KR20190114835A - Photosensitive film laminate and cured product thereof, and electronic component - Google Patents

Abstract

The present invention provides a photosensitive film stack suitable for use in formation of a hollow structure and capable of suppressing peeling of plating or the like, from a part close to the hollow structure, in an electronic component having the hollow structure, such as an SAW filter. More specifically, the photosensitive film stack sequentially includes a support film, a photosensitive film made of a photosensitive composition, and a protective film, wherein formulae, Ra1 >= 0.10 μm and 0.40 <= Ra2/Ra1 < 1.00, are satisfied, when Ra1 is an arithmetic average surface roughness of the surface of the photosensitive film after the surface of the photosensitive film is exposed by peeling the protective film off the photosensitive film stack, and left out under an environment of 23°C and relative humidity of 42% for one minute, and Ra2 is an arithmetic average surface roughness of a surface of the photosensitive film after the surface of the photosensitive film is exposed by peeling the protective film off the photosensitive film stack, and left out under an environment of 23°C and relative humidity of 42% for 180 minutes.

Description

Photosensitive film laminated body and its hardened | cured material, and an electronic component TECHNICAL FIELD [PHOTOSENSITIVE FILM LAMINATE AND CURED PRODUCT THEREOF, AND ELECTRONIC COMPONENT}

The present invention relates to a photosensitive film laminate, and more particularly, to an electronic component having a hollow structure, to a photosensitive film laminate, a cured product thereof, and an electronic component that can be suitably used for forming the hollow structure. .

In recent years, the demand for miniaturization and high functionalization of electronic devices is increasing, and miniaturization, thinning, and complex functionalization are further required for electronic components used therein. Among these, image sensors such as CMOS and CCD sensors, gyro sensors and surface acoustic waves using MEMS (Micro Electro Mechanical Systems) technology in which mechanical and electronic circuit elements are integrated on a substrate by semiconductor microfabrication techniques. The development of microelectronic components, such as package of an element which forms an electrode pattern or a microstructure on the surface of a single crystal wafer represented by a SAW) filter, and exhibits a specific electrical function, attracts attention. In these microelectronic components, a hollow structure is formed in order to prevent other objects from contacting the active surface (movable portion) of the sensor element and to protect the sensor element from moisture and dust, and the like, and a sensor or the like is disposed therein. It is.

As described above, in the above-mentioned electronic components, hollow structures have been formed by processing and joining inorganic materials. However, there is a desire to reduce manufacturing costs and further downsize, and a method of forming a hollow structure by using a photosensitive resin or the like instead of an inorganic material has begun to be studied. For example, a permanent resist is laminated and a photolithography technique is used. It is proposed to form a wall portion (wall surface) or a cover portion to have a hollow structure (for example, WO2009 / 151050).

By the way, the electronic component which has a hollow structure, such as SAW filter mentioned above, is manufactured as a package structure which has the external terminal or external electrode which electrically connected with the wiring electrode of a piezoelectric substrate, in order to mount to a mounting substrate. In that case, in order to obtain the connection reliability with external wiring in the wall part and the cover part which form a hollow structure, forming an internal conductor by a plating method etc. is performed. In addition, in order to improve the handleability with protection of an element, the hollow structure and the proximity part are resin-sealed by the transfer mold method.

However, when the hollow structure was formed by the permanent resist, it was confirmed that when the inner conductor was formed in the proximal portion, peeling of plating or the like occurred, or the sealing material was peeled off from the surface of the wall portion or the lid portion of the hollow structure.

Therefore, this invention provides the photosensitive film laminated body suitable for formation of a hollow structure in the electronic component which has a hollow structure, such as SAW filter, which can suppress peeling, such as plating in the proximal part of a hollow structure. For the purpose of Moreover, another object of this invention is to provide the hardened | cured material formed using the said photosensitive film laminated body, and the electronic component which has a hollow structure.

As a method of forming the above hollow structure by the use of a resin, any number of layers of a photosensitive film are laminated to form a wall portion by exposure and development, and another photosensitive film is placed on the top of the wall portion to expose a predetermined shape, The hollow structure can be formed by developing and forming a lid part and thermosetting a photosensitive resin. MEANS TO SOLVE THE PROBLEM As a result of earnestly examining the said subject, when the hollow structure was formed using the photosensitive film as mentioned above, the developer used at the image development process in the wall part and cover part which comprise a hollow structure remains slightly, and this developer By spreading from this interface, it discovered that adhesiveness with plating etc. was inhibited and peeling off was easy. Furthermore, as a result of further examination, in the photosensitive film laminated body provided with a protective film, the hollow film was formed into the photosensitive film laminated body in which the time-dependent change of the said surface form after peeling a protective film and exposing the photosensitive film surface is a specific range. It has been found that by using in the above, it is possible to suppress the impairment of adhesion to plating or the like and to manufacture an electronic component having a high quality hollow structure.

The present invention is as follows.

[1] A photosensitive film laminate comprising a photosensitive film formed of a supporting film and a photosensitive composition and a protective film in order;

The protective film is peeled from the photosensitive film laminate to expose the surface of the photosensitive film, and the arithmetic mean surface roughness of the surface of the photosensitive film after being left for 1 minute in an environment of 23 ° C. and 42% relative humidity is set to Ra1,

The protective film is peeled off from the photosensitive film laminate to expose the surface of the photosensitive film, and the arithmetic mean surface roughness of the surface of the photosensitive film after being left for 180 minutes in an environment of 23 ° C. and 42% relative humidity is Ra2.

In one case, the following formula:

Ra1≥0.10μm and also 0.40≤Ra2 / Ra1 <1.00

Photosensitive film laminated body which satisfy | fills.

[2] The protective film is peeled from the photosensitive film laminate to expose the surface of the photosensitive film, and the maximum height of the surface of the photosensitive film after standing for 1 minute in an environment of 23 ° C. and 42% relative humidity is determined by Ry1,

The protective film is peeled from the photosensitive film laminate to expose the surface of the photosensitive film, and the maximum height of the surface of the photosensitive film after standing for 180 minutes in an environment of 23 ° C. and 42% relative humidity is Ry2.

In one case, the following formula:

Ry1≥1.00μm and also 0.30≤Ry2 / Ry1 <1.00

The photosensitive film laminated body of [1] which satisfy | fills.

[3] The photosensitive film laminate of [1], wherein the photosensitive composition contains a photocurable compound.

[4] The photosensitive film laminate of [1], wherein the photosensitive composition further contains a photopolymerization initiator.

[5] The photosensitive film laminate according to [1], which is used to form a lid portion or a wall portion that constitutes the hollow structure in an electronic component having a hollow structure.

[6] A cured product obtained by curing the photosensitive film of the photosensitive film laminate according to any one of [1] to [5].

[7] An electronic component having a cured product of [6].

[8] The electronic component of [7], having a hollow structure including a wall portion and a cover portion, and either or both of the wall portion and the cover portion include the cured product.

According to this invention, in the electronic component which has a hollow structure, the photosensitive film laminated body suitable for formation of a hollow structure which can suppress peeling, such as plating in the vicinity of a hollow structure, can be provided. Moreover, according to another aspect of this invention, the hardened | cured material and electronic component formed using the said photosensitive film laminated body can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic cross section which shows the manufacture procedure of the test board | substrate produced in Example 4 and Example 5. FIG.
It is a schematic cross section which shows the manufacture procedure of the test board | substrate produced in Example 4 and Example 5. FIG.
It is a schematic cross section which shows the manufacture procedure of the test board | substrate produced in Example 4 and Example 5. FIG.
It is a schematic cross section which shows the preparation procedure of the test board | substrate produced in Example 4 and Example 5. FIG.

