ℃. The lamination pressure is preferably 0.005MPa to 10MPa, more preferably 0.005MPa to 3 MPa.
The support film constituting the photosensitive film laminate may be peeled off before exposure, may be peeled off after exposure, or may be peeled off after curing of the photosensitive film, and since a state in which a cured product of the photosensitive film serving as the lid portion is supported only by the wall portion is formed, peeling after exposure and peeling after curing are preferable from the viewpoint of stability. The support film may be peeled or not peeled before exposure, and may be subjected to a heat treatment at a temperature of 40 to 150 ℃ for 5 seconds to 60 minutes using a heating furnace or a hot plate. After the exposure, the support film may be peeled or not peeled, and may be subjected to a heat treatment at a temperature of 40 to 150 ℃ for 5 seconds to 60 minutes using a heating furnace or a hot plate. Further, the development or curing may be performed together with the wall portion and the lid portion. The cured film forming the cap portion preferably has a tensile elastic modulus of 2.0GPa or more.
The thickness of the photosensitive film for forming the lid portion is preferably 1 μm to 3,000. mu.m, more preferably 5 μm to 1,000. mu.m, still more preferably 10 μm to 500. mu.m, particularly preferably 20 μm to 200. mu.m, and most preferably 20 μm to 100. mu.m. The final film thickness of the lid portion formed by the curing step is preferably 10 μm to 3,000 μm. If the thickness of the lid is 10 μm or more, the shape of the hollow structure is easily maintained, and large deformation is less likely to occur even under high-temperature and high-pressure conditions during molding. In addition, if the thickness is 3,000 μm or less, it is difficult to suppress the light transmittance of the photosensitive film at the time of exposure. The thickness of the wall portion may be increased by repeating a lamination step of overlapping the photosensitive films.
In the present invention, the wall portion is formed without using the photosensitive film laminate of the present invention, and only the lid portion may be formed using the photosensitive film laminate of the present invention, but if the photosensitive film laminate of the present invention is used for both the pattern of the wall portion and the lid portion, the adhesiveness between both is more excellent, and peeling of the plating layer or the like in the proximal portion of the hollow structure can be suppressed.
According to the present invention, in an electronic component having a hollow structure such as a SAW filter, peeling of a plating layer or the like in an adjacent portion of the hollow structure can be suppressed by forming a wall portion or a lid portion using the photosensitive film laminate of the present invention. Further, the hollow structure is protected from moisture by the wall portion and the lid portion, and the hollow structure can be maintained even at high temperatures, so that the present invention can be applied to electronic components requiring a hollow structure, such as SAW filters, CMOS/CCD sensors, and MEMS, and is useful for miniaturization, height reduction, and high functionality of electronic components. The photosensitive film laminate of the present invention is particularly suitable for forming a wall portion or a lid portion of a hollow structure of a SAW filter, and is particularly suitable for obtaining a highly reliable electronic component in which peeling of a plating layer or the like in a portion close to the hollow structure is suppressed. The present invention can also be used for printed wiring boards such as solder resists, plating resists, resist layers, and interlayer insulating materials.
< SAW Filter and method for producing the same >
A method of forming a hollow structure having a wall portion and a lid portion using the photosensitive film laminate of the present invention will be described, and a Surface Acoustic Wave (SAW) filter and a method of manufacturing the same will be described below as an example of an electronic component having a hollow structure.
First, on a substrate on which a comb-shaped electrode is formed, a protective film is peeled off from the photosensitive film laminate of the present invention, and a photosensitive film surface is laminated. The photosensitive film laminate can be laminated by the same method as described in the method for forming the wall.
Next, after the photosensitive film laminate is laminated, a predetermined portion of the photosensitive film is irradiated with light through a negative mask having a desired pattern as necessary, and the exposed portion is photocured. The exposure may be performed by the same method as that described in the method for forming the wall portion.
Next, the unexposed portion of the photosensitive film other than the exposed portion is removed using a developing solution to form a desired pattern, and then the exposed portion of the photosensitive film is cured by light or heat to form a wall portion made of a cured product. The steps of exposure, development, and curing may be performed by the same method as the method for forming the wall portion.
When the photosensitive film laminate of the present invention is used for forming a lid portion of a hollow structure of a SAW filter as described later, the wall portion may be formed by a method other than the method using the photosensitive film laminate of the present invention.
A lid is provided at the upper end of the wall portion formed as described above, thereby forming a hollow structure. Here, the cap portion can be formed by peeling the protective film from the photosensitive film laminate of the present invention, attaching the photosensitive film surface to the upper end of the wall portion, and then performing exposure, development, and curing. The cover portion and the wall portion can be bonded to each other by, for example, thermal compression bonding using a roll laminator.
