CN110317357A - Photosensitive film lamination body and its solidfied material and electronic component - Google Patents

Photosensitive film lamination body and its solidfied material and electronic component Download PDF

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Publication number
CN110317357A
CN110317357A CN201910243227.1A CN201910243227A CN110317357A CN 110317357 A CN110317357 A CN 110317357A CN 201910243227 A CN201910243227 A CN 201910243227A CN 110317357 A CN110317357 A CN 110317357A
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China
Prior art keywords
photosensitive film
lamination body
film
photosensitive
hollow structure
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Granted
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CN201910243227.1A
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Chinese (zh)
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CN110317357B (en
Inventor
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

The photosensitive film lamination body and its solidfied material and electronic component, the photosensitive film lamination body for providing a kind of formation suitable for hollow structure are able to suppress the peeling of coating of proximity of hollow structure etc. in the electronic component that SAW filter etc. has hollow structure.Form a kind of photosensitive film lamination body, it is successively to have support membrane, photosensitive film made of being formed as photosensitive composite, with the photosensitive film lamination body of protective film, wherein, said protection film is removed from above-mentioned photosensitive film lamination body and exposes above-mentioned photosensitive film surface, at 23 DEG C, the arithmetic mean surface roughness on the above-mentioned photosensitive film surface after placing 1 minute in the environment of relative humidity 42% is set as Ra1, said protection film is removed from above-mentioned photosensitive film lamination body and exposes above-mentioned photosensitive film surface, at 23 DEG C, the arithmetic mean surface roughness on the above-mentioned photosensitive film surface after placing 180 minutes in the environment of relative humidity 42% is set as Ra2, meet following formula at this time: Ra1 >=0.10 μm and 0.40≤Ra2/Ra1 < 1.00.

Description

Photosensitive film lamination body and its solidfied material and electronic component
Technical field
The present invention relates to photosensitive film lamination bodies, more specifically, are related to the energy in the electronic component with hollow structure Enough suitable for the photosensitive film lamination body and its solidfied material and electronic component of the formation of the hollow structure.
Background technique
In recent years, the requirement to the miniaturization of electronic equipment, multifunction increasingly improves, therefore to the used ministry of electronics industry Part also further requirement miniaturization, slimming, Complex Function.Wherein, using CMOS, ccd sensor as the image sensing of representative Device is applied the integrated MEMS on one substrate of element and electronic circuit element through semiconductor fine processing technology The gyro sensor of (Micro Electro Mechanical Systems, microelectromechanical systems) technology, with sound surface Wave (SAW) filter is forming electrode pattern or fine structure on single-crystal wafer surface and playing specific electric breathing exercise for representative The exploitation of the fine electronic components such as the encapsulation of element of energy attracts attention.Following knots are formd in these fine electronic components Structure: in order to contact the active face (moving part) of sensor element with other objects, and in order to protect sensor element From moisture, dust etc. influence and form hollow structure, be configured with sensor etc. wherein.
In the past, above-mentioned electronic component formed hollow structure by processing, the engagement of inorganic material.It is desirable, however, that drop It low manufacturing cost and miniaturises, begins one's study instead of inorganic material and form hollow structure using photoresist etc. Method, such as propose following proposal: the permanent resist of lamination passes through photoetching technique and forms wall portion (wall surface) and cover shape At hollow structure (such as No. WO2009/151050).
Summary of the invention
In addition, for the electronic component that above-mentioned SAW filter etc. has hollow structure, in order to carry out to mounted board It installs and is manufactured as encapsulating structure, which has the outside being electrically connected with the wiring electrode of piezoelectric substrate Terminal or external electrode.At this point, in the proximity for the wall portion or cover for forming hollow structure, in order to obtain the company with outside wiring Reliability is connect, forms inner conductor using plating method etc..In addition, passing through biography to improve operability while protection element It passs method of molding etc. and resin seal is carried out to hollow structure or proximity.
But it in the case where forming hollow structure using permanent resist, confirms: being led if forming inside in proximity Body can then generate the peeling of coating etc. or sealing material is peeled off from the wall portion of hollow structure or the surface of cover.
Therefore, the purpose of the present invention is to provide a kind of photosensitive film lamination body of formation suitable for hollow structure, the senses Photosensitiveness film laminate is able to suppress the plating of the proximity of hollow structure in the electronic component that SAW filter etc. has hollow structure The peeling of layer etc..In addition, another object of the present invention is to provide the solidfied material for using above-mentioned photosensitive film lamination body to be formed and Electronic component with hollow structure.
As the method for forming above-mentioned hollow structure by using resin, by photosensitive film lamination several layers, and pass through Exposure, development are pre-formed wall portion, load other photosensitive films in the upper end of wall portion, carry out in the way of forming regulation shape Exposure develops and forms cover, makes photoresist heat cure, thus, it is possible to form hollow structure.The present inventor is to above-mentioned class Topic has made intensive studies, as a result, it has been found that: in the case where forming hollow structure using photosensitive film as described above, in developing procedure The developer solution used can slightly remain in the wall portion or cover for constituting hollow structure, which can ooze out from interface, thus press down The adaptation of system and coating etc., to be easy to peel off.It is further studying as a result, it has been found that, in the photosensitive film layer for having protective film In product body, make the ongoing change particular range of the configuration of surface after the exposing of photosensitive film surface by the way that protective film will be removed Photosensitive film lamination body be used for hollow structure formation, can inhibit and be hindered with the adaptation of coating etc., tool can be manufactured There is the electronic component of the hollow structure of high-quality.
The present invention is as described below.
[1] a kind of photosensitive film lamination body is photosensitive made of successively having support membrane, being formed as photosensitive composite The photosensitive film lamination body of property film and protective film, which is characterized in that
Said protection film is removed from above-mentioned photosensitive film lamination body and exposes above-mentioned photosensitive film surface, 23 DEG C, The arithmetic mean surface roughness on the above-mentioned photosensitive film surface after placing 1 minute in the environment of relative humidity 42% is set as Ra1,
Said protection film is removed from above-mentioned photosensitive film lamination body and exposes above-mentioned photosensitive film surface, 23 DEG C, The arithmetic mean surface roughness on the above-mentioned photosensitive film surface after placing 180 minutes in the environment of relative humidity 42% is set as Ra2,
Meet following formula at this time:
Ra1>=0.10 μm and 0.40≤Ra2/Ra1<1.00.
[2] the photosensitive film lamination body as described in [1], wherein
Said protection film is removed from above-mentioned photosensitive film lamination body and exposes above-mentioned photosensitive film surface, 23 DEG C, The maximum height on the above-mentioned photosensitive film surface after placing 1 minute in the environment of relative humidity 42% is set as Ry1,
Said protection film is removed from above-mentioned photosensitive film lamination body and exposes above-mentioned photosensitive film surface, 23 DEG C, The maximum height on the above-mentioned photosensitive film surface after placing 180 minutes in the environment of relative humidity 42% is set as Ry2,
Meet following formula at this time:
Ry1>=1.00 μm and 0.30≤Ry2/Ry1<1.00.
[3] the photosensitive film lamination body as described in [1], wherein above-mentioned photosensitive composite includes photocurable compound.
[4] the photosensitive film lamination body as described in [1], wherein above-mentioned photosensitive composite further includes photopolymerization and draws Send out agent.
[5] the photosensitive film lamination body as described in [1], is used to have the composition in the electronic component of hollow structure above-mentioned The formation of the cover or wall portion of hollow structure.
[6] a kind of solidfied material, which is characterized in that it is to make photosensitive film lamination body described in any one of [1]~[5] Obtained from photosensitive film solidification.
[7] a kind of electronic component, which is characterized in that it has solidfied material described in [6].
[8] electronic component as described in [7] has the hollow structure including wall portion and cover, above-mentioned wall portion and cover Any one of or both be made of above-mentioned solidfied material.
According to the present invention it is possible to provide a kind of photosensitive film lamination body of formation suitable for hollow structure, the photosensitive film Laminate is able to suppress the peeling of coating of the proximity of hollow structure etc. in the electronic component with hollow structure.In addition, Another way according to the present invention can provide the solidfied material and electronic component formed using above-mentioned photosensitive film lamination body.
Detailed description of the invention
Fig. 1 is the schematic sectional view for showing the making step of the test substrate made in embodiment 4 and embodiment 5.
Fig. 2 is the schematic sectional view for showing the making step of the test substrate made in embodiment 4 and embodiment 5.
Fig. 3 is the schematic sectional view for showing the making step of the test substrate made in embodiment 4 and embodiment 5.
Fig. 4 is the schematic sectional view for showing the making step of the test substrate made in embodiment 4 and embodiment 5.
Specific embodiment
< photosensitive film lamination body >
Photonasty made of photosensitive film lamination body of the invention successively has support membrane, formed as photosensitive composite Film and protective film.Hereinafter, being illustrated to each component for constituting photosensitive film lamination body of the invention.It needs to illustrate It is to be recorded as long as no special, in the present specification, is referred to comprising its upper limit under using the numberical range that symbol "~" indicates Range (that is, more than its lower limit, its upper limit range below) including the numerical value of limit.
[support membrane]
The support membrane for constituting photosensitive film lamination body of the invention is supported photosensitive film, as long as being that by this The well known support membrane of function, so that it may use without particular limitation, for example, can be properly used poly terephthalic acid second two Polyester film, polyimide film, polyamidoimide film, the polypropylene screen, polystyrene of alcohol ester, polyethylene naphthalate etc. The film that film etc. is made of thermoplastic resin.It, can be in the film forming of film in addition, in the case where stating thermoplastic resin film in use Add filler (being mixed into processing) into resin, carry out the coating processing (coating process) of delustring, to film surface progress blasting treatment it The spray treatment of class, or implement the processing such as hairline processing or chemical etching.Among these, from heat resistance, mechanical strength, processing Property etc. is set out, and can be properly used polyester film.Support membrane can be single layer, can also be with 2 layers of lamination or more.
For the purpose for improving intensity, above-mentioned thermoplastic resin film is preferably used in uniaxial direction or biaxially oriented carries out The film stretched.
In addition, for the purpose for improving intensity, above-mentioned thermoplastic resin film is preferably used in uniaxial direction or twin shaft side To the film stretched.
The thickness of support membrane is not particularly limited, is substantially fitted depending on the application in 10 μm or more 3,000 μm of ranges below Work as selection.
[photosensitive film]
The photosensitive film for constituting photosensitive film lamination body of the invention is formed by photosensitive composite.That is, in support membrane One photosensitive composite of the face coating comprising aftermentioned each ingredient simultaneously makes it dry, it is possible thereby to be formed.Photosensitive film is passing through Exposure is developed after the defined shape of formation, and photosensitive composite is solidified, and thus becomes solidfied material.Therefore, by protective film In the state of the surface exposing that the removing of photosensitive film lamination body makes photosensitive film, photosensitive composite is uncured shape State, therefore the configuration of surface of photosensitive film timely changes.In the present invention, find the configuration of surface of photosensitive film through when There are certain relationships between variation and the peeling of coating etc., and the photosensitive film lamination body of following conditions is met by being made, as long as The hollow structure that electronic component is formed using photosensitive film layer product body, then can inhibit and be hindered with the adaptation of coating etc., It can be realized the electronic component of the hollow structure with high-quality.