<Photosensitive film laminated body>

The photosensitive film laminated body which concerns on this invention is equipped with the photosensitive film formed with the support film and the photosensitive composition, and a protective film in order. Hereinafter, each component which comprises the photosensitive film laminated body of this invention is demonstrated. In addition, unless otherwise indicated, in this specification, the numerical range represented using symbol "-" uses the range containing the numerical value of the upper limit and the lower limit (that is, more than its minimum and below its upper limit). it means.

[Support film]

The support film which comprises the photosensitive film laminated body which concerns on this invention supports a photosensitive film, and if it is a well-known thing if it can achieve the said function, it can be used without a restriction | limiting in particular, For example, polyethylene terephthalate, a polyethylene naphthalate, etc. The film containing thermoplastic resins, such as a polyester film, a polyimide film, a polyamideimide film, a polypropylene film, and a polystyrene film, can be used conveniently. In addition, when using the said thermoplastic resin film, a filler is added to the resin at the time of film-forming, the coating process is carried out, a mat coating (coating process), the film surface is subjected to the blast process like sandblasting process, Alternatively, a treatment such as hairline processing or chemical etching may be performed. Among these, a polyester film can be used suitably from a viewpoint of heat resistance, mechanical strength, handleability, etc. A single layer may be sufficient as a support film, and 2 or more layers may be laminated | stacked.

It is preferable to use the film extended | stretched to the uniaxial direction or the biaxial direction for the thermoplastic resin film as mentioned above in order to improve intensity | strength.

In addition, it is preferable to use the film extended | stretched to the uniaxial direction or the biaxial direction for the thermoplastic resin film as mentioned above in order to improve intensity | strength.

Although the thickness of a support film is not specifically limited, It selects suitably according to a use in the range of about 10 micrometers or more and 3,000 micrometers or less.

[Photosensitive film]

The photosensitive film which comprises the photosensitive film laminated body which concerns on this invention is formed of the photosensitive composition. That is, the photosensitive composition containing each component mentioned later can be apply | coated to one side of a support film, and it can form by drying. A photosensitive film turns into hardened | cured material by hardening | curing a photosensitive composition after making it a predetermined shape by exposure and image development. Therefore, in the state which peeled the protective film from the photosensitive film laminated body and exposed the surface of the photosensitive film, since the photosensitive composition is in an uncured state, the surface form of the photosensitive film changes with time. In the present invention, it has been found that there is a relationship between the change in the surface form of the photosensitive film over time and peeling such as plating, and the hollow structure of the electronic component is made photosensitive by using a photosensitive film laminate that satisfies the following conditions. When it forms using a film laminated body, it can suppress that the adhesiveness with plating etc. is inhibited, and the electronic component which has a high quality hollow structure can be implement | achieved.

In the present invention, the protective film is peeled from the photosensitive film laminate to expose the surface of the photosensitive film, and the arithmetic mean surface roughness of the surface of the photosensitive film after being left for 1 minute in an environment of 23 ° C and 42% relative humidity is set to Ra1,

The protective film is peeled off from the photosensitive film laminate to expose the surface of the photosensitive film, and the arithmetic mean surface roughness of the surface of the photosensitive film after being left for 180 minutes in an environment of 23 ° C. and 42% relative humidity is Ra2.

In one case, the following formula:

Ra1≥0.10μm and also 0.40≤Ra2 / Ra1 <1.00

It is important to satisfy. When the photosensitive film at the time of peeling a protective film has the uneven surface of predetermined | prescribed arithmetic mean surface roughness, the uneven surface tends to become a flat state gradually, and a surface form changes with time. In this invention, paying attention to the time-dependent change of this surface form, peeling, such as plating in the vicinity of a hollow structure, can be suppressed by using the photosensitive film which stays in a specific surface form change.

In this invention, the arithmetic mean surface roughness Ra1 of the photosensitive film of the surface which contacted the protective film after peeling off a protective film is 0.10 micrometer or more, 0.15 micrometer or more is preferable and it is more preferable that it is 0.20 micrometer or more. Moreover, when setting an upper limit, 1.00 micrometers or less are preferable, 0.80 micrometers or less are more preferable, 0.60 micrometers or less are more preferable. In addition, Ra1 is defined as the value measured by peeling a protective film, exposing the said photosensitive film surface, and leaving it to stand for 1 minute in 23 degreeC and 42% of the relative humidity environment.

Moreover, from a viewpoint of further suppressing peeling, such as plating, 1.00 or more are preferable, as for the maximum height Ry1 of the photosensitive film of the surface which contacted the protective film after peeling off a protective film, 1.20 micrometers or more are more preferable, 1.40 More preferably µm or more. Moreover, when setting an upper limit, 5.00 micrometers or less are preferable, 4.00 micrometers or less are more preferable, and 3.00 micrometers or less are more preferable. In addition, Ry1 is defined as the value measured by peeling a protective film, exposing the said photosensitive film surface, and leaving it to stand for 1 minute in the environment of 23 degreeC and 42% of relative humidity.

The shape change over time of the photosensitive film surface can be evaluated by the ratio of the arithmetic mean surface roughness after predetermined time progress with respect to the arithmetic mean surface roughness (namely, Ra1) immediately after peeling off a protective film. In this invention, the arithmetic mean of the photosensitive film of the surface which contacted the protective film after peeling a protective film from the photosensitive film laminated body, exposing the photosensitive film surface, and leaving it to stand for 180 minutes in 23 degreeC and 42% of relative humidity environment. When surface roughness is set to Ra2, if the photosensitive film laminated body which satisfy | fills 0.40 <= Ra2 / Ra1 <1.00 can peel off, such as plating in the proximal part of a hollow structure. This reason is not clear, but it thinks as follows. That is, in the photosensitive film laminate provided with the protective film, if the surface form having a constant roughness after peeling off the protective film and exposing the photosensitive film surface gradually changes over time, and the ratio of such a change is constant, In the case of the wall material, in the case of the base material and the cover material, the degree of close contact with the wall material becomes more appropriate, and the remaining developer used at the time of development is prevented from entering the periphery of the hollow structure, and as a result, plating resulting from the remaining developer It is guessed that peeling of was able to be suppressed. However, it is an area of speculation to the last and is not necessarily so. In addition, in this invention, as a place to leave for 180 minutes in the state which peeled a protective film and exposed the photosensitive film surface, it shall be under a yellow lamp.

As for the shape change over time of the photosensitive film surface, 0.50 <Ra2 / Ra1 <0.95 is preferable and 0.60 <Ra2 / Ra1 <0.90 is more preferable from a viewpoint of suppressing peeling further from a change of a suitable shape.

Moreover, peeling a protective film from the photosensitive film laminated body and exposing the photosensitive film surface and making the maximum height of the photosensitive film of the surface which contact | connected the protective film after leaving for 180 minutes in the environment of 23 degreeC and 42% of a relative humidity as Ry2 In the case, if it is a photosensitive film laminated body which satisfy | fills 0.30 <= Ry2 / Ry1 <1.00, peeling, such as plating, can be suppressed further. In addition, in this invention, as a place to leave for 180 minutes in the state which peeled a protective film and exposed the photosensitive film surface, it shall be under a yellow lamp.

As for shape change with respect to the surface of a photosensitive film, 0.35 <= Ry2 / Ry1 <= 0.80 is preferable and 0.40 <Ry2 / Ry1 <0.70 is more preferable from a viewpoint of suppressing peeling further from a change of a suitable shape.