The lid portion may be formed of a material other than the photosensitive film laminate of the present invention, for example, a known sealing substrate such as a permanent resist or ceramics. Among them, the cover portion is preferably made of a material having excellent moist heat resistance and low water absorption. In this case, at least the wall portion formed using the photosensitive film laminate of the present invention is used as a wall portion for forming a hollow structure of the SAW filter.
After the wall portion and the lid portion are formed as described above, plating, metal ball mounting, and the like may be performed to electrically connect the electrode to the conductor wired on the surface on the opposite side to the electrode in the substrate.
In the formation of the wall portion, a hole for forming the internal conductor may be formed inside the wall portion by exposure and development. Then, the photosensitive film laminated on the support film is laminated on the wall portion, and exposure is performed through a mask. Since the mask shields only a portion corresponding to the diameter of the hole for forming the internal conductor from light, a cap portion is formed in which the remaining portion is photocured. The unexposed portion of the lid portion is patterned by performing a desmear treatment or the like after development so as to completely penetrate the hole in the wall portion formed previously. In addition, patterning of the cap portion may use a laser. As the laser, a known laser such as a YAG laser, a carbon dioxide laser, or an excimer laser can be used. The exposure or laser irradiation may be appropriately selected and used according to the thickness of the wall portion, the shape of the internal conductor formed inside the wall portion, and the shape of the lid surface wiring pattern.
Further, an internal conductor is formed in the hole formed in the wall portion and the lid portion by a plating method or the like, and a wiring is formed on the surface of the lid portion. In the present invention, the internal conductor may be formed in the hole formed in the wall portion and the lid portion by a conductor filling method using a metal paste or a resin paste containing a metal powder, in addition to the plating method. Through these steps, the conductor of the comb-shaped electrode forming wiring on the substrate and the conductor for wiring formed on the surface of the lid are electrically connected. Finally, a SAW filter as an electronic component having a hollow structure can be obtained by mounting metal balls on the surface of the lid portion by reflow or the like.
Further, the SAW filter may be sealed with a sealing material. When sealing is performed with a sealing material, the following steps are generally performed, but the present invention is not limited thereto. First, the SAW filter is set in a molding die. Next, the solid sealant pellet was set in the pot of the molding machine. Further, the sealing material is melted at a mold temperature of 150 to 180 ℃ and pressure is applied to the melted sealing material to be poured into a mold (mold). And finally, pressurizing for 30-120 seconds, opening the mold after the sealing material is thermally cured, and taking out the molded product, thereby completing the sealing of the SAW filter.
Generally, sealing with a sealing material is performed before mounting metal balls, and after sealing, metal balls are mounted by reflow on the surface of the substrate opposite to the surface to be sealed. However, the metal ball may be mounted and then sealed with a sealing material. The number of the SAW filters sealed with the sealing material may be 1 or 2 or more. In this case, a plurality of SAW filters formed on one substrate are sealed with a sealing material and then cut into individual pieces. Specifically, first, a plurality of SAW filters are produced on one substrate, and the wall portion and the lid portion are formed using the photosensitive film laminate of the present invention and the like. Thereafter, the resultant is collectively sealed with a sealing material and separated into individual pieces by a method such as cutting, thereby obtaining a SAW filter.
As described above, in the process of manufacturing the SAW filter, the photosensitive film laminate of the present invention can be used to form a hollow structure having a wall portion and a lid portion. As described above, since the photosensitive film laminate of the present invention has a surface morphology that changes over time within a specific range, a SAW filter can be realized in which peeling of a plating layer or the like in the vicinity of the hollow structure is suppressed. In addition, the inside of the hollow structure can be isolated from the surroundings by the wall portion and the lid portion formed by using the photosensitive film laminate of the present invention, and therefore, the corrosion of the aluminum electrode can be suppressed. Further, since a cured product of the photosensitive film has a high elastic modulus at a high temperature, there is an advantage that the hollow structure can be maintained even at a temperature and a pressure at the time of sealing the resin mold.
Examples
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following description, the terms "part(s)" and "%" are based on mass unless otherwise specified, except for% relative humidity. The operation in the following examples was carried out at room temperature (23 ℃ C.), a relative humidity of 42% and a yellow light.