In the present invention, said protection film is removed from photosensitive film lamination body and exposes above-mentioned photosensitive film surface, 23 DEG C, place 1 minute in the environment of relative humidity 42% after the arithmetic mean surface roughness on above-mentioned photosensitive film surface set For Ra1,
Said protection film is removed from above-mentioned photosensitive film lamination body and exposes above-mentioned photosensitive film surface, 23 DEG C, The arithmetic mean surface roughness on the above-mentioned photosensitive film surface after placing 180 minutes in the environment of relative humidity 42% is set as Ra2,
Meet following formula at this time:
Ra1 >=0.10 μm and 0.40≤Ra2/Ra1 < 1.00, this is critically important.
In the case that photosensitive film when removing protective film has the convex-concave surface of defined arithmetic mean surface roughness, Convex-concave surface has the tendency for gently becoming flat condition, and configuration of surface timely changes.In the present invention, it is conceived to this The ongoing change of configuration of surface, using the photosensitive film for resting on specific configuration of surface variation, thus, it is possible to inhibit hollow knot The peeling of the coating of the proximity of structure etc..
It is in the present invention, the arithmetical average surface of the photosensitive film in the face contacted with protective film after protection film stripping is coarse Spending Ra1 is 0.10 μm or more, preferably 0.15 μm or more, more preferably 0.20 μm or more.In addition, the case where the upper limit is arranged Under, under preferably 1.00 μm, it is more preferably 0.80 μm or less, further preferably 0.60 μm or less.It should be noted that Ra1 Is defined as: protection film stripping is made above-mentioned photosensitive film surface expose, places 1 in the environment of 23 DEG C, relative humidity 42% Minute and measure value.
In addition, from the peeling aspect for further suppressing coating etc., by being contacted with protective film after protection film stripping Face photosensitive film maximum height Ry1 be preferably 1.00 or more, more preferably 1.20 μm or more, be more preferably 1.40 μm or more.In addition, in the case where the upper limit is arranged, preferably 5.00 μm or less, more preferably 4.00 μm or less, further preferred It is 3.00 μm or less.It should be noted that Ry1 is defined as: make protection film stripping above-mentioned photosensitive film surface to expose, 23 DEG C, the value placing 1 minute in the environment of relative humidity 42% and measure.
Photosensitive film surface through when change in shape pass through the arithmetic mean surface roughness phase after the stipulated time It is evaluated for just removing the ratio between arithmetic mean surface roughness (that is, Ra1) after protective film.In the present invention, as long as being following Photosensitive film lamination body be then able to suppress the peeling of coating of proximity of hollow structure etc., wherein by protective film from photosensitive Property film laminate removing and make photosensitive film surface expose, after being placed 180 minutes in the environment of 23 DEG C, relative humidity 42% The arithmetic mean surface roughness of the photosensitive film in the face contacted with protective film is set as Ra2, meets 0.40≤Ra2/Ra1 < at this time 1.00.Its reason is simultaneously confirmed, but considers as follows.I.e., thus it is speculated that: in the photosensitive film lamination body for having protective film, it will protect Film stripping and make photosensitive film surface expose after the configuration of surface with certain roughness it is timely slowly varying, if the change The ratio of change is certain, more appropriate with the closed intensity of substrate in the case where wall material, closely sealed with wall material in the case where lid material Degree is more appropriate, can prevent development when use remaining developer solution intrusion hollow structure peripheral portion, as a result, it is possible to inhibit because The peeling of coating caused by the developer solution of remaining etc..But this is only to speculate, may not be defined in this.It should be noted that this hair It is amber light as the place for placing 180 minutes in the state of will protect film stripping and expose photosensitive film surface in bright Under.
From based on appropriateness change in shape and further suppress peeling aspect, photosensitive film surface through when shape Shape variation preferably satisfies 0.50≤Ra2/Ra1≤0.95, more preferably meets 0.60≤Ra2/Ra1≤0.90.
In addition, then can further inhibit the peeling of coating etc. if following photosensitive film lamination bodies, wherein will protect Cuticula is removed from photosensitive film lamination body and exposes photosensitive film surface, places in the environment of 23 DEG C, relative humidity 42% The maximum height of the photosensitive film in the face contacted with protective film after 180 minutes is set as Ry2, meets 0.30≤Ry2/Ry1 at this time < 1.00.It should be noted that being put in the present invention as in the state of will protect film stripping and make the exposing of photosensitive film surface 180 minutes places are set, are under amber light.
From based on appropriateness change in shape and further suppress peeling aspect, photosensitive film surface through when shape Shape variation preferably satisfies 0.35≤Ry2/Ry1≤0.80, more preferably meets 0.40≤Ry2/Ry1≤0.70.
In addition, the arithmetic surface roughness Ra in the face contacted with support membrane in photosensitive film ", maximum height Ry " it is also excellent Choosing is in and the arithmetic surface roughness Ra in the above-mentioned face contacted with protective film, the same range of maximum height Ry or change rate. The photosensitive film lamination of photosensitive film made of especially successively having support membrane in unprotect film, formed as photosensitive composite In the case where body effectively.In this case, support membrane is preferably material same as aftermentioned protective film and thickness.
It should be noted that above-mentioned " arithmetic mean surface roughness Ra " and " maximum height Ry " refer to benefit in the present invention The value measured with the measurement device according to JIS B0601-1994.Hereinafter, being illustrated to specific measuring method.Arithmetic average Surface roughness Ra and maximum height Ry can be used measuring shape laser microscope (such as Co., Ltd. KEYENCE manufacture VK-X100 it) is measured.Starting measuring shape laser microscope (identical VK-X100) main body (control unit) and VK observation are answered After program (VK-H1VX that Co., Ltd. KEYENCE is manufactured), the sample being measured (photosensitive film) is placed in x-y and is carried On platform.The lens converter for rotating microscope portion (VK-X110 of Co., Ltd. KEYENCE manufacture), selects 10 times of multiplying power of object Mirror is roughly focused, brightness with the image viewing mode of VK observation application program (identical VK-H1VX).X-y is operated to carry Screen center is come in platform, the part for being adjusted to the hope measurement of specimen surface.Change 10 times of object lens of multiplying power into multiplying power 50 times, benefit With the automatic focusing function of the image viewing mode of VK observation application program (identical VK-H1VX), focus on the surface of sample. The simple mode for selecting the measuring shape label of VK observation application program (identical VK-H1VX), presses measurement start button, into The measurement of the surface shape of row sample, available surface image file.Start VK and analyzes application program (Co., Ltd. The VK-H1XA of KEYENCE manufacture), after showing obtained surface image file, carry out slant correction.It should be noted that Observe and measure range (transverse direction) in the measurement of the surface shape of sample is 270 μm.Line roughness window is shown, in parameter setting After selecting JIS B0601-1994 in region, horizontal line is selected from measurement line button, any position in surface image is shown Horizontal line presses OK button, and thus obtains the numerical value of arithmetic mean surface roughness Ra and maximum height Ry.In addition, on surface Different display horizontal lines everywhere in image, obtain the numerical value of each arithmetic mean surface roughness Ra and maximum height Ry.Point The average value of obtained 5 numerical value, arithmetic mean surface roughness Ra and maximum height as specimen surface are not calculated Ry value.It should be noted that being used in utilization in the measurement of above-mentioned arithmetic mean surface roughness Ra and maximum height Ry Photosensitive film in the state of before the curing process of exposure etc. is as measurement sample.As laminate photosensitive as the present invention Property film be laminated with protective film in the case where, be used in front of being laminated to substrate by protect film stripping in the state of measurement try Sample.In this case, (1 minute) and sample is carried out after 180 minutes soon after exposing photosensitive film will protect film stripping The measurement of " the arithmetic mean surface roughness Ra " and " maximum height Ry " on surface.It should be noted that as in the present invention Determination of the environment is set as 23 DEG C of temperature, relative humidity 42%.
In order to make the above-mentioned specific arithmetic mean surface roughness Ra and maximum height Ry of the configuration of surface of photosensitive film Range, known customary way can be applied, wherein from the easiness aspect for being formed as above-mentioned configuration of surface, In aftermentioned protective film, can be used have adjusted arithmetic mean surface roughness Ra and maximum height Ry protective film it is photosensitive to be formed Property film.Alternatively, it is also possible to be incited somebody to action after pasting the protective film with specific arithmetic mean surface roughness Ra and maximum height Ry The protection film stripping then glues other protective films with different arithmetic mean surface roughness Ra and maximum height Ry It is labelled to photosensitive film surface, the roughness on photosensitive film surface is adjusted.
In addition, can be by constituting photosensitive film by the ongoing change of the configuration of surface of the photosensitive film after protection film stripping Photosensitive composite before curing in include ingredient type or blend amount adjust.For example, can be dissolved by mixture The different material of property parameter (SP value) using glass transition temperature (Tg) or weight average molecular weight material appropriate or suitably makes It is adjusted with filler, but is not limited to these.In the present invention, the composition for forming the photosensitive composite of photosensitive film is not special Limitation, may include photocurable compound, Photoepolymerizationinitiater initiater, heat cross-linking material, inorganic filler etc..Hereinafter, feeling to constituting Each ingredient of photosensitiveness composition is illustrated.
[photocurable compound]
Photosensitive composite used in photosensitive film lamination body of the invention includes by ionizing rays such as ultraviolet lights Irradiation and cured ingredient can enumerate photocurable compound as an example.Photocurable compound be with ethylenic bond not It is saturated the compound of double bond, compound includes resin, oligomer, monomer whole.It, can be with as such photocurable compound Enumerate such as (methyl) alkyl-acrylates such as (methyl) acrylic acid-2-ethyl caproite, (methyl) cyclohexyl acrylate；(first Base) (methyl) acrylic acid hydroxy alkyl ester classes such as acrylic acid -2- hydroxyl ethyl ester, (methyl) 2-hydroxypropyl acrylate；Ethylene glycol, the third two List (methyl) acrylate of the alkylene oxide derivatives such as alcohol, diethylene glycol, dipropylene glycol or two (methyl) esters of acrylic acid；Oneself two The polyalcohols such as alcohol, trimethylolpropane, pentaerythrite, double trimethylolpropane, dipentaerythritol, tris(2-hydroxy ethyl)isocyanurate They ethylene oxide or propylene oxide adduct polynary (methyl) esters of acrylic acid；(methyl) acrylic acid phenoxy group second The ethylene oxide of phenols or (methyl) of propylene oxide adduct such as polyethoxy two (methyl) acrylate of ester, bisphenol-A Esters of acrylic acid；Diglycidyl ether, trimethylolpropane tris glycidyl ether, triglycidyl group isocyanuric acid (methyl) esters of acrylic acid of the glycidyl ethers such as ester；With melamine (methyl) acrylate etc..It should be noted that this In specification, (methyl) acrylate is the term being referred to as to acrylate, methacrylate and their mixture, It is also identical about other similar statements.
In addition, in addition to those specified above, (methyl) acrylate compounds with amido bond can also be enumerated, had The carbamate monomers or oligourethane etc. such as (methyl) acrylate compounds of urethane bond.