Moreover, it is preferable that arithmetic surface roughness Ra "and the maximum height Ry" of the surface which contact | connect the support film in a photosensitive film also exist in the same range and change rate as arithmetic surface roughness Ra and the maximum height Ry of the surface which contact | connect the said protective film. It is especially effective when there is no protective film and it is a photosensitive film laminated body provided with the support film and the photosensitive film formed with the photosensitive composition in order. In this case, it is preferable that a support film is the same material and thickness as the protective film mentioned later.

In addition, in this invention, said "arithmetic mean surface roughness Ra" and "maximum height Ry" mean the value measured by the measuring apparatus based on JISB0601-1994. Hereinafter, the specific measuring method is demonstrated. Arithmetic mean surface roughness Ra and maximum height Ry can be measured using a shape-measuring laser microscope (for example, VK-X100 by Kyens Co., Ltd.). After starting a shape measuring laser microscope (VK-X100) main body (control part) and a VK observation application (VK-H1VX made from Keyence Co., Ltd.), the sample (photosensitive film) to measure on an x-y stage is loaded. By rotating the lens revolver of the microscope unit (VK-X110 manufactured by Keyence Co., Ltd.), the objective lens with a magnification of 10 times is selected, and the focus and brightness are adjusted in the image observation mode of the VK observation application (the same VK-H1VX). By operating the x-y stage, the portion of the sample surface to be measured is adjusted to be in the center of the screen. We change objective lens of magnification 10 times to magnification 50 times and focus on sample surface with autofocus function of image observation mode of VK observation application (the same VK-H1VX). The simple mode of the shape measurement tab of the VK observation application (the same VK-H1VX) is selected, the measurement start button is pressed, the surface shape of the sample can be measured, and a surface image file can be obtained. After starting the VK analysis application (VK-H1XA manufactured by Keyence Co., Ltd.) to display the obtained surface image file, the tilt correction is performed. In addition, the observation measurement range (width) in the measurement of the surface shape of a sample shall be 270 micrometers. Display the line roughness window, select JIS B0601-1994 in the parameter setting area, select a horizontal line from the measurement line button, display a horizontal line at an arbitrary place in the surface image, and press the OK button to select the arithmetic average surface roughness. Get the value of Ra and the maximum height Ry. In addition, horizontal lines are displayed at four different places in the surface image to obtain numerical values of the respective arithmetic mean surface roughness Ra and the maximum height Ry. The average value of five obtained numerical values is respectively computed, and it is set as the arithmetic mean surface roughness Ra and the maximum height Ry value of a sample surface. In addition, in the measurement of said arithmetic mean surface roughness Ra and maximum height Ry, the photosensitive film in the state before the hardening process by exposure etc. shall be used as a measurement sample. When the protective film is laminated | stacked on the photosensitive film as a laminated body like this invention, the measurement sample in the state which peeled the protective film before lamination to a base material shall be used. In this case, "arithmetic mean surface roughness Ra" and "maximum height Ry" of a sample surface shall be measured immediately after peeling a protective film and exposing the photosensitive film (1 minute) and 180 minutes. In addition, as a measurement environment in this invention, it is set as temperature of 23 degreeC, and 42% of a relative humidity.

In order to make the surface form of the photosensitive film into the range of the above-mentioned specific arithmetic mean surface roughness Ra and the maximum height Ry, well-known conventional methods can be applied, but in particular, from the viewpoint of the ease with which the surface form is formed as described above. In the protective film as mentioned later, the photosensitive film can be formed using what adjusted arithmetic mean surface roughness Ra and maximum height Ry. In addition, after adhering the protective film having a specific arithmetic mean surface roughness Ra and the maximum height Ry, the protective film is peeled off, and then a separate protective film having another arithmetic mean surface roughness Ra and the maximum height Ry is adhered to the photosensitive film surface. The roughness of the photosensitive film surface may be adjusted.

In addition, the aging change of the surface form of the photosensitive film after peeling a protective film can be adjusted with the kind and compounding quantity of the component contained in the photosensitive composition before hardening which comprises a photosensitive film. For example, although it can adjust by mix | blending the material from which a solubility parameter (SP value) differs, using a material with suitable glass transition temperature (Tg) and a weight average molecular weight, or using a filler suitably, it is not limited to these. In this invention, although the photosensitive composition which forms a photosensitive film does not have a restriction | limiting in particular in the composition, A photocurable compound, a photoinitiator, a thermal crosslinking material, an inorganic filler, etc. may be contained. Hereinafter, each component which comprises the photosensitive composition is demonstrated.

[Photocurable Compound]

The photosensitive composition used for the photosensitive film laminated body of this invention contains the component hardened | cured by irradiation of ionizing radiation, such as an ultraviolet-ray, and a photocurable compound is mentioned as an example. A photocurable compound is a compound which has an ethylenically unsaturated double bond, and a compound contains all resin, an oligomer, and a monomer. As such a photocurable compound, For example, alkyl (meth) acrylates, such as 2-ethylhexyl (meth) acrylate and cyclohexyl (meth) acrylate; Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; Mono or di (meth) acrylates of alkylene oxide derivatives such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol; Polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, trishydroxyethyl isocyanurate or polyhydric (meth) acrylates of ethylene oxide or propylene oxide adducts thereof ; (Meth) acrylates of ethylene oxide or propylene oxide adducts of phenols such as phenoxyethyl (meth) acrylate and polyethoxydi (meth) acrylate of bisphenol A; (Meth) acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether and triglycidyl isocyanurate; And melamine (meth) acrylate etc. are mentioned. In addition, in this specification, (meth) acrylate is a term which generically mentions acrylate, methacrylate, and mixtures thereof, and is the same also about another similar expression.

Moreover, besides what was mentioned above, urethane monomers, urethane oligomers, etc., such as a (meth) acrylate compound which has an amide bond, and a (meth) acrylate compound which have a urethane bond, are mentioned.

Moreover, a photocurable compound can be made into carboxyl group-containing photosensitive resin by making unsaturated carboxylic acid, such as acrylic acid and methacrylic acid, react with an epoxy resin or a phenol resin. Such carboxyl group-containing photosensitive resin is preferable at the point which can superpose | polymerize, bridge | crosslink, and harden | cure by light irradiation, and can be made not only solvent image development but alkali developability by containing a carboxyl group. It is especially preferable at the point which can make excellent developing property also about weak alkaline property, specifically, pH 7.0 or more and 12.0 or less.

As a specific example of carboxyl group-containing photosensitive resin, the compound (any of an oligomer or a polymer) enumerated below is mentioned.