< Synthesis example 1>
< Synthesis of carboxyl group-containing resin >
A2L flask equipped with a stirrer and a reflux tube was charged with 367.0 parts of a bifunctional bisphenol-A type epoxy resin (RE-310S, epoxy equivalent: 183.5 g/eq, manufactured by Nippon chemical Co., Ltd.), 144.1 parts of acrylic acid (molecular weight: 72.06) as a monocarboxylic acid compound having an ethylenically unsaturated group, 1.02 parts of hydroquinone monomethyl ether as a thermal polymerization inhibitor and 1.53 parts of triphenylphosphine as a reaction catalyst, and reacted at 98 ℃ until the acid value of the reaction solution became 0.5mgKOH/g or less to obtain an epoxycarboxylate compound (theoretical molecular weight: 511.1).
Next, 445.93 parts of carbitol acetate as a solvent for reaction, 0.70 part of 2-methylhydroquinone as a thermal polymerization inhibitor, and118.8 parts of dimethylolpropionic acid (molecular weight: 134.1) as a diol compound having a carboxyl group was heated to 60 ℃. 209.6 parts of isophorone diisocyanate (molecular weight: 222.29) as a diisocyanate compound is slowly added dropwise to the solution in such a manner that the reaction temperature does not exceed 65 ℃. After the addition, the temperature was raised to 80 ℃ and the reaction was carried out for 6 hours to 2250cm by infrared absorption spectrometry-1Until the nearby absorption disappears. To the solution were added 36.7 parts of succinic anhydride (molecular weight: 100.1) as a polybasic acid anhydride and 43.0 parts of carbitol acetate. After the addition, the temperature was raised to 95 ℃ to conduct a reaction for 6 hours, thereby obtaining a carboxyl group-containing photosensitive resin varnish 1 containing 65% by weight of a carboxyl group-containing polyester urethane resin having a weight average molecular weight of 10,000. The acid value was measured, and it was 66.61mgKOH/g (solid acid value: 102.5 mgKOH/g). The weight average molecular weight is measured by a general method using a Gel Permeation Chromatography (GPC) method (polystyrene standard).
Synthesis example 2
< Synthesis of carboxyl group-containing resin >
119.4g of novolak-type cresol resin (ショーノール CRG951, OH equivalent: 119.4, manufactured by AICA KOGYO Co., Ltd.), 1.19g of potassium hydroxide and 119.4g of toluene were charged into an autoclave equipped with a thermometer, a nitrogen introducing device and an alkylene oxide introducing device, and a stirring device, and the inside of the system was replaced with nitrogen gas under stirring, followed by heating to raise the temperature. Then, 63.8g of propylene oxide was slowly dropped at 125-132 ℃ at 0-4.8 kg/cm2The reaction was carried out for 16 hours. Then, the reaction solution was cooled to room temperature, and 1.56g of 89% phosphoric acid was added and mixed to the reaction solution to neutralize potassium hydroxide, thereby obtaining a propylene oxide reaction solution of a novolak-type cresol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2g/eq. The obtained novolak-type cresol resin is a substance in which an alkylene oxide is added in an amount of 1.08 moles on average per 1 equivalent of the phenolic hydroxyl group.
293.0g of the obtained alkylene oxide reaction solution of novolak-type cresol resin, 43.2g of acrylic acid, 11.53g of methanesulfonic acid, 0.18g of methylhydroquinone and 252.9g of toluene were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml/min to react at 110 ℃ for 12 hours with stirring. As for the water produced by the reaction, 12.6g of water was distilled off as an azeotropic mixture with toluene. After that, the reaction solution was cooled to room temperature, and the resulting reaction solution was neutralized with 35.35g of a 15% aqueous sodium hydroxide solution, followed by water washing. Then, the toluene was replaced with 118.1g of diethylene glycol monoethyl ether acetate in an evaporator while distilling off, to obtain a novolak-type acrylate resin solution. Next, 332.5g of the novolak type acrylic resin solution and 1.22g of triphenylphosphine were put into a reactor equipped with a stirrer, a thermometer and an air blowing tube, air was blown at a rate of 10 ml/min, 62.3g of tetrahydrophthalic anhydride was slowly added under stirring, and the mixture was reacted at 95 to 101 ℃ for 6 hours to obtain a carboxyl group-containing photosensitive resin varnish 2 having an acid value of 88mgKOH/g and a nonvolatile content of 71%.
< Synthesis example 3>
< Synthesis of carboxyl group-containing resin >
220 parts (1 equivalent) of cresol novolak type epoxy resin (EOCN-104S, epoxy equivalent 220g/eq, manufactured by Nippon chemical Co., Ltd.), 140.1 parts of carbitol acetate and 60.3 parts of solvent naphtha were put in a flask, heated to 90 ℃ and stirred to dissolve them.