In addition, photocurable compound can make the unsaturated carboxylic acids such as acrylic or methacrylic acid and epoxy resin or phenol Urea formaldehyde etc. reacts and photoresist containing carboxyl is made.It is poly- that such photoresist containing carboxyl can inject row by illumination It closes or crosslinking is to solidify, and then by the inclusion of carboxyl, not only can be solvent development, can be also alkali-developable, go out from this respect Hair is preferred.Especially for alkalescent, specifically pH is 7.0 or more 12.0 developer solutions below, can also be formed excellent Developability, be preferred from this point.
As the concrete example of the photoresist containing carboxyl, can enumerate be exemplified below compound (can for oligomer or Any one of polymer).
It can enumerate:
(1) it reacts 2 functions or multifunctional (solid-state) epoxy resin more than it with (methyl) acrylic acid, is being present in side The dibasic acid anhydrides such as addition phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride on the hydroxyl of chain and obtain Photoresist containing carboxyl；
(2) the multifunctional ring for obtaining the further epoxidation of hydroxyl of 2 functions (solid-state) epoxy resin with epoxychloropropane Oxygen resin is reacted with (methyl) acrylic acid, and the tree of photonasty containing carboxyl obtained from addition dibasic acid anhydride on the hydroxyl of generation Rouge；
(3) make in the epoxide and 1 molecule with 2 or more epoxy groups in 1 molecule have at least one alcoholic extract hydroxyl group and The monocarboxylic acid reaction containing unsaturated group such as the compound of 1 phenolic hydroxyl group and (methyl) acrylic acid, for obtained reaction The alcoholic extract hydroxyl group of product keeps maleic anhydride, tetrabydrophthalic anhydride, trimellitic anhydride, pyromellitic acid dianhydride, adipic anhydride etc. more Photoresist containing carboxyl obtained from first anhydride reaction；
(4) make bisphenol-A, Bisphenol F, bisphenol S, novolak phenolics, poly(4-hydroxystyrene), naphthols and aldehydes With the compound and ethylene oxide, ring of 2 or more phenolic hydroxyl groups in 1 molecule such as condensation product of condensation product, dihydroxy naphthlene and aldehydes The reaction of the epoxyalkane such as Ethylene Oxide, makes the monocarboxylic acid containing unsaturated group such as obtained reaction product and (methyl) acrylic acid Reaction, photoresist containing carboxyl obtained from reacting obtained reaction product with multi-anhydride；
(5) make the cyclic annular carbon such as compound and ethylene carbonate, propylene carbonate in 1 molecule with 2 or more phenolic hydroxyl groups Ester compound reaction, reacts obtained reaction product with the monocarboxylic acid containing unsaturated group, makes obtained reaction Photoresist containing carboxyl obtained from product is reacted with multi-anhydride；
(6) for by aliphatic diisocyanate, Branched fatty (cyclo) aliphatic diisocyanates, ester ring type diisocyanate, fragrance The diisocyanate cpds such as (cyclo) aliphatic diisocyanates and polycarbonate-based polyalcohol, polyester-based polyols, gather polyether system polyalcohol Olefin-based polyalcohol, acrylic acid series multiple alcohol, bisphenol-A system alkylene oxide adducts glycol, the change with phenolic hydroxyl group and alcoholic extract hydroxyl group The end for the carbamate resins that the polyaddition of the diol compounds such as conjunction object obtains makes made of anhydride reaction containing end The carbamate resins of carboxyl；
(7) by the compounds containing carboxylic diol such as diisocyanate, dihydromethyl propionic acid, dimethylolpropionic acid and glycol In the synthesis for the carboxylic carbamate resins that the polyaddition of compound carries out, (methyl) acrylic acid hydroxy alkyl is added Compound with 1 hydroxyl and 1 or more (methyl) acryloyl group in the molecules such as ester, so that (methyl) acryloyl occurs for end The carboxylic photonasty carbamate resins changed；
(8) contain carboxylic in the polyaddition progress by diisocyanate, compound containing carboxylic diol and diol compound In the synthesis of the carbamate resins of base, the equimolar of isophorone diisocyanate and pentaerythritol triacrylate is added Compound with 1 isocyanate group and 1 or more (methyl) acryloyl group in the molecules such as reactant, so that end occurs (methyl) acrylated carboxylic photonasty carbamate resins；
(9) make the dicarboxylic acids such as multifunctional oxetane resin and adipic acid, phthalic acid, hexahydrophthalic acid anti- It answers, the addition dibasic acid anhydride on the primary hydroxyl of generation, makes the obtained further addition containing carboxyl polyester resin (methyl) propylene There is 1 epoxy group and 1 or more (first in 1 molecules such as acid glycidyl ester, (methyl) acrylic acid Alpha-Methyl ethylene oxidic ester Base) acryloyl group compound made of photoresist containing carboxyl；
(10) on any photoresist containing carboxyl of above-mentioned (1)~(9) in 1 molecule of addition have cyclic ether group and Photoresist containing carboxyl made of the compound of (methyl) acryloyl group；
(11) for passing through the unsaturated carboxylic acids such as (methyl) acrylic acid and styrene, α-methylstyrene, (methyl) propylene What the copolymerization of the compound containing unsaturated group such as sour lower alkyl esters, isobutene obtained contains carboxy resin, makes 3,4- epoxide ring Contain obtained from compound reaction with cyclic ether group and (methyl) acryloyl group in one molecule such as hexyl methacrylate Carboxyl photoresist；Etc..It should be noted that herein, (methyl) acrylate is to acrylate, methacrylate The term being referred to as with their mixture, hereinafter, also identical about other similar statements.
The weight average molecular weight of above-mentioned photocurable compound is different according to resin matrix, it is often preferred that 2,000~ 200,000.By making weight average molecular weight 2,000 or more, non-adhesion behavior, resolution ratio can be improved.In turn, the warp of film coated surface When state change become appropriateness, can further improve the adaptation with substrate.In addition, by making weight average molecular weight 200, 000 hereinafter, can be improved developability, storage stability.Weight average molecular weight is more preferably 4,000~150,000, further preferably It is 5,000~100,000.It should be noted that weight average molecular weight can use gel permeation chromatography (GPC) method (polystyrene Standard) it is measured.
About the blend amount of photocurable compound, in the case where also containing aftermentioned heat cross-linking material in the composition, with Solid component conversion meter, when the total amount of photocurable compound and heat cross-linking material is set as 100 mass parts, preferably 50 mass Part~90 mass parts.In blend amount above range by making photocurable compound, it is capable of forming with more in intensity Hollow structure.In addition, film coated surface through when state change become appropriateness, can further improve the adaptation with substrate.
[heat cross-linking material]
By the way that heat cross-linking material is added, it can expect that the heat resistance of photosensitive film improves.Heat cross-linking material can individually make It is applied in combination with a kind or by two or more.As heat cross-linking material, well known heat cross-linking material be can be used.It can be used for example The amino resins such as melamine resin, benzoguano amine resin, melamine derivative, benzoguanamine derivative, isocyanate compound, It is blocked isocyanate compounds, cyclic carbonate compound, epoxide, oxetane compound, episulfide resin, double Maleimide, carbodiimides resin, melamine resin, carbamide resin, polyimide resin, phenol novolacs, cresols Heat curable component well known to novolac resins such as novolaks etc..Among these, from the solidfied material and base of photosensitive composite It sets out in terms of the adaptation of plate, preferred epoxy, melamine resin, carbamide resin, more preferable epoxy resin.
About the blend amount of heat cross-linking material, in the case where also containing above-mentioned photocurable compound in the composition, with Solid component conversion meter, when the total amount of photocurable compound and heat cross-linking material is set as 100 mass parts, preferably 10 mass Part~40 mass parts.By making the blend amount above range of heat cross-linking material, it is capable of forming the hollow structure with more intensity. In addition, the ratio of photocurable compound increases, therefore differentiates by making the blend amount 40 of heat cross-linking material below the mass Rate further increases.
In the case where using epoxy resin etc. as heat cross-linking material, can also further include for making epoxy resin Cured curing agent.As curing agent, including for example amine, imidazoles, multifunctional phenols, acid anhydrides, isocyanates and comprising The polymerization species of these functional groups can be used two or more in these as needed.
[Photoepolymerizationinitiater initiater]
As Photoepolymerizationinitiater initiater, specifically, it can be cited for example that: bis- (2,6- dichloro-benzoyl base) phenyl oxidations Phosphine, double-(2,6- dichloro-benzoyl base) -2,5- 3,5-dimethylphenyl phosphine oxide, double-(2,6- dichloro-benzoyl base) -4- propylbenzene Base phosphine oxide, double-(2,6- dichloro-benzoyl base) -1- naphthalene phosphine oxide, double-(2,6- Dimethoxybenzoyl) phenyl oxidation Phosphine, double-(2,6- Dimethoxybenzoyl) -2,4,4- trimethylpentylphosphine oxide, double-(2,6- dimethoxybenzoyl Base) double acylphosphine oxides such as -2,5- 3,5-dimethylphenyl phosphine oxide, double-(2,4,6- trimethylbenzoyl)-phenyl phosphine oxide Class；2,6- Dimethoxybenzoyl diphenyl phosphine oxide, 2,6- dichloro-benzoyl base diphenyl phosphine oxide, 2,4,6- trimethyl Benzoylphenyl methyl-phosphonate, 2- methyl benzoyl diphenyl phosphine oxide, valeryl phenyl-phosphonic acid isopropyl ester, 2,4,6- The monoacylphosphine oxides phosphine such as trimethyl benzoyl diphenyl base phosphine oxide；Phenyl (2,4,6- trimethylbenzoyl) phosphinic acids second Ester, 1- hydroxy-cyciohexyl phenyl ketone, 1- [4- (2- hydroxyl-oxethyl)-phenyl] -2- hydroxy-2-methyl -1- propane -1- ketone, 2- Hydroxyl -1- { 4- [4- (2- hydroxy-2-methyl-propiono)-benzyl] phenyl } -2- methyl-propan -1- ketone, 2- hydroxyl -2- first The hydroxy acetophenones classes such as base -1- phenyl-propane -1- ketone；Benzoin, benzil, benzoin methylether, benzoin ethyl ether, benzoin are just The benzoin class such as propyl ether, benzoin iso-propylether, benzoin n-butylether；Benzoin alkyl ethers；Benzophenone, to methyldiphenyl first The hexichol such as ketone, michler's ketone, methyl benzophenone, 4,4 '-dichloro benzophenones, 4,4 '-bis- (diethylamino) benzophenone Ketone class；Acetophenone, 2,2- dimethoxy -2- phenyl acetophenone, 2,2- diethoxy -2- phenyl acetophenone, 1,1- dichloro-benzenes Ethyl ketone, 1- hydroxycyclohexylphenylketone, 2- methyl-1-[4- (methyl mercapto) phenyl]-2- morpholino-1- acetone, 2- benzyl-2- two Methylamino -1- (4- morphlinophenyl) -1- butanone, 2- (dimethylamino) -2- [(4- aminomethyl phenyl) methyl) -1- [4- (4- morpholine Base) phenyl] -1- butanone, N, the acetophenones such as N- dimethylamino acetophenone；Thioxanthones, 2- ethyl thioxanthones, 2- isopropylthioxanthones The thioxanthene ketone class such as ketone, 2,4- dimethyl thioxanthone, 2,4- diethyl thioxanthone, 2-chlorothioxanthone, 2,4- diisopropylthioxanthone； Anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2- ethyl hydrazine, 2- tert-butyl anthraquinone, 1- chloroanthraquinone, 2- amyl anthraquinone, 2- amino anthraquinones Equal Anthraquinones；The ketals class such as acetophenone dimethyl ketal, benzoin dimethylether；Ethyl -4- dimethylaminobenzoic acid ester, 2- (two Methylamino) ethylamino benzonitrile acid esters, to benzoates such as mesitylenic acid ethyl esters；1,2- acetyl caproyl, 1- [4- (thiophenyl)-, 2- (O- benzoyl oximes)], ethyl ketone, 1- [9- ethyl -6- (2- methyl benzoyl) -9H- carbazole -3- base] -, 1- (O- acetyl Base oxime) etc. oximes esters；It is bis- (η 5-2,4- cyclopentadiene -1- bases)-bis- (the fluoro- 3- of 2,6- bis- (1H- pyrroles -1- base) phenyl) titaniums, double The cyclopentadienyltitaniums classes such as (cyclopentadiene)-bis- [the fluoro- 3- of 2,6- bis- (2- (1- pyrroles -1- base) ethyl) phenyl] titaniums；Two sulphur of phenyl Compound 2- nitrofluorene, butyroin, anisoin ethyl ether, azodiisobutyronitrile, tetramethyl thiuram disulfide etc..