(1) (meth) acrylic acid is made to react with bifunctional or more than polyfunctional (solid) epoxy resin, and dibasic acid anhydrides, such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride, are added to the hydroxyl group which exists in a side chain. Carboxyl group-containing photosensitive resin

(2) Containing the carboxyl group in which the hydroxyl group of the bifunctional (solid) epoxy resin was further epoxidized with epichlorohydrin, (meth) acrylic acid was reacted to add the dibasic anhydride to the generated hydroxyl group. Photosensitive resin,

(3) A compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, and an unsaturated group-containing monocarboxylic acid such as (meth) acrylic acid is reacted with an epoxy compound having two or more epoxy groups in one molecule. The carboxyl group-containing photosensitive resin obtained by making polybasic acid anhydrides, such as maleic anhydride, tetrahydro phthalic anhydride, trimellitic anhydride, a pyromellitic anhydride, adipic acid, react with the alcoholic hydroxyl group of the obtained reaction product,

(4) 2 in 1 molecule, such as bisphenol A, bisphenol F, bisphenol S, a novolac phenol resin, poly-p-hydroxystyrene, a condensate of naphthol and aldehydes, and a condensate of dihydroxynaphthalene and aldehydes The polybasic acid is reacted with a reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups with an alkylene oxide such as ethylene oxide or propylene oxide, and an unsaturated group-containing monocarboxylic acid such as (meth) acrylic acid. Carboxyl group-containing photosensitive resin obtained by making anhydride react,

(5) Polybasic acid to the reaction product obtained by making unsaturated group containing monocarboxylic acid react with the reaction product obtained by making the compound which has two or more phenolic hydroxyl groups in 1 molecule, and cyclic carbonate compounds, such as ethylene carbonate and a propylene carbonate, react. Carboxyl group-containing photosensitive resin obtained by making anhydride react,

(6) diisocyanate compounds such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, polycarbonate polyol, polyether polyol, polyester polyol, polyolefin polyol, acrylic polyol, bisphenol Terminal carboxyl group-containing photosensitive urethane resin which makes acid anhydride react with the terminal of the urethane resin by polyaddition reaction of diol compounds, such as A type alkylene oxide adduct diol, a compound which has a phenolic hydroxyl group, and alcoholic hydroxyl group. ,

(7) Molecules, such as hydroxyalkyl (meth) acrylate, during synthesis of the carboxyl group-containing urethane resin by the polyaddition reaction of diisocyanate, carboxyl group-containing dialcohol compounds, such as dimethylolpropionic acid and dimethylol butyric acid, and a diol compound The carboxyl group-containing photosensitive urethane resin which added the compound which has one hydroxyl group and one or more (meth) acryloyl groups in the terminal, and was terminal (meth) acrylated,

(8) During synthesis of the carboxyl group-containing urethane resin by the polyaddition reaction of the diisocyanate, the carboxyl group-containing dialcohol compound, and the diol compound, one of the molecules, such as an equimolar reactant of isophorone diisocyanate and pentaerythritol triacrylate. The carboxyl group-containing photosensitive urethane resin which added the compound which has an isocyanate group and at least one (meth) acryloyl group, and was terminal (meth) acrylated,

(9) To carboxyl group-containing polyester resin which made dibasic acid, such as adipic acid, phthalic acid, and hexahydrophthalic acid, react with polyfunctional oxetane resin, and added dibasic acid anhydride to the produced | generated primary hydroxyl group, Carboxyl group-containing photosensitive resin formed by adding the compound which has one epoxy group and one or more (meth) acryloyl groups in 1 molecule, such as glycidyl (meth) acrylate and (alpha) -methyl glycidyl (meth) acrylate, ,

(10) The carboxyl group-containing photosensitive resin which added the compound which has a cyclic ether group and a (meth) acryloyl group in 1 molecule to the carboxyl group-containing photosensitive resin in any one of said (1)-(9),

(11) About carboxyl group-containing resin obtained by copolymerization of unsaturated carboxylic acids, such as (meth) acrylic acid, and unsaturated group containing compounds, such as styrene, (alpha) -methylstyrene, lower alkyl (meth) acrylate, and isobutylene, 3 Carboxyl group containing photosensitive resin which made the compound which has a cyclic ether group and a (meth) acryloyl group react in 1 molecule, such as a 4-4-epoxy cyclohexyl methacrylate, etc. are mentioned. In addition, the term (meth) acrylate here is generic terms for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions below.

Although the weight average molecular weight of said photocurable compound changes with resin skeleton, it is preferable that it is generally 2,000-200,000. When the weight average molecular weight is 2,000 or more, the touch drying performance and the resolution can be improved. Moreover, the state change with time of the coating film surface becomes suitable, and adhesiveness with a base can be improved more. Moreover, developability and storage stability can be improved because a weight average molecular weight is 200,000 or less. More preferable weight average molecular weights are 4,000-150,000, More preferably, they are 5,000-100,000. In addition, a weight average molecular weight can be measured by the gel permeation chromatography (GPC) method (polystyrene standard).

When the compounding quantity of a photocurable compound also contains the thermal crosslinking material mentioned later in a composition, when the total amount of a photocurable compound and a thermal crosslinking material is 100 mass parts in conversion of solid content, it is preferable that it is 50-90 mass parts. By carrying out the compounding quantity of a photocurable compound in the said range, a hollow structure with more intensity | strength can be formed. Moreover, the state change with time of the coating film surface becomes moderate, and adhesiveness with a base can be improved more.

[Thermal Materials]

By adding a thermal crosslinking material, the heat resistance of a photosensitive film can be expected to improve. A thermal crosslinking material can be used individually by 1 type or in combination of 2 or more types. As a thermal crosslinking material, all well-known things can be used. For example, amino resins such as melamine resin, benzoguanamine resin, melamine derivatives, benzoguanamine derivatives, isocyanate compounds, block isocyanate compounds, cyclocarbonate compounds, epoxy compounds, oxetane compounds, episulfide resins, bismaleimides Known thermosetting components, such as novolak resins, such as carbodiimide resin, a melamine resin, urea resin, a polyimide resin, a phenol novolak, and a cresol novolak, can be used. Among these, an epoxy resin, a melamine resin, and urea resin are preferable from a viewpoint of the adhesiveness of the hardened | cured material of a photosensitive composition and a board | substrate, and an epoxy resin is more preferable.

When the compounding quantity of a thermal crosslinking material also contains the photocurable compound mentioned above in a composition, when the total amount of a photocurable compound and a thermal crosslinking material is 100 mass parts in conversion of solid content, it is preferable that it is 10-40 mass parts. By making the compounding quantity of a thermal crosslinking material into the said range, a hollow structure with more strength can be formed. Moreover, since the ratio of a photocurable compound increases by making the compounding quantity of a thermal crosslinking material into 40 mass parts or less, the resolution improves more.

When using an epoxy resin etc. as a heat crosslinking material, the hardening | curing agent for hardening an epoxy resin may be contained further. Examples of the curing agent include amines, imidazoles, polyfunctional phenols, acid anhydrides, isocyanates, and polymers containing these functional groups, and a plurality thereof may be used as necessary.

[Photopolymerization Initiator]

Specific examples of the photopolymerization initiator include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, and bis- (2 , 6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, Bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphineoxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphineoxide, bis- (2 Bisacyl phosphine oxides such as 4,6-trimethylbenzoyl) -phenylphosphine oxide; 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, p Monoacyl phosphine oxides such as isopropyl phenylphosphinic acid isopropyl ester and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Phenyl (2,4,6-trimethylbenzoyl) ethylphosphinate, 1-hydroxy-cyclohexylphenylketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl -1-Propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane-1-one Hydroxyacetophenones such as 2-hydroxy-2-methyl-1-phenylpropan-1-one; Benzoin such as benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, and benzoin n-butyl ether; Benzoin alkyl ethers; Benzophenones such as benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone and 4,4'-bisdiethylaminobenzophenone; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl- 1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- Acetophenones such as (dimethylamino) -2-[(4-methylphenyl) methyl) -1- [4- (4-morpholinyl) phenyl] -1-butanone and N, N-dimethylaminoacetophenone; Thioxanthone, 2-ethyl thioxanthone, 2-isopropyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2-chloro thioxanthone, 2,4-di Thioxanthones, such as isopropyl thioxanthone; Anthraquinones such as anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2- (dimethylamino) ethylbenzoate and p-dimethylbenzoic acid ethyl ester; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbox Oxime esters such as bazol-3-yl]-, 1- (O-acetyl oxime); Bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium, bis (cyclopentadienyl)- Titanocenes such as bis [2,6-difluoro-3- (2- (1-phyl-1-yl) ethyl) phenyl] titanium; Phenyl disulfide 2-nitrofluorene, butyroline, anisoin ethyl ether, azobisisobutyronitrile, tetramethyl thiuram disulfide, etc. are mentioned.