The resulting solution was once cooled to 60 ℃ and 72 parts (1 mol) of acrylic acid, 0.5 part of methylhydroquinone and 2 parts of triphenylphosphine were added thereto, and the mixture was heated to 100 ℃ to react for about 12 hours, thereby obtaining a reactant having an acid value of 0.2 mgKOH/g. 80.6 parts (0.53 mol) of tetrahydrophthalic anhydride was added thereto, and the mixture was heated to 90 ℃ to react for about 6 hours to obtain carboxyl group-containing photosensitive resin varnish 3 having an acid value of a solid content of 85mgKOH/g and a solid content of 64.9%.
< Synthesis example 4>
< Synthesis of carboxyl group-containing resin >
190 parts of EPPN-201 (epoxy equivalent 190, manufactured by Nippon chemical Co., Ltd.) of a phenol novolak type epoxy resin was charged into a four-necked flask equipped with a stirrer and a reflux condenser, 184 parts of carbitol acetate was added thereto, and the mixture was dissolved by heating. Then, 0.46 parts of methylhydroquinone as a polymerization inhibitor and 1.38 parts of triphenylphosphine as a reaction catalyst were added. The mixture was heated to 95 ℃ to 105 ℃ and 72 parts (1 equivalent) of acrylic acid was slowly added dropwise to the mixture, followed by reaction for 16 hours. The resulting reaction product (hydroxyl group: 1 equivalent) was cooled to 80 ℃ to 90 ℃, 50 parts (0.5 equivalent) of succinic anhydride was added, reacted for 8 hours, and taken out after cooling. Thus, a carboxyl group-containing photosensitive resin varnish 4 having a nonvolatile content of 65%, an acid value of a solid matter of 89mgKOH/g, and a solid content of 65.0% was obtained.
< production of photosensitive composition >
The photosensitive compositions 1 to 5 were prepared by mixing the components in the amounts and proportions (parts by mass) shown in table 1 below and kneading the components uniformly. Note that, in table 1,1 to 22 represent the following components.
1 methylated Melamine resin, manufactured by Sanwa Chemical Co., Ltd
2 fluorene skeleton-containing epoxy resin, OSAKA GAS CHEMICALS Co., Ltd
3 bisphenol A epoxy resin (DIC corporation)
4 Biphenylaralkyl epoxy resin (manufactured by Nippon Kabushiki Kaisha)
5 phenol novolac epoxy resin (DIC corporation)
6 Dicyclopentadiene type epoxy resin (available from DIC Co., Ltd.)
Synthesis example 1 (amount of solid component to be mixed)
Synthesis example 2 (amount of solid component to be mixed)
9 Synthesis example 3 (amount of solid component to be mixed)
10 Synthesis example 4 (amount of solid component to be blended)
11 alkali-soluble photosensitive resin having an amide imide structure (solid content: 20%, manufactured by NIPPON KODOSHI CORPORATION)
Acrylate of 12 dipentaerythritol, manufactured by Kyoeisha chemical Co., Ltd
13 ε -caprolactone-modified dipentaerythritol acrylate, Kyoeisha chemical Co., Ltd
14 Dicidodecane Dimethylacrylate manufactured by Xinzhongcun chemical industries, Ltd
15 Oxime ester photopolymerization initiator (ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (0-acetyloxime), BASF Japan K.K.)
16 Diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide (manufactured by IGM Resins Co., Ltd.)
172-ethyl-4-methylimidazole (manufactured by four chemical industry Co., Ltd.)
18 spherical silica, manufactured by Admatechs, Inc
19 spherical silica particles with an average particle size of 100nm
20 c.i. pigment blue 15: 3
Pigment yellow 147
22 Pileo red K3580 (manufactured by BASF Japan Co., Ltd.)
[ Table 1]
Figure BDA0002010310970000241
< production of protective film >
Production example 1
The weight average molecular weight (Mw) was 3.0X 105Polypropylene resin pellets having a molecular weight distribution (Mw/Mn) of 5.0 and an isotactic component fraction of 95.0% were fed to an extruder, melted at a resin temperature of 250 ℃, extruded through a T die, and wound on a metal drum having a surface temperature of 150 ℃ to form a film, thereby producing a casting web having a thickness of about 225 μm. Subsequently, the cast unstretched web was stretched 5 times in the flow direction at a temperature of 120 ℃ and immediately cooled to room temperature, and then stretched 10 times in the transverse direction at a temperature of 160 ℃ by a tenter to obtain a biaxially stretched polypropylene film 1 having a thickness of 12 μm. The biaxially oriented polypropylene film 1 was used as a protective film 1.