About the blend amount of Photoepolymerizationinitiater initiater, in the case where containing above-mentioned photocurable compound in the composition, phase For 100 mass parts of photocurable compound, in terms of solid component conversion, preferably 0.1 mass parts~10 mass parts.By making The blend amount of Photoepolymerizationinitiater initiater is above range, and resolution ratio further increases.
It can also be shared with above-mentioned Photoepolymerizationinitiater initiater and use light-initiated auxiliary agent or sensitizer.As light-initiated auxiliary agent or Sensitizer, can enumerate benzoin compound, acetophenone compound, anthraquinone compounds, thioxanthone compounds, ketal compound, Benzophenone cpd, tertiary amine compound and xanthone compound etc..These compounds are also used as photopolymerization sometimes and draw It sends out agent to use, but preferably shares and use with Photoepolymerizationinitiater initiater.In addition, light-initiated auxiliary agent or sensitizer can be used alone one Kind, it can also share two or more.
It should be noted that these Photoepolymerizationinitiater initiaters, light-initiated auxiliary agent and sensitizer be due to absorbing specific wavelength, because And according to circumstances sensitivity decrease, there is the case where working as ultraviolet absorbing agent.But these reagents are not only used In the purpose for the sensitivity for improving composition.It can according to need the light for making it absorb specific wavelength, can be improved the light on surface Reactivity improves the precision of shape when exposure, development.
[filler]
By filler mixed in photosensitive composite, hardness or heat resistance of film etc. can be improved, while can mention The ongoing change of the configuration of surface of high photosensitivity film.As such filler, it is able to use well known inorganic or organic filler, it is excellent It is selected as inorganic filler.As inorganic filler, barium sulfate, silica, mica, hydrotalcite, talcum, metal oxidation can be enumerated Metal hydroxides such as object, aluminium hydroxide etc..Among these, preferably silica, mica.Silica can enumerate spherical two Silica, amorphous silica etc..
As needed, can also be added in photosensitive composite other resins other than the above, thermal free radical initiator, Polymerization inhibitor, bonding additives, organic solvent etc..
For example, can be improved heat resistance by the other resins of mixture.As other resins, it can be cited for example that polyamides is sub- It is the novolac resins such as amine, poly- oxazole and their precursor, phenol novolacs, cresol novolak, polyamidoimide, poly- Amide, phenoxy resin, polyether sulfone etc..They can be used alone, and can also share two or more.
In addition, alkali solubility can also be made in polyimide resin.Specifically, other than imide, have carboxyl, The alkali solubilities group such as anhydride group.Known customary way can be used in the importing of alkali solubility group.For example, can enumerate makes carboxylic acid Resin obtained from anhydride component is reacted with any at least one in amine component and isocyanate prepolymer composition.Imidizate can be with warm Imidizate carries out, and can also be carried out with chemical imidization, in addition can be shared them to manufacture.
In addition, photocurable compound can be made to solidify with the short time at low temperature by mixed thermal free radical initiator. As thermal free radical initiator, it can be cited for example that peroxide, azo-compound etc..
As polymerization inhibitor, quinhydrones, hydroquinone monomethyl ether, tert-butyl catechol, phenthazine etc. can be enumerated.In addition, As bonding additives, it can be cited for example that the silane coupling agents such as γ-glycidoxy silane, amino silane, γ-ureido silane Deng.
Photosensitive film can be by being coated with above-mentioned photosensitive composite on a face in support membrane and making it dry and shape At.In view of the coating of photosensitive composite, photosensitive composite organic solvent diluting can be adjusted to appropriate Viscosity using comma coater, knife type coater, lip type coating machine, bar coater, extrusion coating machine, reversed coating machine, transfers roller Coating machine, gravure coater, Bracewell coater, bar coater, roll coater, comma coater, the extrusion coated machine of slit coventry type die head coventry, rotation Painting machine etc. is coated in a face of support membrane with uniform thickness, by drying so that organic solvent is volatilized, it is available not The film of viscosity.Coating film thickness is not particularly limited, it is usually suitable in 0.5 μm~500 μm of range with the film thickness gauge after drying Work as selection.The aspect that uses from the material as the wall portion or cover that form hollow structure, preferably 1 μm~300 μm Range.
It is not particularly limited as workable organic solvent, it can be cited for example that ketone, aromatic hydrocarbon, glycol ethers Class, glycol ethers acetate esters, esters, alcohols, aliphatic hydrocarbon, petroleum series solvent etc..More specifically, are as follows: methyl ethyl ketone (MEK), The ketones such as cyclohexanone；Toluene, dimethylbenzene, durene etc. are aromatic hydrocarbon；Cellosolve, methyl cellosolve, butyl cellosolve, card must Alcohol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol The glycol ethers such as single ether；Ethyl acetate, butyl acetate, diethylene glycol monoethyl ether acetic acid esters, dipropylene glycol methyl ether acetic acid esters, The esters such as propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters, propandiol butyl ether acetic acid esters；Ethyl alcohol, propyl alcohol, ethylene glycol, third The alcohols such as glycol；The aliphatic hydrocarbons such as octane, decane；The petroleums such as petroleum ether, naphtha, hydrogenated naphtha, solvent naphtha are molten Agent and n-methyl-2-pyrrolidone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, γ-Ding Nei Ester etc..Such organic solvent can be used alone, and can also be used as mixture of more than two kinds and uses.
Heated air circulation type drying oven, IR furnace, hot plate, convective oven etc., which can be used, in the volatile dry of organic solvent (makes And have using steam air heating method heat source device, the method for contact hot air convection in drying machine and lead to Cross the mode that nozzle is ejected into supporter) Lai Jinhang.It is 60 DEG C~120 DEG C, time 1 in temperature as volatile dry condition Minute~60 minutes ranges suitably select.
[protective film]
For preventing dust etc. to be attached to the surface of above-mentioned photosensitive film and improve the purpose of treatability, and then for adjustment The purpose of the arithmetic mean surface roughness Ra on photosensitive film surface, photosensitive film lamination body of the invention photosensitive film with The opposite face of support membrane is equipped with protective film.
As protective film, can be used for example polyester film, polyethylene film, polytetrafluoroethylene film, polypropylene screen, through surface at The paper etc. of reason, particularly preferably polypropylene screen.Additionally, it is preferred that selection protective film and photosensitive film bonding force be less than protective film with The material of the bonding force of photosensitive film.In addition, in photosensitive film lamination body in use, in order to be easily peeled off protective film, it can Implement above-mentioned demoulding with the face contacted with photosensitive film to protective film to handle.
The thickness of protective film is not particularly limited, and suitably selects depending on the application in substantially 10 μm~200 μm of ranges.
The arithmetic mean surface roughness of the protection film surface of in the present invention, it is preferable to use surface side contacted with photosensitive film The protective film that Ra ' is 0.10 μm or more.In addition, more preferably using the arithmetic of the protection film surface of the surface side contacted with photosensitive film The protective film that average surface roughness Ry ' is 1.00 μm or more.By using the protective film with this configuration of surface, it is easy shape At the photosensitive film with 0.10 μm or more of arithmetic mean surface roughness Ra, and then easy to form there are 1.00 μm or more The photosensitive film of arithmetic mean surface roughness Ry.The arithmetic mean surface roughness Ra ' of protective film be more preferably 0.15 μm with Above, further preferably 0.20 μm or more.In addition in the case where the upper limit is arranged, preferably 1.00 μm or less, more preferably 0.80 μm or less, more preferably 0.60 μm or less.
In addition, the maximum height Ry ' of the protective film of the surface side contacted with photosensitive film is more preferably 1.20 μm or more, into one Preferably 1.40 μm or more of step.In addition in the case where the upper limit is arranged, preferably 5.00 μm or less, more preferably 4.00 μm with Under, further preferably 3.00 μm or less.Herein, about the difference of arithmetic mean surface roughness Ra ' and maximum height Ry ' institute The position of finger and its specific measuring method are illustrated in above-mentioned [photosensitive film].It should be noted that the arithmetic of protective film The maximum height Ry ' and photonasty of the arithmetic mean surface roughness Ra of average surface roughness Ra ' and photosensitive film, protective film The maximum height Ry of film respectively may not be consistent, by appropriate adjustment, can make the arithmetic mean surface roughness Ra of photosensitive film It is in above-mentioned specific range with maximum height Ry.
As the method for adjustment with above-mentioned arithmetic mean surface roughness Ra ' and the protective film of maximum height Ry ', do not have In the case where being particularly limited to, such as add in the resin of protective film filler, can enumerate to the partial size of filler or additive amount into Row adjustment, by carrying out blasting treatment or hairline processing, the coating processing of delustring or chemical etching etc., energy to protection film surface Enough make the defined form in surface.
[solidfied material]
Solidfied material is formed using photosensitive film lamination body of the invention.As an example of the solidfied material, to using the present invention Photosensitive film lamination body form the method for hollow structure for having wall portion and cover and be illustrated.
[forming method of wall portion]
Firstly, forming wall portion using photosensitive film layer product body.Specifically, can be formed by following processes desired Wall portion: lamination process removes protective film from photosensitive film lamination body, will be in the adherend such as photosensitive film lamination to substrate； Exposure process carries out light irradiation across prescribed portion of the mask to photosensitive film, exposure portion is made to carry out photocuring；Developing procedure, The position of photosensitive film carried out other than photocuring is removed using developer solution；Formal solidification process makes to feel using light or heat Photosensitiveness film has carried out the site curing of photocuring, forms solidfied material.Hereinafter, being illustrated to each process.