When the compounding quantity of a photoinitiator contains the photocurable compound mentioned above in a composition, it is preferable that it is 0.1-10 mass parts in solid content conversion with respect to 100 mass parts of photocurable compounds. By making the compounding quantity of a photoinitiator into the said range, resolution improves more.

You may use photoinitiator or a sensitizer in combination with said photoinitiator. As a photoinitiation adjuvant or a sensitizer, a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, a benzophenone compound, a tertiary amine compound, a xanthone compound, etc. are mentioned. Although these compounds can be used as a photoinitiator, it is preferable to use together with a photoinitiator. In addition, a photoinitiation adjuvant or a sensitizer may be used individually by 1 type, and may use 2 or more types together.

Moreover, since these photoinitiators, photoinitiation adjuvant, and a sensitizer absorb a specific wavelength, in some cases, a sensitivity becomes low and may function as an ultraviolet absorber. However, they are not used for the sole purpose of improving the sensitivity of the composition. The light of a specific wavelength can be absorbed as needed, the photoreactivity of a surface can be improved, and the precision of the shape at the time of exposure and development can be improved.

[filler]

By mix | blending a filler with the photosensitive composition, while improving hardness, heat resistance, etc. of a coating film, the time-dependent change of the surface form of a photosensitive film can be adjusted. As such a filler, a known inorganic or organic filler can be used, but an inorganic filler is preferable. Examples of the inorganic fillers include barium sulfate, silica, mica, hydrotalcite, talc, metal oxides and metal hydroxides such as aluminum hydroxide. Among these, silica and mica are preferable. Examples of the silica include spherical silica and amorphous silica.

To the photosensitive composition, other resins other than those described above, thermal radical generators, polymerization inhibitors, adhesion aids, organic solvents, and the like may be added.

For example, heat resistance can be improved by mix | blending other resin. Examples of other resins include polyimide, polyoxazole and precursors thereof, novolac resins such as phenol novolac and cresol novolac, polyamideimide, polyamide, phenoxy resin, and polyether sulfone. These may be used individually by 1 type and may use 2 or more types together.

In addition, the polyimide resin may be alkali-soluble. Specifically, it has alkali-soluble groups, such as a carboxyl group and an acid anhydride group, in addition to an imide group. A well-known conventional method can be used for introduction of an alkali soluble group. For example, resin obtained by making at least 1 sort (s) of a carboxylic anhydride component, an amine component, and an isocyanate component react is mentioned. The imidation may be performed by thermal imidization, or by chemical imidation, and may be used in combination.

Moreover, by mix | blending a thermal radical generating agent, a photocurable compound can be hardened at low temperature for a short time. As a thermal radical generating agent, a peroxide, an azo compound, etc. are mentioned, for example.

Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, t-butyl catechol, phenothiazine, and the like. Moreover, as an adhesion | attachment adjuvant, silane coupling agents, such as (gamma)-glycidoxy silane, aminosilane, (gamma) -ureidosilane, etc. are mentioned, for example.

The photosensitive film can apply | coat the above-mentioned photosensitive composition to one surface of a support film, and can dry and form it. Considering the applicability of the photosensitive composition, the photosensitive composition is diluted with an organic solvent and adjusted to an appropriate viscosity, and a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure coater, spray coater It can apply | coat with a uniform thickness to one side of a support film with a bar coater, a roll coater, a comma coater, a slit die coater, a spin coater, etc., and can volatilize the organic solvent by drying, and can obtain the coating film of a touch drying. There is no restriction | limiting in particular about coating film thickness, Generally, it is suitably selected in the range of 0.5-500 micrometers in the film thickness after drying. It is preferable that it is the range of 1-300 micrometers from a viewpoint of using as a material which forms a wall part and a cover part of a hollow structure.

Although there is no restriction | limiting in particular as an organic solvent which can be used, For example, ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, ester, alcohol, aliphatic hydrocarbon, petroleum solvent, etc. are mentioned. More specifically, ketones, such as methyl ethyl ketone (MEK) and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; Cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether Glycol ethers such as these; Esters such as ethyl acetate, butyl acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol butyl ether acetate; Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; Aliphatic hydrocarbons such as octane and decane; Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, other N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone and the like. These organic solvents may be used individually by 1 type, and may be used as 2 or more types of mixtures.

The volatilization drying of the organic solvent is a hot air circulation drying furnace, an IR plate, a hot plate, a convection oven, or the like. Spraying method). As volatilization drying conditions, temperature is suitably selected in 60-120 degreeC, and time is 1 to 60 minutes.

[Protective film]

The photosensitive film laminate according to the present invention is for the purpose of preventing dust from adhering to the surface of the photosensitive film as described above, for improving the handleability, and for adjusting the arithmetic average surface roughness Ra of the surface of the photosensitive film, The protective film is provided in the surface on the opposite side to the support film of the photosensitive film.

As a protective film, although a polyester film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, the surface-treated paper etc. can be used, it is especially preferable that it is a polypropylene film. Moreover, it is preferable to select the material from which the adhesive force of a protective film and the photosensitive film becomes smaller than the adhesive force of the photosensitive film. In addition, when using a photosensitive film laminated body, in order to make it easy to peel a protective film, you may perform the above-mentioned mold release process to the surface which contact | connects the photosensitive film of a protective film.

Although the thickness in particular of a protective film is not restrict | limited, It selects suitably according to a use in the range of about 10-200 micrometers.

In this invention, it is preferable to use the protective film whose arithmetic mean surface roughness Ra 'of the surface of the protective film in contact with the photosensitive film is 0.10 micrometer or more. Moreover, it is more preferable to use the protective film whose arithmetic mean surface roughness Ry 'of the surface of the protective film on the surface side which contact | connects a photosensitive film is 1.00 micrometers or more. By using the protective film which has such a surface form, it becomes easy to form the photosensitive film which has arithmetic mean surface roughness Ra of 0.10 micrometer or more, and also becomes easy to form the photosensitive film which has arithmetic mean surface roughness Ry of 1.00 micrometer or more. It is more preferable that it is 0.15 micrometer or more, and, as for the arithmetic mean surface roughness Ra 'of a protective film, it is still more preferable that it is 0.20 micrometer or more. Moreover, when setting an upper limit, it is preferable that it is 1.00 micrometers or less, It is more preferable that it is 0.80 micrometer or less, It is more preferable that it is 0.60 micrometer or less.

Moreover, it is more preferable that it is 1.20 micrometers or more, and, as for the maximum height Ry 'of the protective film of the surface side which contact | connects a photosensitive film, it is still more preferable that it is 1.40 micrometers or more. Moreover, when setting an upper limit, it is preferable that it is 5.00 micrometers or less, It is more preferable that it is 4.00 micrometers or less, It is further more preferable that it is 3.00 micrometers or less. Here, the arithmetic mean surface roughness Ra 'and the maximum height Ry' mean each, but the specific measuring method is explained in the above-mentioned [photosensitive film]. In addition, the arithmetic mean surface roughness Ra 'of a protective film, the arithmetic mean surface roughness Ra of a photosensitive film, the maximum height Ry' of a protective film, and the maximum height Ry of a photosensitive film do not necessarily correspond, respectively, but are adjusted suitably, Arithmetic mean surface roughness Ra and maximum height Ry can be made into the specific range as mentioned above.