Production example 2
The weight average molecular weight (Mw) was 3.1X 105Polypropylene resin pellets having a molecular weight distribution (Mw/Mn) of 5.5 and an isotactic component fraction of 93.0% were fed to an extruder to prepare a resinThe molten film was melted at a temperature of 250 ℃ and extruded through a T die, and the film was wound around a metal drum having a surface temperature of 150 ℃ to form a film, thereby producing a casting blank sheet having a thickness of about 225 μm. Subsequently, the cast unstretched web was stretched 5 times in the flow direction at a temperature of 200 ℃ and immediately cooled to room temperature, and then stretched 10 times in the transverse direction at a temperature of 160 ℃ by a tenter to obtain a biaxially stretched polypropylene film 2 having a thickness of 15 μm. The biaxially oriented polypropylene film 2 was used as the protective film 2.
Production example 3
The weight average molecular weight (Mw) was 3.0X 105Polypropylene resin pellets having a molecular weight distribution (Mw/Mn) of 5.0 and an isotactic component fraction of 95.0% were fed to an extruder, melted at a resin temperature of 250 ℃, extruded through a T die, and wound around a metal drum having a surface temperature of 100 ℃ to form a film, thereby producing a green casting sheet having a thickness of about 225 μm. Subsequently, the cast unstretched web was stretched 5 times in the flow direction at a temperature of 120 ℃ and immediately cooled to room temperature, and then stretched 10 times in the transverse direction at a temperature of 160 ℃ by a tenter to obtain a biaxially stretched polypropylene film 3 having a thickness of 12 μm. The biaxially oriented polypropylene film 3 was used as the protective film 3.
< production of supporting film >
Polyethylene terephthalate and a polyethylene terephthalate master batch containing 1.0 mass% of silica having an average primary particle diameter of 1 μm were dried at 170 ℃ respectively, and then supplied to a twin-screw extruder, melted at 290 ℃, and subjected to T-die coextrusion to form a film, thereby producing an unstretched film. Subsequently, the unstretched film was biaxially stretched to obtain a support film 1 having a thickness of 40 μm.
< production of photosensitive film laminate >
Example 1
The arithmetic average surface roughness Ra 'and the maximum height Ry' of the protective film 1 obtained as described above were measured in the following manner, and as a result, Ra 'was 0.18 μm and the maximum height Ry' was 1.28. mu.m.
The arithmetic mean surface roughness Ra 'and Ry' were measured using a shape measuring laser microscope (VK-X100, manufactured by KEYENCE K.K.). After a main body (control unit) of a shape measurement laser microscope (same VK-X100) and a VK observation application (VK-H1 VX manufactured by KEYENCE K.K.) were started, a protective film for measurement (with the surface contacting the photosensitive film being the upper part) was placed on an X-y stage. The focal length and brightness were roughly adjusted in an image observation mode of a VK observation application (same VK-H1VX) by rotating a lens converter of a microscope unit (VK-X110 manufactured by KEYENCE K.K.) and selecting an objective lens with a magnification of 10 times. The x-y stage is operated to adjust the desired measured portion of the sample surface to the center of the screen. The objective lens having the magnification of 10 times was changed to the magnification of 50 times, and the surface of the sample was focused by the autofocus function in the image observation mode of the VK observation application (same VK-H1 VX). The surface shape of the sample was measured by selecting a simple mode of a shape measurement tab of a VK observation application (same VK-H1VX) and pressing a measurement start button, to obtain a surface image file. The VK analysis application (VK-H1 XA manufactured by KEYENCE corporation) was started, and the resulting surface image file was displayed and then subjected to tilt correction.
[ example 5]
The measurement range (lateral direction) for observation in the measurement of the surface shape of the sample was 270 μm. A line roughness window is displayed, and after JIS B0601-1994 is selected in the parameter setting area, a horizontal line is selected from the measuring line button, the horizontal line is displayed at an arbitrary position in the surface image, and an OK button is pressed, thereby obtaining numerical values of arithmetic average surface roughness Ra 'and maximum height Ry'. Further, horizontal lines are displayed at four different positions in the surface image, and numerical values of the respective arithmetic average surface roughness Ra 'and the maximum height Ry' are obtained. The average values of the obtained 5 values were calculated as the arithmetic average surface roughness Ra 'value and the maximum height Ry' value of the sample surface. The measurement was performed at room temperature (23 ℃) and a relative humidity of 42% RH.