In lamination process, protective film is removed from photosensitive film lamination body, the photosensitive film surface side lamination of exposing is arrived On substrate.Lamination can be carried out by bonding using thermo-compression bonding etc..As adherend substrate, it can be cited for example that silicon wafer Piece, glass substrate, ceramic substrate, aluminium base substrate, stainless steel substrate, glass epoxy substrate, polyester substrate, polyimide substrate Deng.As the method for thermo-compression bonding, hot-pressing processing, roll laminating processing, vacuum roll laminating, vacuum compression process, diaphragm can be enumerated Formula vacuum lamination etc..From with the adaptation of substrate, imbedibility in terms of；And thermo-compression bonding when photosensitive composite solidification not into It goes and maintains to set out in terms of good resolution ratio, hot pressing jointing temp is preferably 20 DEG C~150 DEG C, more preferably 35 DEG C~100 DEG C, further preferably 40 DEG C~85 DEG C.In addition, lamination pressure is preferably 0.005MPa~10MPa, more preferably 0.005MPa ~3MPa.
Then, implement exposure process.As exposure, including minus and eurymeric, preferably minus.In the case where minus, every The negative mask with the desired pattern for forming wall portion shape, to lamination on substrate photosensitive film lamination body carry out Light irradiation makes the exposure portion of photosensitive film carry out photocuring.Herein, as active ray used in exposure, purple can be enumerated Outside line, luminous ray, electron ray, X-ray etc..Among these, particularly preferred ultraviolet light, luminous ray.Additionally, it is preferred that across Photomask using the i ray (365nm) of ultrahigh pressure mercury lamp, h ray (405nm), g ray (436nm) mask exposure.In addition, The method directly described on photosensitive film in a manner of maskless using the laser of wavelength 405nm can also be enumerated.This work In sequence, the support membrane for constituting photosensitive film lamination body can be removed before exposure, can also remove after exposure.In addition, can also Will support film stripping before exposure or not remove, and implemented 5 seconds using heating furnace or heating plate with 40 DEG C~150 DEG C of temperature Heat treatment in~60 minutes.Alternatively, it is also possible to support film stripping after exposure or do not remove, and use heating furnace or heating Plate implements heat treatment in 5 seconds~60 minutes with 40 DEG C~150 DEG C of temperature.
Then, using the developer solution of organic solvent system or aqueous alkali system by photosensitive film carry out photocuring other than portion Position (unexposed portion) removes, and the pattern of wall portion is consequently formed.
As developer solution, N-Methyl pyrrolidone, ethyl alcohol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetic acid can be used The organic solvents such as ester, gamma-butyrolacton, triethylene glycol dimethyl ether, methyl amyl ketone (2-HEPTANONE), butyl acetate.Furthermore it is possible to make With sodium carbonate, sodium hydroxide, potassium hydroxide, sodium metasilicate, ammonia, ethamine, diethylamine, triethylamine, triethanolamine, tetramethyl hydroxide The aqueous alkalis such as ammonium (TMAH).Among these, from developing powder aspect, for solvent development, preferably make Use methyl proxitol acetate.On the other hand, for alkali development, preferably sodium carbonate, sodium hydroxide, tetramethyl Ammonium hydroxide (TMAH).
As developing method, it can enumerate to photosensitive film spray development liquid, be impregnated into developer solution or impregnate on one side Apply ultrasonic wave etc. on one side.
In addition, after development, preferably using water as needed；The alcohol such as methanol, ethyl alcohol, isopropanol；Positive butyl acetate, propylene glycol Methyl ether acetate, diethylene glycol dimethyl ether acetic acid esters etc. are rinsed.As rinse method, can enumerate to photonasty film surface Spray development liquid is impregnated into developer solution or applies while impregnating ultrasonic wave etc..
Then, solidify the position (exposure portion) for having carried out photocuring of photosensitive film using light or heat, form wall portion.It closes Solidification (cure) after development preferably selects temperature in the case where making its cured situation using heat, periodically heats up one on one side Implement 1~2 hour on side.It is appropriate in the range of the temperature of heat cure is 120 DEG C~400 DEG C, the time is 60 minutes~120 minutes Selection.Temperature can be fixed as certain temperature, can also periodically heat up.When solidification, preferably in the inert gases such as nitrogen, argon Heated.Final heating temperature is preferably 150 DEG C~350 DEG C.Furthermore it is possible to before and after heat cure or instead of thermosetting Change and carries out photocuring.
The film thickness for being used to form the photosensitive film of wall portion is preferably 1 μm~3,000 μm, more preferably 5 μm~1,000 μm, Further preferably 10 μm~500 μm, particularly preferably 20 μm~200 μm, most preferably 20 μm~100 μm.If photosensitive film With a thickness of 1 μm or more, be easy maintain wall portion shape, be difficult to happen under the high-temperature and high-pressure conditions in mold larger Deformation.In addition, if with a thickness of 3,000 μm of thickness below is then difficult to inhibit the translucency of photosensitive film when exposure.It needs Illustrate, the lamination process for being overlapped photosensitive film can also be repeated, thus increases the thickness of wall portion.In addition, by solidification The final film thickness for the wall portion that process is formed is preferably also 1 μm~3,000 μm, more preferably 5 μm~500 μm, is more preferably 10 μm~200 μm.
[formation of cover]
There is sufficient film thickness using the wall portion being made of the solidfied material of photosensitive film that above-mentioned forming method is formed, pass through Ceramic substrate, Si substrate, glass substrate, metal substrate etc. are covered on to the upper end of wall portion as lid, additionally it is possible to form hollow knot Structure also can be used photosensitive film lamination body and form cover.Hereinafter, to use photosensitive film layer product body formed cover method into Row explanation.
In the upper end of the wall portion formed as described above, lamination has removed the photosensitive film lamination body of protective film, is exposed With development as needed, makes the photosensitive film solidification for having carried out photocuring, cover is consequently formed, so as to form hollow knot Structure body.It when forming cover using photosensitive film layer product body, is not necessarily required by developing procedure, such as manufactures together at the same time more When a hollow structure device, it is exposed through mask pair and the comparable size of cover of hollow device, later by its periphery Unexposed portion development, thus, it is possible to be divided into monolithic.
Lamination, exposure, development and the solidification of photosensitive film lamination body can be carried out similarly with the formation of above-mentioned wall portion.This Place, bonding when forming the lamination of the laminate of wall portion and cover can be carried out by being thermally compressed.It, can as thermal pressure welding method To enumerate such as hot-pressing processing, roll laminating processing, vacuum roll laminating, vacuum compression process, diaphragm type vacuum lamination, wherein excellent Roll laminating is selected to handle.From with the adaptation of adherend, imbedibility aspect, hot pressing jointing temp is preferably 20 DEG C or more. In addition, from the resolution ratio for solidifying the pattern in carrying out and making exposure, develop and being formed of photoresist ingredient when preventing from being thermally compressed It sets out in terms of variation, hot pressing jointing temp is preferably 150 DEG C or less.That is, from the adaptation of substrate, imbedibility in terms of；With And when thermo-compression bonding photosensitive composite solidification without and set out in terms of maintaining good resolution ratio, hot pressing jointing temp is preferred It is 20 DEG C~150 DEG C, more preferably 35 DEG C~100 DEG C, further preferably 40 DEG C~85 DEG C.In addition, lamination pressure is preferably 0.005MPa~10MPa, more preferably 0.005MPa~3MPa.
The support membrane for constituting photosensitive film lamination body can be removed before exposure, can remove after exposure, can also be It is removed after the solidification of photosensitive film, only becomes the state of the solidfied material of photosensitive film of cover with wall portion support due to being formed, from It sets out in terms of stability, the removing after preferably exposing, the removing after solidification.Furthermore it is possible to which film stripping will be supported before exposure Or it does not remove, and using heating furnace or heating plate with the heat treatment of 40 DEG C~150 DEG C of temperature implementation 5 seconds~60 minutes.Separately Outside, it by support film stripping or can not remove after exposure, and real with 40 DEG C~150 DEG C of temperature using heating furnace or heating plate Apply heat treatment in 5 seconds~60 minutes.In turn, it about development or solidification, can be carried out together with wall portion and cover.Form cover The tensile modulus of elasticity of cured film is preferably 2.0GPa or more.
The film thickness for being used to form the photosensitive film of cover is preferably 1 μm~3,000 μm, more preferably 5 μm~1,000 μm, Further preferably 10 μm~500 μm, particularly preferably 20 μm~200 μm, most preferably 20 μm~100 μm.Cured process The final film thickness of the cover of formation is preferably 10 μm~3,000 μm.If cover with a thickness of 10 μm or more, be easy to maintain hollow knot The shape of structure is difficult to happen biggish deformation under the high-temperature and high-pressure conditions in mold.In addition, if with a thickness of 3,000 μ M is hereinafter, be then difficult to inhibit the translucency of photosensitive film when exposure.It should be noted that can also repeat photosensitive film weight Thus the lamination process of conjunction increases the thickness of wall portion.
It should be noted that wall portion is formed without using photosensitive film lamination body of the invention in the present invention, can only make Cover is formed using photosensitive film lamination body of the invention, if but wall portion pattern and cover both sides use it is of the invention photosensitive Property film laminate, cementability between the two is more excellent, while the peeling of coating for being able to suppress the proximity of hollow structure etc..
According to the present invention, in the electronic component that SAW filter etc. has hollow structure, by using of the invention photosensitive Property film layer product body form wall portion or cover, be able to suppress the peeling of coating of the proximity of hollow structure etc..In addition, hollow structure It is interior damp proof using wall portion and cover progress, and hollow structure can also be kept at high temperature, therefore can be applied to SAW filtering Device, CMOSCCD sensor, MEMS etc. need the electronic component of hollow structure, to the miniaturization of electronic component, low level, Multifunction is useful.The wall portion or lid of the hollow structure of photosensitive film lamination body of the invention particularly suitable as SAW filter Portion, which is formed, to be used, and the electronic component for inhibiting the high reliablity of the peeling of coating of the proximity of hollow structure etc. can be obtained, from this Point sets out especially suitable.In addition, the present invention is also used as solder resist or coating resist, resist layer, interlayer dielectic etc. Printed circuit board purposes.
< SAW filter and its manufacturing method >
To using photosensitive film lamination body of the invention to be formed there is the method for the hollow structure of wall portion and cover to carry out Illustrate, as an example of the electronic component with hollow structure, below to surface acoustic wave (SAW) filter and its manufacturing method into Row explanation.
Firstly, protective film is removed from photosensitive film lamination body of the invention, layer on the substrate for being formed with comb-type electrode Product photonasty film surface.It is identical that the method recorded in the forming method with above-mentioned wall portion can be used in the lamination of photosensitive film lamination body Method.
Then, after lamination photosensitive film lamination body, as needed across the negative mask with desired pattern Light irradiation is carried out to the prescribed portion of photosensitive film, exposure portion is made to carry out photocuring.The shape with above-mentioned wall portion can be used in exposure At the identical method of the method recorded in method.
Then, position, the i.e. unexposed portion other than the exposure portion of photosensitive film are removed using developer solution and forms institute's phase It hopes pattern, solidifies the exposure portion of photosensitive film by light or heat later, form the wall portion being made of solidfied material.It needs to illustrate Be expose, develop, method identical with the forming method of above-mentioned wall portion can be used in cured each process.