The method for adjusting the protective film having the arithmetic mean surface roughness Ra 'and the maximum height Ry' as described above is not particularly limited. For example, when the filler is added to the resin of the protective film, the particle size and the amount of the filler are adjusted. Although adjustment is mentioned, the surface can be made into a predetermined form by blasting the protective film surface, or by hairline processing, mat coating, or chemical etching.

[Hardened]

Hardened | cured material is formed using the photosensitive film laminated body of this invention. As an example of such a hardened | cured material, the method of forming the hollow structure provided with the wall part and the cover part using the photosensitive film laminated body of this invention is demonstrated.

[Formation of wall part]

First, a wall part is formed using the photosensitive film laminated body. Specifically, the lamination process of peeling a protective film from a photosensitive film laminated body, and laminating | stacking a photosensitive film on to-be-adhered bodies, such as a board | substrate, and the exposure process which irradiates a predetermined part of the photosensitive film through a mask and photocures an exposure part, The desired wall part is formed through the image development process of removing the photocured part of the photosensitive film using a developing solution, and the main hardening process which hardens the photocured location of the photosensitive film with light or heat, and forms hardened | cured material. can do. Hereinafter, each process is demonstrated.

In a lamination process, a protective film is peeled from the photosensitive film laminated body and the exposed photosensitive film surface side is laminated | stacked on a board | substrate. Lamination can be performed by adhesion or the like by thermocompression bonding. As a board | substrate which is a to-be-adhered body, a silicon wafer, a glass substrate, a ceramic substrate, an aluminum base substrate, a stainless steel substrate, a glass epoxy substrate, a polyester substrate, a polyimide substrate, etc. are mentioned, for example. As a method of thermocompression bonding, a hot press process, a roll lamination process, a vacuum roll lamination, a vacuum press process, a diaphragm type vacuum lamination, etc. are mentioned. The thermal crimping temperature is preferably 20 to 150 ° C, preferably 35 to 100 ° C, from the viewpoint of adhesion to the substrate, embedding properties, and curing of the photosensitive composition at the time of thermal compression, and maintaining good resolution. It is more preferable, and it is still more preferable that it is 40-85 degreeC. Moreover, it is preferable that lamination pressure is 0.005-10 Mpa, More preferably, it is 0.005-3 Mpa.

Next, an exposure process is performed. As exposure, there are a negative type and a positive type, but a negative type is preferable. In the case of the negative type, the photosensitive film laminated body laminated | stacked on the board | substrate is irradiated with light through the negative mask which has a desired pattern used as the shape of a wall part, and the photosensitive part of the photosensitive film is photocured. Here, as an active light ray used for exposure, an ultraviolet-ray, a visible ray, an electron beam, X-rays, etc. are mentioned. Especially among these, an ultraviolet-ray and a visible ray are preferable. Moreover, the mask exposure which uses i line | wire (365 nm), h line | wire (405 nm), and g line | wire (436 nm) of an ultrahigh pressure mercury lamp is preferable through a photomask. Moreover, the method of masklessly drawing on a photosensitive film using the laser of wavelength 405nm is also mentioned. In this process, the support film which comprises the photosensitive film laminated body may peel before exposure, and may peel after exposure. In addition, you may heat-process for 5 second-60 minutes at the temperature of 40 degreeC-150 degreeC using an oven or a hotplate, without peeling or peeling a support film before exposure. In addition, you may heat-process for 5 second-60 minutes at 40-150 degreeC temperature using oven or a hotplate, without peeling or peeling a support film after exposure.

Next, the pattern of a wall part is formed by removing the part (non-exposed part) other than photocured of the photosensitive film using the developing solution of the organic solvent type or alkaline aqueous solution type.

As the developer, N-methylpyrrolidone, ethanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate, γ-butyrolactone, triethylene glycol dimethyl ether, methyl amyl ketone (2-heptanone), butyl acetate Organic solvents, such as these, can be used. Moreover, aqueous alkali solution, such as sodium carbonate, sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH), can be used. Among these, in the case of solvent development, it is preferable to use propylene glycol methyl ether acetate. On the other hand, in the case of alkali development, it is preferable that they are sodium carbonate, sodium hydroxide, and tetramethylammonium hydroxide (TMAH).

As a developing method, the developing solution is sprayed on the photosensitive film, immersed in the developing solution, or an ultrasonic wave is applied while immersing.

Moreover, after image development, it is preferable to rinse with water, alcohol, such as methanol, ethanol, isopropyl alcohol, n-butyl acetate, a propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether acetate, etc. as needed. As a rinse method, the developing solution is sprayed on the photosensitive film surface, immersed in the developing solution, or an ultrasonic wave is applied while immersing.

Next, the photocured part (exposure part) of the photosensitive film is hardened | cured by light or heat, and a wall part is formed. When hardening (cure) after image development hardens by heat, it is preferable to carry out for 1 to 2 hours, selecting a temperature and heating up stepwise. The temperature of thermosetting is suitably selected in 120-400 degreeC, and time is 60-120 minutes. The temperature may be fixed at a constant temperature or may be elevated in stages. At the time of hardening, it is preferable to heat-process in inert gas, such as nitrogen and argon. It is preferable that final heating temperature is 150-350 degreeC. Moreover, you may perform photocuring before and after thermosetting or instead of thermosetting.

1-3,000 micrometers is preferable, as for the film thickness of the photosensitive film for forming a wall part, 5-1,000 micrometers is more preferable, 10-500 micrometers is still more preferable, 20-200 micrometers is especially preferable, 20-100 micrometers Most preferred. When the thickness of the photosensitive film is 1 µm or more, it is easy to maintain the shape of the wall portion, and large deformation hardly occurs even under high temperature and high pressure conditions at the time of molding. Moreover, as long as thickness is 3000 micrometers or less, the light transmittance of the photosensitive film at the time of exposure is hard to be inhibited. Moreover, you may increase the thickness of a wall part by repeating the lamination process which superimposes a photosensitive film. Moreover, 1-3000 micrometers is preferable, as for the final film thickness of the wall part formed through a hardening process, 5-500 micrometers is more preferable, 10-200 micrometers is still more preferable.

[Formation of cover part]

The wall part containing the hardened | cured material of the photosensitive film formed by the formation method mentioned above has a sufficient film thickness, and a hollow structure is made by covering a ceramic substrate, a Si substrate, a glass substrate, a metal substrate, etc. as a cover on the upper end of a wall part. Although may be formed, the lid portion may be formed using the photosensitive film laminate. Hereinafter, the method of forming a lid part using the photosensitive film laminated body is demonstrated.

On the upper end of the wall portion formed as described above, a photosensitive film laminate obtained by peeling off a protective film is laminated, developed as necessary for exposure and necessity, and a lid is formed by curing the photocured photosensitive film to form a hollow structure. Can be. When forming a cover part using the photosensitive film laminated body, it does not necessarily need to go through the image development process, but when manufacturing several hollow structural devices simultaneously, for example, the size equivalent to the cover part of a hollow device is carried out. After exposing through a mask, it can divide into individual pieces by developing the unexposed part of the periphery.