Then, methyl ethyl ketone was added to 700 parts of the photosensitive composition 1 obtained as described above in an amount of 300 parts to dilute the composition, and the mixture was stirred with a stirrer for 15 minutes to obtain a coating solution. The coating liquid was uniformly applied to the support film 1 using a slit die extrusion coater, and dried at 80 ℃ for 15 minutes to produce a photosensitive film 1 having a thickness of 25 μm after drying. Next, a protective film 1 was laminated on the photosensitive film 1 using a roll laminator so that the measurement surfaces of the arithmetic average surface roughness Ra 'and the maximum height Ry' of the protective film 1 were in contact with the surface of the photosensitive film 1, thereby producing a photosensitive film laminate 1 (thickness of photosensitive film: 25 μm) composed of 3 layers of support film/photosensitive film/protective film. The laminating conditions of the roll laminator are appropriately adjusted to a roll temperature of 40 to 60 ℃ and a roll pressure of 0.2 to 0.4 MPa.
< production of test substrate >
A test substrate was produced using the photosensitive film laminate 1 obtained as described above. The steps for producing the test substrate will be described with reference to the drawings.
First, the protective film was peeled from the photosensitive film laminate 1 at an angle of 90 ° and at a speed of 2.5 sec/cm with respect to the other 2 layers (support film/photosensitive film) to expose the photosensitive film, the exposed surface of the photosensitive film was bonded to the surface of the prepared silicon wafer, and heat lamination was performed using a roll laminator to bring the silicon wafer into close contact with the photosensitive film. The laminating conditions of the roll laminator were 60 ℃ for the roll temperature and 0.25MPa for the roll pressure.
Then, from the support film in contact with the photosensitive film through
(i) A negative mask having an aperture pattern with a lattice size of 150 μm square and 50 μm square (see FIG. 1), or
(ii) A negative mask (not shown) having an opening pattern with a lattice size of 150 μm square and 100 μm square,
in each of the examples and comparative examples, the photosensitive film was exposed to light by a metal halide lamp in combination of pattern opening and exposure amount described in table 2, and then the support film was peeled off to expose the photosensitive film.
Then, the exposed surface of the exposed photosensitive film was immersed in propylene glycol monomethyl ether acetate (PMA) at 23 ℃ for 1 minute in examples 1 to 3 and comparative examples 1 to 2, and 1 wt% Na in example 42CO3Development was carried out in an aqueous solution at 30 ℃ under 2MPa for 60 seconds, in example 5, 1 wt% Na2CO3The resultant was developed in an aqueous solution at 30 ℃ under 2MPa for 300 seconds. Each test substrate after development was sufficiently washed with water so that no developer remained. Note that 1 wt% Na was confirmed2CO3The pH of the aqueous solution was 11.6.
Then, each test substrate was heated at 120 ℃ for 30 minutes to cure the photosensitive film, and the photosensitive film was obtained around a region having a lattice-shaped opening of 150 μm square
(i) A cured film pattern having a pattern opening of 50 μm square at the center and a width of 150 μm corresponding to the wall portion (see fig. 2); or
(ii) A cured pattern (not shown) having a pattern opening of 100 μm square at the center and a width of 300 μm corresponding to the wall portion.
The protective film is peeled off from the photosensitive film laminate 1 to expose the photosensitive film, and the exposed surface of the photosensitive film is bonded to the cured film pattern corresponding to the wall portion obtained above, followed by heat lamination. The lamination was performed by placing a 1.0kg weight on the photosensitive film and heating at 80 ℃ for 5 minutes.
Then, the photosensitive film laminate is bonded to the cured film pattern corresponding to the wall portion through the support film
(i) A negative mask having an opening pattern with a grid size of 50 μm square (see FIG. 3), or
(ii) A negative mask (not shown) having an opening pattern with a grid size of 100 μm square,
in each of the examples and comparative examples, the photosensitive film was exposed to light by a metal halide lamp in combination of pattern opening and exposure amount described in table 2, and then the support film was peeled off to expose the photosensitive film. The laminated photosensitive film laminate is bonded to the substrate with the photosensitive film laminate interposed therebetween
(i) A pattern opening of 50 μm square of the wall part is overlapped with a pattern opening of 50 μm square of the grid size of the negative mask (see FIG. 3), or
(ii) In a manner (not shown) that the pattern openings of the wall portion 100 μm square are overlapped with the pattern openings of the negative mask 100 μm square in lattice size,
and (6) carrying out exposure. Then, the exposed surface of the exposed photosensitive film was immersed in propylene glycol monomethyl ether acetate (PMA) at 23 ℃ for 1 minute in examples 1 to 3 and comparative examples 1 to 2, and 1 wt% Na in example 42CO3Development was carried out in an aqueous solution at 30 ℃ under 2MPa for 60 seconds, in example 5, 1 wt% Na2CO3The resultant was developed in an aqueous solution at 30 ℃ under 2MPa for 300 seconds. Each test substrate after development was sufficiently washed with water so that no developer remained.