It should be noted that photosensitive film lamination body of the invention to be used for the hollow structure of SAW filter as described later Cover formation when, the method that wall portion also can use other than the method using photosensitive film lamination body of the invention is formed.
Cover is set in the upper end of the wall portion formed as described above, forms hollow structure.Herein, it about cover, will protect Film is removed from photosensitive film lamination body of the invention, and photonasty film surface is affixed to the upper end of wall portion, is exposed, shows later Shadow, solidification, are capable of forming cover.Cover is Nian Jie with wall portion for example can be by viscous based on the thermo-compression bonding for using layer of rolls press It connects etc. to carry out.
It should be noted that cover also can use material other than photosensitive film lamination body of the invention, for example known Permanent resist or Substrate for seal such as ceramics etc. constitute.Wherein, cover is preferably excellent by humidity resistance and water absorption rate is low Material is constituted.In this case, at least the wall portion for using photosensitive film lamination body of the invention to be formed is used as in SAW filter The wall portion of hollow structure formation.
After the formation for having carried out wall portion and cover as described above, in order to carry out electrode and the phase in the inside of substrate and electrode The electrical connection of the conductor of opposite side surface wiring can carry out formation and carrying of metal ball of coating etc..
In the formation of wall portion, the hole of inner conductor can be used to form by exposing, being developed in be formed inside wall portion.It Afterwards, by lamination in the photosensitive film lamination on support membrane in above-mentioned wall portion, be exposed across mask.Mask according to only with It is covered in the comparable part of diameter in the hole for forming inner conductor through the mode of light, therefore forms position in addition to this The cover of photocuring has occurred.About the unexposed portion of cover, in order to the hole inside the wall portion that is formed before completely through, Desmear processing etc. is carried out after being developed, and is thus patterned.In addition, the patterning of cover can be used it is sharp Light device.As laser, laser well known to YAG laser, carbon dioxide laser, excimer laser etc. can be used. Exposure or laser irradiation can match according to the thickness of wall portion, the shape of the inner conductor for the inside for being formed in wall portion and cover portion surface The shape of line pattern suitably selects to use.
In addition, forming inner conductor in the hole for being formed in the inside of wall portion and cover using plating method etc., and in cover Surface formed wiring.In the present invention, in the hole for the inside for being formed in wall portion and cover, it not only can use plating method, may be used also To use metal paste material or the resin thickener containing metal-powder forms inner conductor by conductor filled method.By these works Sequence, the conductor that the comb-type electrode on substrate forms wiring are electrically connected with the Wiring conductor for being formed in cover portion surface.Most Afterwards, metal ball, the available SAW filter as the electronic component with hollow structure are carried on the surface of cover by reflow etc. Wave device.
It is sealed in addition, SAW filter can use sealing material.The case where being sealed using sealing material Under, it is usually carried out according to process below, but not limited thereto.Firstly, SAW filter is set to molding die.Then, will The sealing material small pieces of solid-like are set in the kettle of molding machine.It in turn, will under conditions of 150 DEG C~180 DEG C of mold temperature Sealing material melting, applies pressure and is poured into mold (mold).It finally pressurizes 30 seconds~120 seconds, in sealing material thermosetting Mold is opened after change, molded product is taken out, and thus completes the sealing of SAW filter.
In general, using sealing material be sealed in carry metal ball before carry out, after sealing, in the face of substrate sealed Opposing face carries metal ball by reflow.But it is also possible to carry out the sealing using sealing material after carrying metal ball.Benefit The SAW filter sealed with sealing material can not only manufacture 1, can also manufacture 2 or more.In this case, will be formed After multiple SAW filters on a substrate are sealed with sealing material, monolithic is cut into, it is hereby achieved that.Specifically, Firstly, forming wall portion and cover using photosensitive film lamination body of the invention etc. in the multiple SAW filters of substrate manufacture. Later, it is sealed together with sealing material, monolithic, available SAW filter is divided by the methods of cutting.
As described above, tool can be formed using photosensitive film lamination body of the invention in the manufacturing process of SAW filter There is the hollow structure of wall portion and cover.As described above, photosensitive film lamination body of the invention due to through when configuration of surface change Change in particular range, therefore the SAW filter that the peeling of coating that the proximity of hollow structure may be implemented etc. is inhibited. In addition, being isolated with surrounding, energy in hollow structure by using the wall portion and cover of photosensitive film lamination body formation of the invention It is enough damp proof, therefore it is able to suppress the corrosion of aluminium electrode.In addition, the solidfied material of photosensitive film has high elastic modulus at high temperature, Therefore have the advantages that also maintain hollow structure under the temperature and pressure in sealing resin mold.
Embodiment
Enumerate embodiment below the present invention is described in more detail, however, the present invention is not limited to these examples.It needs It is bright, it is quality base as long as not special declaration in addition to the % for being related to relative humidity when " part " mentioned below and " % " It is quasi-.In addition, the operation in following embodiments carries out under room temperature (23 DEG C), relative humidity 42%, amber light.
< synthesis example 1 >
Synthesis of the < containing carboxy resin >
Into the 2L flask with agitating device, return pipe, investment is as the epoxy in molecule with 2 or more epoxy groups The two function bisphenol-A-type epoxy resins of compound (Japanese chemical drug corporation makes RE-310S, epoxide equivalent: 183.5g/ equivalent) 367.0 parts, as the acrylic acid (molecular weight: 72.06) 144.1 of the monocarboxylic acid compound with ethylenically unsaturated groups Part, 1.02 parts of the hydroquinone monomethyl ether as hot polymerization inhibitor and 1.53 parts of triphenylphosphine as catalysts, in 98 DEG C of temperature The lower reaction of degree until the acid value of reaction solution reaches 0.5mgKOH/g or less, obtain epoxy carboxylic acids' ester compounds (theoretical molecular weight: 511.1)。
Then, 445.93 parts of the carbitol acetate as anti-solvent-applied is added into the reaction solution, gathers as thermal resistance 0.70 part of the 2- methylnaphthohydroquinone of agent, the dihydromethyl propionic acid (molecular weight: 134.1) as the diol compound with carboxyl 118.8 parts, it is warming up to 60 DEG C.In such a way that reaction temperature is no more than 65 DEG C, slowly it is added dropwise into the solution different as two Isophorone diisocyanate (the molecular weight: 222.29) 209.6 parts of cyanate esters.After completion of dropwise addition, increase temperature To 80 DEG C, by infrared absorption spectrometry method, reaction 6 hours until 2250cm-1Until neighbouring absorption disappears.To the solution Succinic anhydride (molecular weight: 100.1) 36.7 part, carbitol acetate 43.0 part of the middle addition as multi-anhydride.It will after addition Temperature is warming up to 95 DEG C, reacts 6 hours, obtains the carbamate resins containing carboxyl polyester for being 10,000 comprising weight average molecular weight The varnish of photoresist containing carboxyl 1 of 65 weight %.Acid value is measured, result is 66.61mgKOH/g (solid component acid Value: 102.5mgKOH/g).It should be noted that weight average molecular weight utilizes gel permeation chromatography (GPC) method (polystyrene standard) It is measured according to general method.
<synthesis example 2>
<synthesis containing carboxy resin>
It is clear that phenolic aldehyde is put into the autoclave for having thermometer, nitrogen gatherer and alkylene oxide gatherer and agitating device (AICA KOGYO Co., Ltd. manufactures シ ョ ー ノ ー Le CRG951, OH equivalent: 119.4) 119.4g, hydrogen-oxygen to paint shaped cresol resin Change potassium 1.19g and toluene 119.4g, under stiring to carrying out nitrogen displacement, and heat temperature raising in system.Then, it is slowly added dropwise Propylene oxide 63.8g, 125 DEG C~132 DEG C, 0~4.8kg/cm2Under the conditions of react 16 hours.Later, it is cooled to room temperature, to Addition 89% phosphatase 11 .56g of mixing in the reaction solution and neutralize potassium hydroxide, obtain that nonvolatile component is 62.1%, hydroxyl value is The propylene oxide reaction solution of the phenolic varnish type cresol resin of 182.2g/eq..Obtained phenolic varnish type cresol resin is It is averaged the substance of 1.08 mol of alkylene oxide relative to every 1 equivalent of phenolic hydroxyl addition.
By alkylene oxide reaction solution 293.0g, the acrylic acid 43.2g, methanesulfonic acid of obtained phenolic varnish type cresol resin 11.53g, methylnaphthohydroquinone 0.18g and toluene 252.9g investment have blender, thermometer and air and are blown into the reactor of pipe, It is blown into air with 10ml/ minutes speed, is reacted 12 hours in 110 DEG C under stiring.About by reaction generate water, as with The azeotropic mixture of toluene distillates the water of 12.6g.Later, it is cooled to room temperature, is neutralized with 15% sodium hydrate aqueous solution 35.35g Obtained reaction solution, is then washed.Later, it is replaced in evaporator with diethylene glycol monoethyl ether acetic acid esters 118.1g Toluene is simultaneously distilled off simultaneously, obtains phenolic varnish type acrylic ester resin solution.Then, by obtained phenolic varnish type third Olefin(e) acid ester resin solution 332.5g and triphenylphosphine 1.22g investment have the reactor that blender, thermometer and air are blown into pipe In, air was blown into 10ml/ minutes speed, is slowly added into tetrabydrophthalic anhydride 62.3g under stiring, 95 DEG C~ It is reacted 6 hours at 101 DEG C, obtains the varnish of photoresist containing carboxyl that acid value is 88mgKOH/g, that nonvolatile component is 71% 2。
<synthesis example 3>
<synthesis containing carboxy resin>
By cresol novolak type epoxy resin (Japanese chemical drug corporation make, EOCN-104S, epoxide equivalent 220g/eq) 220 parts (1 equivalent), in 60.3 parts of investment flasks of 140.1 parts of carbitol acetate and solvent naphtha, be heated to 90 DEG C and stir It mixes, is dissolved.
Obtained solution is temporarily cooled to 60 DEG C, 72 parts of acrylic acid (1 mole), 0.5 part of methylnaphthohydroquinone, triphen is added 2 parts of base phosphine, 100 DEG C are heated to, is reacted about 12 hours, the reactant that acid value is 0.2mgKOH/g is obtained.Tetrahydro is added thereto 80.6 parts of phthalic anhydride (0.53 mole) is heated to 90 DEG C, reacts about 6 hours, and the acid value for obtaining solid component is 85mgKOH/g, the varnish of photoresist containing carboxyl 3 that solid component is 64.9%.
<synthesis example 4>
<synthesis containing carboxy resin>
By the EPPN-201 of phenol novolak type epoxy resin (Nippon Kayaku K. K's manufacture, epoxide equivalent= 190) it is added into the four-hole boiling flask with blender and reflux condenser for 190 parts, is added 184 parts of carbitol acetate, carry out It dissolves by heating.Then, 0.46 part of the methylnaphthohydroquinone as polymerization inhibitor, 1.38 parts of triphenylphosphine as catalysts is added. The mixture is heated to 95 DEG C~105 DEG C, 72 parts of acrylic acid (1 equivalent) slowly is added dropwise, is reacted 16 hours.It will be obtained Reaction product (hydroxyl: 1 equivalent) is cooled to 80 DEG C~90 DEG C, is added 50 parts of succinic anhydride (0.5 equivalent), reacts 8 hours, cooling After take out.So obtain that nonvolatile component is 65%, the acid value of solid matter is 89mgKOH/g, solid component is 65.0% The varnish of photoresist containing carboxyl 4.