Lamination | stacking, exposure, image development, and hardening of the photosensitive film laminated body can be performed similarly to formation of the wall part mentioned above. Here, adhesion | attachment at the time of lamination | stacking of the laminated body which forms a wall part and a cover part can be performed by thermocompression bonding. As a thermocompression method, a hot press process, a roll lamination process, a vacuum roll lamination, a vacuum press process, a diaphragm type vacuum lamination, etc. are mentioned, for example, Roll lamination process is especially preferable. As for thermocompression bonding temperature, 20 degreeC or more is preferable from a viewpoint of adhesiveness to a to-be-adhered body, and embedding. Moreover, at the time of thermocompression bonding, from the viewpoint of hardening of the photosensitive resin component advancing and preventing the deterioration of the resolution of pattern formation in exposure and image development, 150 degreeC or less is preferable. That is, the thermal compression temperature is preferably from 20 to 150 ° C, from 35 to 100 ° C, from the viewpoint of adhesion to the substrate, embedding point, and curing of the photosensitive composition at the time of thermal compression, and maintaining good resolution. It is more preferable that it is and it is further more preferable that it is 40-85 degreeC. Moreover, it is preferable that lamination pressure is 0.005-10 Mpa, More preferably, it is 0.005-3 Mpa.

Although the support film which comprises the photosensitive film laminated body may peel before exposure, may peel after exposure, and may peel after hardening of the photosensitive film, in the point which becomes a state which supports the hardened | cured material of the photosensitive film used as a cover part only by a wall part. From the standpoint of stability, peeling after exposure and peeling after curing are preferable. In addition, you may heat-process for 5 second-60 minutes at the temperature of 40-150 degreeC using an oven or a hotplate, without peeling or peeling a support film before exposure. In addition, you may heat-process in 5 second-60 minutes at 40-150 degreeC temperature using oven or a hotplate, without exfoliating or peeling a support film after exposure. In addition, about image development and hardening, you may perform a wall part and a cover part collectively. It is preferable that the tensile elasticity modulus of the cured film which forms a lid part is 2.0 GPa or more.

1-3,000 micrometers is preferable, as for the film thickness of the photosensitive film for forming a cover part, 5-1,000 micrometers is more preferable, 10-500 micrometers is still more preferable, 20-200 micrometers is especially preferable, 20-100 micrometers Most preferred. As for the final film thickness of the cover part formed through a hardening process, 10 micrometers-3,000 micrometers are preferable. If the thickness of the lid portion is 10 µm or more, it is easy to maintain the shape of the hollow structure, and large deformation hardly occurs even under high temperature and high pressure conditions at the time of molding. Moreover, as long as it is thickness 3,000 micrometers or less, the light transmittance of the photosensitive film at the time of exposure is hard to be inhibited. Moreover, you may increase the thickness of a lid part by repeating the lamination process which overlaps a photosensitive film.

In the present invention, the wall portion may be formed without using the photosensitive film laminate of the present invention, and only the lid portion may be formed using the photosensitive film laminate of the present invention. When the photosensitive film laminated body of this invention is used, while adhesiveness between them is more excellent, peeling, such as plating in the vicinity of a hollow structure, can be suppressed.

According to the present invention, in an electronic component having a hollow structure such as a SAW filter, by forming the wall portion and the lid portion using the photosensitive film laminate of the present invention, peeling such as plating in the proximal portion of the hollow structure can be suppressed. Can be. In addition, since the inside of the hollow structure is damp-proof by the wall part and the cover part, and the hollow structure is maintained even at a high temperature, the hollow structure is applicable to electronic parts requiring hollow structures such as SAW filters, CMOS, CCD sensors, MEMS, and the like. It is useful for miniaturization, low magnification and high functionality of parts. Especially the photosensitive film laminated body of this invention is suitable for formation of the wall part or cover part of the hollow structure of SAW filter, and the highly reliable electronic component which suppressed peeling, such as plating in the proximal part of a hollow structure, is obtained. Particularly suitable in Moreover, you may use this invention also as a printed wiring board use, such as a soldering resist, plating resist, an etching resist, an interlayer insulation material.

<SAW filter and its manufacturing method>

Although the method of forming the hollow structure which has a wall part and a cover part was demonstrated using the photosensitive film laminated body of this invention, As an example of the electronic component which has a hollow structure, about a surface acoustic wave (SAW) filter and its manufacturing method, It demonstrates below.

First, the protective film is peeled from the photosensitive film laminated body of this invention on the board | substrate with which the comb-shaped electrode was formed, and the photosensitive film surface is laminated | stacked. The lamination | stacking of the photosensitive film laminated body can use the method similar to the method described by the formation method of the wall part mentioned above.

Subsequently, after laminating | stacking the photosensitive film laminated body, the predetermined part of the photosensitive film is irradiated light through the negative mask which has a desired pattern as needed, and an exposure part is photocured. Exposure can use the same method as the method described by the formation method of the wall part mentioned above.

Subsequently, after forming a desired pattern by removing a part other than the exposure part of the photosensitive film, ie, an unexposed part using a developing solution, the exposure part of the photosensitive film is hardened by light or heat, and the wall part containing hardened | cured material is formed. do. In addition, the process similar to the formation method of the wall part mentioned above can be used for each process of exposure, image development, and hardening.

In addition, as mentioned later, when using the photosensitive film laminated body of this invention for formation of the cover part of the hollow structure of SAW filter, the wall part may be formed by methods other than the method of using the photosensitive film laminated body of this invention. do.

The cover part is provided in the upper end of the wall part formed as mentioned above, and a hollow structure is formed. Here, a cover part can peel a protective film from the photosensitive film laminated body of this invention, adhere | attach the photosensitive film surface to the upper end of a wall part, and can expose, develop, and harden | cure, and can form a cover part. Bonding of a lid part and a wall part can be performed by adhesion | attachment by thermocompression bonding using a roll laminator, etc., for example.

Moreover, the cover part may be comprised from materials other than the photosensitive film laminated body of this invention, for example, sealing substrates, such as a well-known permanent resist and a ceramic. However, it is preferable that a cover part is comprised with the material excellent in moisture heat resistance and low water absorption. In this case, at least, the wall part formed using the photosensitive film laminated body of this invention is used as a hollow structure formation wall part of SAW filter.

After the wall portion and the lid portion are formed as described above, in order to perform electrical connection between the electrode and the conductors wired on the surface of the substrate and on the opposite side of the electrode, the formation of plating and the mounting of metal balls may be performed. .

In the formation of the wall portion, a hole for forming the inner conductor may be formed in the wall portion by exposure and development. Then, the photosensitive film laminated | stacked on the support film is laminated | stacked on the said wall part, and exposure is performed through a mask. Since only the part corresponding to the hole diameter for forming an inner conductor is shielded so that light may not permeate | transmit a mask, the other part forms the photocured cover part. In order to completely penetrate the unexposed part of a lid part through the hole inside the wall part formed previously, after image development, it performs patterning by performing a desmear process etc. In addition, you may use a laser for patterning of a cover part. As a laser, a well-known thing, such as a YAG laser, a carbon dioxide laser, an excimer laser, can be used. Exposure or laser irradiation can be suitably selected and used according to the thickness of a wall part, the shape of the internal conductor formed in the inside of a wall part, and the shape of a cover part surface wiring pattern.

In addition, an internal conductor is formed in a hole formed in the wall portion and the lid portion by a plating method or the like, and wiring is formed on the surface of the lid portion. In the present invention, not only the plating method but also the metal paste or the resin paste containing the metal powder can be formed in the hole formed in the wall and the lid, and the inner conductor can be formed by the conductor filling method. Through these steps, the conductors connected to the comb-shaped electrodes on the substrate are electrically connected to the wiring conductors formed on the surface of the lid portion. Finally, a metal ball is mounted on the surface of the lid by reflow or the like to obtain a SAW filter, which is an electronic component having a hollow structure.

In addition, the SAW filter may be sealed by a sealing material. When sealing with a sealing material, although generally performed by the following process, it is not limited to this. First, the SAW filter is set in the molding die. Next, a solid encapsulant tablet is set in the pot of the molding machine. Further, the encapsulant is melted under conditions of a mold temperature of 150 to 180 ° C, and pressure is introduced into the mold (molding). Finally, after pressurizing for 30 to 120 seconds, the mold is opened after the sealing material is thermoset, and the sealing of the SAW filter is completed by taking out the molded product.