Next, each test substrate was heated at 200 ℃ for 60 minutes to cure the photosensitive film, and a cured film pattern corresponding to the lid portion was formed, thereby producing a test substrate having a hollow structure including a wall portion and a lid portion. The test substrate obtained had no comb-shaped electrodes inside, but the upper end of the wall portion was covered with a lid, and a joint portion between the lid and the wall portion was formed
(i) A 50 μm square pattern opening (see FIG. 4), or
(ii)100 μm square pattern opening (not shown)
The hollow structure of (3).
Example 2
A test substrate was produced in the same manner as in example 1, except that in example 1, the photosensitive composition 2 was used instead of the photosensitive composition 1, and the protective film 2 was used instead of the protective film 1. The arithmetic average surface roughness Ra 'and the maximum height Ry' of the protective film 2 were measured in the same manner as described above, and as a result, Ra 'was 0.46 μm and the maximum height Ry' was 1.37 μm. The protective film 2 is in a roll form, and the wound inner surface thereof is measured.
Example 3
A test substrate was produced in the same manner as in example 1, except that the protective film 2 was used instead of the protective film 1 in example 1.
Example 4
In example 2, instead of development with propylene glycol monomethyl ether acetate (PMA), at 1 wt% Na2CO3A test substrate was produced in the same manner as in example 2 except that development was performed at 30 ℃ and 2MPa in an aqueous solution for 60 seconds.
Example 5
In example 4, a photosensitive composition 3 was used in place of the photosensitive composition 2, and 1 wt% of Na was added2CO3A test substrate was produced in the same manner as in example 4 except that the development was carried out in an aqueous solution at 30 ℃ and 2MPa for 300 seconds.
Comparative example 1
A test substrate was produced in the same manner as in example 2 except that in example 2, the photosensitive composition 4 was used instead of the photosensitive composition 2.
Comparative example 2
A test substrate was produced in the same manner as in example 1, except that the protective film 3 was used instead of the protective film 1 in example 1. As a result of measuring the arithmetic average surface roughness Ra 'and the maximum height Ry' of the protective film 3 in the same manner as described above, Ra 'was 0.07 μm, and the maximum height Ry' was 0.98 μm. The protective film 3 is in a roll shape, and the inner surface of the roll is measured.
< measurement of arithmetic average surface roughness Ra and maximum height Ry >
Each of the photosensitive film laminates (35 mm. times.20 mm) used in examples 1 to 5 and comparative examples 1 to 2 was bonded to the surface of a clean glass substrate (76 mm. times.26 mm. times.1.1 mmt) using a double-sided tape (KZ-12, manufactured by Nitoms corporation), and the glass substrate and the photosensitive film laminate were brought into contact with each other on the side of the support film of the photosensitive film to bond them together.
Then, the protective film of the photosensitive film laminate was peeled off at an angle of 90 ° and a speed of 2.5 sec/cm with respect to the glass substrate, thereby exposing the photosensitive film. The arithmetic average surface roughness Ra1 and the maximum height Ry1 of the exposed photosensitive film surface immediately after the protective film was peeled (after 1 minute had elapsed) were measured within 5 minutes immediately after the protective film was peeled. Ra1 and Ry1 were measured as follows.
The "arithmetic average surface roughness Ra" of the exposed photosensitive film surface was measured in the same manner as described above except that the sample was replaced with the protective film by the same device as the measurement of the arithmetic average surface roughness Ra' of the protective film surface to prepare a substrate to which the exposed photosensitive film was bonded (with the exposed photosensitive film surface being the upper portion). The "maximum height Ry" of the exposed photosensitive film surface was also measured in the same manner as described above, except that the sample was replaced with the protective film to prepare a substrate to which the exposed photosensitive film was bonded (with the exposed photosensitive film surface being the upper portion), using the same device as the measurement of the maximum height Ry' of the support film surface. The "arithmetic average surface roughness Ra 1" and "maximum height Ry 1" of each photosensitive film surface were measured and are shown in table 2.
In addition, each measurement sample was left under a yellow lamp for 180 minutes under a measurement environment (room temperature (23 ℃) and a relative humidity of 42% RH) in a state where the surface of the photosensitive film was exposed by peeling off the protective film, and then the arithmetic average surface roughness Ra and the maximum height Ry of the exposed surface of the photosensitive film were measured in the same manner as described above. The "arithmetic average surface roughness Ra 2" and "maximum height Ry 2" of each photosensitive film surface were measured and are shown in table 2.