The preparation of < photosensitive composite >
Mixture is carried out according to content shown in following table 1 and ratio (mass parts), is carried out according to the uniform mode of each ingredient It is kneaded, prepares photosensitive composite 1~5.It should be noted that * 1~* 22 in table 1 indicate following component.
* 1 methylated melamine resins, Co., Ltd. Sanwa Chemical manufacture
* 2 epoxy resin containing fluorene skeleton, the manufacture of OSAKA GAS CHEMICALS Co., Ltd.
* 3 bisphenol A type epoxy resins (Dainippon Ink Chemicals's manufacture)
* 4 xenyl aralkyl-type epoxy resins (Nippon Kayaku K. K's manufacture)
* 5 phenol novolak type epoxy resins (Dainippon Ink Chemicals's manufacture)
* 6 dicyclopentadiene type epoxy resins (Dainippon Ink Chemicals's manufacture)
* 7 synthesis examples 1 (blend amount is solid content)
* 8 synthesis examples 2 (blend amount is solid content)
* 9 synthesis examples 3 (blend amount is solid content)
* 10 synthesis examples 4 (blend amount is solid content)
* 11 alkali-soluble photosensitive resin (solid components 20%, NIPPON KODOSHI with amide imide structure CORPORATION manufacture)
The acrylate of * 12 dipentaerythritols, Kyoeisha Chemical Co., Ltd.'s manufacture
The acrylate of the modified dipentaerythritol of * 13 6-caprolactones, Kyoeisha Chemical Co., Ltd.'s manufacture
* 14 Tricyclodecane Dimethanol diacrylates, the manufacture of chemical industry Co., Ltd., the village Xin Zhong
* 15 oxime ester system Photoepolymerizationinitiater initiaters (ethyl ketone, 1- [9- ethyl -6- (2- methyl benzoyl) -9H- carbazole -3- Base]-, 1- (0- acetyl group oxime)), BASF Japan Co., Ltd. manufacture
* 16 diphenyl (2,4,6- trimethylbenzoyl) phosphine oxide (manufacture of IGM Resins company)
* 17 2-ethyl-4-methylimidazoles (Shikoku Chem's manufacture)
* 18 spherical silicon dioxides, Co., Ltd. Admatechs manufacture
* 19 average grain diameters are the spherical silica particles of 100nm
* 20 C.I. pigment blue 15s: 3
* 21 C.I. pigment yellow 147s
The * 22 red K3580 of Palio root (manufacture of BASF Japan company)
[table 1]
The production of < protective film >
Make example 1
It is 3.0 × 10 by weight average molecular weight (Mw)5, molecular weight distribution (Mw/Mn) be 5.0, isotaxy ingredient score be 95.0% profax resin granular material is supplied to extruder, is melted with 250 DEG C of resin temperature of temperature, is squeezed out by T mould, is wound It remains in 150 DEG C of metal drum and is film-made to surface temperature, produce about 225 μm of thickness of casting blank sheet.Then, by this Non-stretched casting blank sheet stretches 5 times, after being cooled to room temperature immediately with 120 DEG C of temperature in the flowing direction, followed by drawing Width machine horizontally stretches 10 times with 160 DEG C of temperature, obtains 12 μm of thickness of biaxially oriented polypropylene film 1.By the two-way drawing Stretched polypropylene film 1 is used as protective film 1.
Make example 2
It is 3.1 × 10 by weight average molecular weight (Mw)5, molecular weight distribution (Mw/Mn) be 5.5, isotaxy ingredient score be 93.0% profax resin granular material is supplied to extruder, is melted with 250 DEG C of resin temperature of temperature, is squeezed out by T mould, is wound It remains in 150 DEG C of metal drum and is film-made to surface temperature, produce about 225 μm of thickness of casting blank sheet.Then, by this Non-stretched casting blank sheet stretches 5 times, after being cooled to room temperature immediately with 200 DEG C of temperature in the flowing direction, followed by drawing Width machine horizontally stretches 10 times with 160 DEG C of temperature, obtains 15 μm of thickness of biaxially oriented polypropylene film 2.By the two-way drawing Stretched polypropylene film 2 is used as protective film 2.
Make example 3
It is 3.0 × 10 by weight average molecular weight (Mw)5, molecular weight distribution (Mw/Mn) be 5.0, isotaxy ingredient score be 95.0% profax resin granular material is supplied to extruder, is melted with 250 DEG C of resin temperature of temperature, is squeezed out by T mould, is wound It remains in 100 DEG C of metal drum and is film-made to surface temperature, produce about 225 μm of thickness of casting blank sheet.Then, by this Non-stretched casting blank sheet stretches 5 times, after being cooled to room temperature immediately with 120 DEG C of temperature in the flowing direction, followed by drawing Width machine horizontally stretches 10 times with 160 DEG C of temperature, obtains 12 μm of thickness of biaxially oriented polypropylene film 3.By the two-way drawing Stretched polypropylene film 3 is used as protective film 3.
The production of < support membrane >
Make the poly- of polyethylene terephthalate and the silica containing 1.0 1 μm of mass % average primary particle diameters The two in 170 DEG C of dryings, is respectively fed to double screw extruder later, 290 respectively by ethylene glycol terephthalate masterbatch It is melted at DEG C, is coextruded and is film-made by T mould, produce unstretching film.Then, biaxial tension is carried out to the unstretching film, obtained To 40 μm of thickness of support membrane 1.
The production of < photosensitive film lamination body >
Embodiment 1
Arithmetic mean surface roughness Ra ' and the maximum for measuring the protective film 1 obtained as described above in the following manner are high Ry ' is spent, as a result Ra ' is 0.18 μm, maximum height Ry ' is 1.28 μm.
The measurement of arithmetic mean surface roughness Ra ' and Ry ' have used measuring shape laser microscope (Co., Ltd. The VK-X100 of KEYENCE manufacture).Start measuring shape laser microscope (identical VK-X100) main body (control unit) and VK is seen After examining application program (VK-H1VX of Co., Ltd. KEYENCE manufacture), the protective film being measured (is made to contact photosensitive film Face be top) be placed on x-y microscope carrier.The lens for rotating microscope portion (VK-X110 of Co., Ltd. KEYENCE manufacture) turn Parallel operation selects 10 times of multiplying power of object lens, is roughly adjusted with the image viewing mode of VK observation application program (identical VK-H1VX) Save focal length, brightness.X-y microscope carrier is operated, screen center is come in the part for being adjusted to the hope measurement of specimen surface.By 10 times of multiplying power Object lens change 50 times of multiplying power into, utilize VK observation application program (identical VK-H1VX) image viewing mode auto-focusing Function is focused on the surface of sample.Select the simple mould of the measuring shape label of VK observation application program (identical VK-H1VX) Formula presses measurement start button, carries out the measurement of the surface shape of sample, obtains surface image file.Start VK analysis application Program (VK-H1XA of Co., Ltd. KEYENCE manufacture), after showing obtained surface image file, carries out slant correction.
[embodiment 5]
It should be noted that the Observe and measure range (transverse direction) in the measurement of the surface shape of sample is 270 μm.Show line Roughness window after selecting JIS B0601-1994 in parameter setting region, selects horizontal line from measurement line button, on surface Any position display horizontal line in image, presses OK button, and thus obtains arithmetic mean surface roughness Ra ' and maximum height The numerical value of Ry '.In turn, the different display horizontal lines everywhere in surface image, obtain each arithmetic mean surface roughness Ra ' With the numerical value of maximum height Ry '.Calculate separately out the average value of obtained 5 numerical value, the arithmetic average as specimen surface Surface roughness Ra ' value and maximum height Ry ' value.It should be noted that measurement is in room temperature (23 DEG C), relative humidity 42%RH It is carried out under environment.
Then, relative to 700 parts of the photosensitive composite 1 obtained as described above, methyl ethyl ketone is added with 300 parts of ratio It is diluted, is stirred 15 minutes using blender, obtain coating fluid.Using the extrusion coated machine of slit coventry type die head coventry, by the coating fluid Equably be applied on support membrane 1,80 DEG C at a temperature of it is 15 minutes dry, produce it is dry after it is photosensitive with a thickness of 25 μm Property film 1.Then, protective film 1 is bonded on photosensitive film 1 using layer of rolls press, so that the arithmetical average surface of the protective film 1 Roughness Ra ' and the aspect of measure of maximum height Ry ' connect with 1 surface of photosensitive film, produce by support membrane/photonasty The photosensitive film lamination body 1 (photosensitive film with a thickness of 25 μm) of this 3 layers of film/protective film composition.It should be noted that as institute The lamination for stating layer of rolls press is suitable for adjustment in the range of 40 DEG C~60 DEG C of roll temperature, roll-in 0.2MPa~0.4MPa.
The production of < test substrate >
Substrate is tested using the system of photosensitive film lamination body 1 obtained as described above.Referring to attached drawing to test substrate Making step is illustrated.
Firstly, will be protected relative to other 2 layers (support membranes/photosensitive film) with 90 ° of angle and the speed of 2.5 seconds/cm Film is removed from photosensitive film lamination body 1 and exposes photosensitive film, in the surface of the silicon wafer prepared fitting photosensitive film Exposed surface carries out heated lamination using layer of rolls press, keeps silicon wafer closely sealed with photosensitive film.It should be noted that as described The lamination of layer of rolls press, roll temperature is 60 DEG C, roll-in 0.25MPa.
Then, from the support membrane contacted with photosensitive film, across
(i) negative mask (referring to Fig.1) of the patterns of openings with 150 μm of square of grid size and 50 μm of square or
(ii) negative mask (not shown) of the patterns of openings with 150 μm of square of grid size and 100 μm of square,
To each embodiment and each comparative example, the pattern openings recorded in table 2 using metal halide lamp and light exposure Combination exposes photosensitive film, will support film stripping later, and expose photosensitive film.
Later, for the exposing surface of the photosensitive film of exposing, in propylene glycol in Examples 1 to 3 and comparative example 1~2 In the dipping of 23 DEG C of progress 1 minute in methyl ether acetate (PMA), in addition in example 4 in 1wt%Na2CO3In aqueous solution 30 DEG C, 2MPa, development in 60 seconds are carried out, in 1wt%Na in embodiment 52CO330 DEG C, 2MPa, 300 seconds are carried out in aqueous solution Development.Each test substrate after development is sufficiently washed, with not remaining developer solution.It should be noted that confirmation 1wt% Na2CO3The pH of aqueous solution, result 11.6.
Then, each test substrate is heated 30 minutes at 120 DEG C, solidifies photosensitive film, with grid shaped opening at Around 150 μm of square, obtain
(i) center have 50 μm of square pattern openings, it is wide 150 μm with the comparable solidification film figure (reference of wall portion Fig. 2)；Or
(ii) center have it is the pattern openings of 100 μm of square, wide 300 μm (do not scheme with the comparable cured pattern of wall portion Show).
In addition, protective film is removed from photosensitive film lamination body 1 and exposes photosensitive film, in obtained above and wall portion It is bonded the exposed surface of photosensitive film on comparable solidification film figure, and carries out heated lamination.It should be noted that lamination by The counterweight of 1.0kg is loaded on photosensitive film and is heated 5 minutes and is carried out at 80 DEG C.
Then, from the comparable support membrane side for solidifying the photosensitive film lamination body being bonded on film figure of wall portion, across
(i) negative mask (referring to Fig. 3) of the patterns of openings with 50 μm of square of grid size or
(ii) negative mask (not shown) of the patterns of openings with 100 μm of square of grid size,
For each embodiment and each comparative example, pattern openings and exposure using metal halide lamp to be recorded in table 2 The combination of amount exposes photosensitive film, will support film stripping later, and expose photosensitive film.It should be noted that across fitting Photosensitive film lamination body afterwards, according to
(i) pattern openings of 50 μm of square of wall portion are Chong Die with the pattern openings of 50 μm of square of grid size of negative mask Mode (referring to Fig. 3), or
(ii) pattern openings of 100 μm of square of grid size of the pattern openings and negative mask of 100 μm of square of wall portion The mode (not shown) of overlapping,
It is exposed.Later, for the exposing surface of the photosensitive film of exposing, in Examples 1 to 3 and comparative example 1~2 In the dipping of 23 DEG C of progress 1 minute in propylene glycol methyl ether acetate (PMA), in addition in example 4 in 1wt%Na2CO3 30 DEG C, 2MPa, development in 60 seconds are carried out in aqueous solution, in 1wt%Na in embodiment 52CO3In aqueous solution carry out 30 DEG C, 2MPa, development in 300 seconds.Each test substrate after development is sufficiently washed, with not remaining developer solution.
Then, each test substrate is heated 60 minutes at 200 DEG C, solidifies photosensitive film, formed comparable with cover Solidify film figure, thus produces with the test substrate including wall portion and the hollow structure of cover.Obtained test substrate In inside without comb-type electrode, but the upper end partes tegmentalis of wall portion covers, and has and forms at the joint portion of the cover and wall portion
(i) pattern openings (referring to Fig. 4) of 50 μm of square or
(ii) pattern openings (not shown) of 100 μm of square
Hollow structure.
Embodiment 2
In embodiment 1, photosensitive composite 2 is used instead of photosensitive composite 1, and replaces protective film 1 and makes With protective film 2, substrate is tested in production similarly to Example 1 in addition to this.It should be noted that being measured in the same manner as described above guarantor The measurement of the arithmetic mean surface roughness Ra ' and maximum height Ry ' of cuticula 2, as a result Ra ' is 0.46 μm, maximum height Ry ' is 1.37μm.It should be noted that protective film 2 is web-like, medial surface is batched to it and is measured.
Embodiment 3
In embodiment 1, protective film 2 is used instead of protective film 1, produces examination similarly to Example 1 in addition to this Test substrate.
Embodiment 4
In example 2, instead of the development using propylene glycol methyl ether acetate (PMA) in 1wt%Na2CO3Aqueous solution Middle progress 30 DEG C, 2MPa, development in 60 seconds, produce test substrate similarly to Example 2 in addition to this.
Embodiment 5
In example 4, photosensitive composite 3 is used instead of photosensitive composite 2, and in 1wt%Na2CO3It is water-soluble 30 DEG C, 2MPa, development in 300 seconds are carried out in liquid, produce test substrate similarly to Example 4 in addition to this.
Comparative example 1
In example 2, photosensitive composite 4 is used instead of photosensitive composite 2, it is same with embodiment 2 in addition to this Produce to sample test substrate.
Comparative example 2
In embodiment 1, protective film 3 is used instead of protective film 1, produces examination similarly to Example 1 in addition to this Test substrate.It should be noted that being measured in the same manner as described above the arithmetic mean surface roughness Ra ' and maximum height of protective film 3 The measurement of Ry ', as a result Ra ' is 0.07 μm, maximum height Ry ' is 0.98 μm.It should be noted that protective film 3 is web-like, to it Medial surface is batched to be measured.
The measurement of < arithmetic mean surface roughness Ra and maximum height Ry >
Using double faced adhesive tape (KZ-12, Co., Ltd. Nitoms are manufactured), will be used in Examples 1 to 5 and comparative example 1~2 Each photosensitive film lamination body (35mm × 20mm) conform to clean surface glass substrate (76mm × 26mm × 1.1mmt), make The support membrane side contacts of glass substrate and photosensitive film keep glass substrate and photosensitive film lamination body closely sealed.
Later, by the protective film of photosensitive film lamination body relative to glass substrate with 90 ° of angle and the speed of 2.5 seconds/cm Degree removing, exposes photosensitive film.In 5 minutes after the protection film stripping soon, (passed through soon after measurement protection film stripping After spending 1 minute) exposing photosensitive film surface arithmetic mean surface roughness Ra1 and maximum height Ry1.Ra1's and Ry1 Measurement is following to be carried out.
" the arithmetic mean surface roughness Ra " on the photosensitive film surface about exposing uses the arithmetic with protection film surface The identical device of the measurement of average surface roughness Ra ', replaces with protective film for sample, and the photosensitive film for being fitted with exposing is made Substrate (make expose photosensitive film surface top), be measured in the same manner as described above measurement in addition to this.In addition, about exposing Photosensitive film surface " maximum height Ry ", also use with the identical device of the support measurement of maximum height Ry ' of film surface, Sample is replaced with into protective film, the substrate for being fitted with the photosensitive film of exposing is made (on the photosensitive film surface for making exposing Portion), it is measured in the same manner as described above measurement in addition to this." the arithmetic mean surface roughness on each photosensitive film surface measured Ra1 " and " maximum height Ry1 " are as shown in table 2.
In addition, each measurement sample is existed in the state of exposing photosensitive film surface by removing the protective film (room temperature (23 DEG C), relative humidity 42%RH) is placed 180 minutes under amber light under determination of the environment, is measured as described above later The arithmetic mean surface roughness Ra and maximum height Ry on the photosensitive film surface of exposing.Each photosensitive film surface measured " arithmetic mean surface roughness Ra2 " and " maximum height Ry2 " is as shown in table 2.
The evaluation of < plating adaptation >
Electroless copper facing is carried out for each test substrate of the Examples 1 to 5 and comparative example 1~2 that make as described above.Plating Patch part is as described below.
Electroless plating copper liquid: Melplate CU-390 (manufacture of Meltex Co., Ltd.)
Plating liquid temperature: 80 DEG C
Plating times: 1 hour
Plating film thickness: 2.0 μm
PH:13.0 (room temperature)
After plating, the pure water for being formed with each test substrate room temperature of electroless plating overlay film is subjected to 5 minutes water It washes, is dried later at 80 DEG C.Utilize the wall portion of the obtained each test substrate of optical microscopy and electron microscope observation With the section on the boundary of electroless plating overlay film.Evaluation criteria is as described below.
◎: gap is not generated, closely sealed there is no problem.
Zero: slightly generation gap, but closely sealed there is no problem.
×: gap is generated, it is closely sealed problematic.
Evaluation result is as described in Table 2.
As shown in Table 2, using the arithmetic mean surface roughness Ra1 of photonasty film surface be 0.1 μm or more and Ra2/Ra1 is the (implementation of test substrate 1~5 that the 0.40 photosensitive film lamination body more than and less than 1.00 has formed hollow structure Example 1~5) in, it is high with the adaptation of the coating of wall portion and cover, the electronic component with the hollow structure of high-quality can be obtained.
On the other hand, it is known that: it is photosensitive less than 0.1 μm using the arithmetic mean surface roughness Ra1 of photonasty film surface Property film layer product body form in the test substrate 7 (comparative example 2) of hollow structure, even if Ra2/Ra1 be 0.40 more than and less than 1.00, it is also insufficient with the adaptation of the coating of wall portion and cover, sealing material.
In addition, knowing: the arithmetic mean surface roughness Ra1 using photonasty film surface is 0.1 μm or more but Ra2/ Ra1 (does not compare in the test substrate 6 that the photosensitive film lamination body of 0.40 range more than and less than 1.00 has formed hollow structure Example 1) in, it is also insufficient with the adaptation of the coating of wall portion and cover.

Claims (8)

1. a kind of photosensitive film lamination body, for photosensitive film made of successively having support membrane, being formed as photosensitive composite, With the photosensitive film lamination body of protective film, which is characterized in that
The protective film is removed from the photosensitive film lamination body and exposes the photosensitive film surface, 23 DEG C, it is opposite The arithmetic mean surface roughness on the photosensitive film surface after placing 1 minute in the environment of humidity 42% is set as Ra1,
The protective film is removed from the photosensitive film lamination body and exposes the photosensitive film surface, 23 DEG C, it is opposite The arithmetic mean surface roughness on the photosensitive film surface after placing 180 minutes in the environment of humidity 42% is set as Ra2,
Meet following formula at this time:
Ra1>=0.10 μm and 0.40≤Ra2/Ra1<1.00.
2. photosensitive film lamination body as described in claim 1, wherein
The protective film is removed from the photosensitive film lamination body and exposes the photosensitive film surface, 23 DEG C, it is opposite The maximum height on the photosensitive film surface after placing 1 minute in the environment of humidity 42% is set as Ry1,
The protective film is removed from the photosensitive film lamination body and exposes the photosensitive film surface, 23 DEG C, it is opposite The maximum height on the photosensitive film surface after placing 180 minutes in the environment of humidity 42% is set as Ry2,
Meet following formula at this time:
Ry1>=1.00 μm and 0.30≤Ry2/Ry1<1.00.
3. photosensitive film lamination body as described in claim 1, wherein the photosensitive composite includes photo-curable chemical combination Object.
4. photosensitive film lamination body as described in claim 1, wherein the photosensitive composite further includes photopolymerization and draws Send out agent.
5. photosensitive film lamination body as described in claim 1, the composition institute for being used to have in the electronic component of hollow structure State the formation of the cover or wall portion of hollow structure.
6. a kind of solidfied material, which is characterized in that it makes photosensitive film lamination body according to any one of claims 1 to 5 Obtained from photosensitive film solidification.
7. a kind of electronic component, which is characterized in that it is with solidfied material as claimed in claim 6.
8. electronic component as claimed in claim 7 has the hollow structure including wall portion and cover, the wall portion and cover Any one of or both be made of the solidfied material.
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JP6748478B2 (en) * 2016-04-25 2020-09-02 太陽インキ製造株式会社 Dry film, cured product and printed wiring board
JP6767153B2 (en) * 2016-04-25 2020-10-14 太陽インキ製造株式会社 Dry film, hardened material and printed wiring board
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US20130076458A1 (en) * 2010-05-20 2013-03-28 Sadaaki Katou Photosensitive resin composition, photosensitive film, rib pattern formation method, hollow structure and formation method for same, and electronic component
JP2017120393A (en) * 2015-12-28 2017-07-06 旭化成株式会社 Laminate

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