< evaluation of plating adhesion >
Each of the test substrates of examples 1 to 5 and comparative examples 1 to 2 produced as described above was subjected to electroless copper plating. The plating conditions are as follows.
Electroless copper plating solution: melplate CU-390 (manufactured by Meltex corporation)
Plating solution temperature: 80 deg.C
Plating time: 1 hour (h)
Plating film thickness: 2.0 μm
pH: 13.0 (Room temperature)
After the plating treatment, each test substrate on which the electroless plating film was formed was washed with pure water at room temperature for 5 minutes, and then dried at 80 ℃. The cross-sectional portion of the boundary between the wall portion of each of the obtained test substrates and the electroless plated film was observed by an optical microscope and an electron microscope. The evaluation criteria are as follows.
Excellent: no gap was formed, and no problem was found in adhesion.
O: a slight gap was formed, but the adhesion was not problematic.
X: a gap is generated, and the adhesion is problematic.
The evaluation results are shown in table 2 below.
Figure BDA0002010310970000311
From the results shown in table 2, it was found that in the test substrates 1 to 5 (examples 1 to 5) in which the hollow structure was formed using the photosensitive film laminate in which the arithmetic average surface roughness Ra1 of the photosensitive film surface was 0.1 μm or more and Ra2/Ra1 was 0.40 or more and less than 1.00, the adhesion to the plating layers of the wall portion and the lid portion was high, and an electronic component having a high-quality hollow structure was obtained.
On the other hand, it is known that: in the test substrate 7 (comparative example 2) in which the hollow structure was formed using the photosensitive film laminate having the arithmetic average surface roughness Ra1 of less than 0.1 μm on the surface of the photosensitive film, even if Ra2/Ra1 was 0.40 or more and less than 1.00, the adhesion to the plating layer and the sealing material of the wall portion and the lid portion was insufficient.
In addition, it is known that: in the test substrate 6 (comparative example 1) in which the hollow structure was formed using the photosensitive film laminate in which the arithmetic average surface roughness Ra1 of the photosensitive film surface was 0.1 μm or more but Ra2/Ra1 was not in the range of 0.40 or more and less than 1.00, adhesion to the plating layer of the wall portion and the lid portion was insufficient.

Claims (8)

1. A photosensitive film laminate comprising a support film, a photosensitive film formed from a photosensitive composition, and a protective film in this order,
the protective film was peeled off from the photosensitive film laminate to expose the photosensitive film surface, and the arithmetic average surface roughness of the photosensitive film surface after leaving in an environment of 23 ℃ and a relative humidity of 42% for 1 minute was Ra1,
the protective film was peeled off from the photosensitive film laminate to expose the photosensitive film surface, and the arithmetic average surface roughness of the photosensitive film surface after leaving in an environment of 23 ℃ and a relative humidity of 42% for 180 minutes was Ra2,
at this time, the following equation is satisfied:
ra1 is more than or equal to 0.10 mu m and Ra2/Ra1 is more than or equal to 0.40 and less than 1.00.
2. The photosensitive film laminate of claim 1 wherein,
peeling the protective film from the photosensitive film laminate to expose the photosensitive film surface, wherein Ry1 represents the maximum height of the photosensitive film surface after the photosensitive film laminate is left in an environment of 23 ℃ and 42% relative humidity for 1 minute,
peeling the protective film from the photosensitive film laminate to expose the photosensitive film surface, wherein Ry2 represents the maximum height of the photosensitive film surface after leaving the photosensitive film laminate in an environment of 23 ℃ and 42% relative humidity for 180 minutes,
at this time, the following equation is satisfied:
ry1 is more than or equal to 1.00 mu m, Ry2/Ry1 is more than or equal to 0.30 and less than 1.00.
3. The photosensitive film laminate of claim 1, wherein said photosensitive composition comprises a photocurable compound.
4. The photosensitive film laminate of claim 1, wherein said photosensitive composition further comprises a photopolymerization initiator.
5. The photosensitive film laminate according to claim 1, which is used for forming a lid or a wall constituting a hollow structure in an electronic component having the hollow structure.
6. A cured product obtained by curing the photosensitive film of the photosensitive film laminate according to any one of claims 1 to 5.
7. An electronic component comprising the cured product according to claim 6.
8. The electronic component according to claim 7, which has a hollow structure comprising a wall portion and a lid portion, wherein either one or both of the wall portion and the lid portion are formed of the cured product.
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