Usually, sealing with a sealing material is performed before metal ball is mounted, and after sealing, a metal ball is mounted by reflow from the sealed surface of the board | substrate to the opposite surface. However, after the metal ball is mounted, sealing with the sealing material may be performed. Not only one SAW filter sealed with the sealing material but also several can also be manufactured. In this case, it can obtain by cutting into several pieces after sealing several SAW filter formed on one board | substrate with sealing material. Specifically, first, a plurality of SAW filters are produced on one substrate to form a wall portion and a lid portion using the photosensitive film laminate of the present invention. Thereafter, the sealing material is encapsulated in a batch and divided into pieces by a method such as cutting to obtain a SAW filter.

As mentioned above, in the manufacturing process of SAW filter, the hollow structure which has a wall part and a cover part can be formed using the photosensitive film laminated body of this invention. As mentioned above, since the change of the surface form with time is in the specific range, the photosensitive film laminated body of this invention can implement SAW filter by which peeling, such as plating of the proximal part of a hollow structure, was suppressed. Moreover, since the inside of a hollow structure can be isolated and moisture-proof by the wall part and lid part formed using the photosensitive film laminated body of this invention, and moisture-proof, corrosion of an aluminum electrode can be suppressed. Moreover, since the hardened | cured material of the photosensitive film has high elasticity modulus at high temperature, there exists an advantage that a hollow structure can be maintained also in the temperature and the pressure at the time of sealing resin mold.

Example

Next, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples. In addition, below "part" and "%" are mass references | standards unless there is particular notice except% concerning relative humidity. In addition, the operation in the following example was performed under room temperature (23 degreeC), relative humidity 42%, and a yellow lamp.

Synthesis Example 1

<Synthesis of carboxyl group-containing resin>

In a 2L flask equipped with a stirring device and a reflux tube, a bifunctional bisphenol-A type epoxy resin (RE-310S manufactured by Nippon Kayaku Co., Epoxy equivalent: 183.5 g / equivalent) was used as an epoxy compound having two or more epoxy groups in a molecule. 367.0 parts, 144.1 parts of acrylic acid (molecular weight: 72.06) as a monocarboxylic acid compound having an ethylenically unsaturated group, 1.02 parts of hydroquinone monomethyl ether as a thermal polymerization inhibitor, and 1.53 parts of triphenylphosphine as a reaction catalyst Then, it was made to react until the acid value of the reaction liquid became 0.5 mgKOH / g or less at the temperature of 98 degreeC, and the epoxy carboxylate compound (theoretical molecular weight: 511.1) was obtained.

Subsequently, 445.93 parts of carbitol acetate as a solvent for reaction, 0.70 parts of 2-methylhydroquinone as a thermal polymerization inhibitor, and 118.8 parts of dimethylol propionic acid (molecular weight: 134.1) are added as a diol compound which has a carboxyl group to this reaction liquid. And it heated up at 60 degreeC. 209.6 parts of isophorone diisocyanate (molecular weight: 222.29) as a diisocyanate compound were slowly dripped at this solution so that reaction temperature might not exceed 65 degreeC. After completion of the dropwise addition, the temperature was raised to 80 ° C and allowed to react for 6 hours until absorption of 2250 cm ^-1 was lost by infrared absorption spectrometry. 36.7 parts of succinic anhydride (molecular weight: 100.1) and 43.0 parts of carbitol acetate were added to this solution as polybasic acid anhydride. After addition, the temperature was raised to 95 degreeC, it was made to react for 6 hours, and carboxyl group-containing photosensitive resin varnish 1 was obtained for 65 weight% of carboxyl group-containing polyesterurethane resins whose weight average molecular weight is 10,000. The acid value was measured, and found to be 66.61 mgKOH / g (solid acid value: 102.5 mgKOH / g). In addition, the weight average molecular weight was measured according to the conventional method by the gel permeation chromatography (GPC) method (polystyrene standard).

Synthesis Example 2

<Synthesis of carboxyl group-containing resin>

In an autoclave equipped with a thermometer, a nitrogen introducing device, an alkylene oxide introducing device, and a stirring device, 119.4 g of a novolak-type cresol resin (Shonol CRG951, OH equivalent: 119.4 manufactured by Aika Kogyo Co., Ltd.), 1.19 g of potassium hydroxide, and toluene 119.4g was thrown in, the inside of a system was nitrogen-substituted and stirred, and it heated up. Subsequently, 63.8 g of propylene oxide was slowly added dropwise and reacted at 125 to 132 ° C and 0 to 4.8 kg / cm ² for 16 hours. Thereafter, the mixture was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide, and a propylene oxide reaction of a novolak-type cresol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g / eq. A solution was obtained. In the obtained novolak-type cresol resin, an average of 1.08 mol of alkylene oxide was added per equivalent of phenolic hydroxyl group.

293.0 g of the alkylene oxide reaction solution of the obtained novolak-type cresol resin, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone and 252.9 g of toluene were introduced into a reactor equipped with a stirrer, a thermometer, and an air suction tube. Then, air was blown at a rate of 10 ml / min and reacted at 110 ° C for 12 hours while stirring. The water produced by the reaction was an azeotropic mixture with toluene, and 12.6 g of water flowed out. Thereafter, the mixture was cooled to room temperature, and the obtained reaction solution was neutralized with 35.35 g of an aqueous 15% sodium hydroxide solution, followed by washing with water. Thereafter, toluene was distilled off while replacing toluene with 118.1 g of diethylene glycol monoethyl ether acetate in an evaporator to obtain a novolak-type acrylate resin solution. Subsequently, 332.5 g of the obtained novolak-type acrylate resin solution and 1.22 g of triphenylphosphine were introduced into a reactor equipped with a stirrer, a thermometer, and an air intake tube, and the air was blown at a rate of 10 ml / min, followed by stirring with tetrahydro. 62.3 g of phthalic anhydride was added gradually, and it was made to react at 95-101 degreeC for 6 hours, and the carboxyl group-containing photosensitive resin varnish 2 was obtained as 71% of non volatile matters of the acid value 88 mgKOH / g.

Synthesis Example 3

<Synthesis of carboxyl group-containing resin>

220 parts (1 equivalent) of cresol novolak-type epoxy resin (manufactured by Nippon Kayaku Co., EOCN-104S, epoxy equivalent 220 g / eq), 140.1 parts of carbitol acetate and 60.3 parts of solvent naphtha, were heated and stirred at 90 ° C. And dissolved.

The obtained solution was once cooled to 60 ° C, 72 parts (1 mol) of acrylic acid, 0.5 part of methylhydroquinone and 2 parts of triphenylphosphine were added, heated to 100 ° C, and reacted for about 12 hours. The acid value was 0.2 mgKOH / g reactant was obtained. 80.6 parts (0.53 mol) of tetrahydro phthalic anhydride were added to this, it heated at 90 degreeC, it was made to react for about 6 hours, and the acid value 85 mgKOH / g of solid content and the carboxyl group-containing photosensitive resin varnish 3 of 64.9% of solid content were obtained.

Synthesis Example 4

<Synthesis of carboxyl group-containing resin>

190 parts of EPPN-201 (made by Nippon Kayaku Co., Ltd., epoxy equivalent = 190) of a phenol novolak-type epoxy resin were put into the four neck flask equipped with the stirrer and the reflux condenser, 184 parts of carbitol acetate were added, and it melt | dissolved by heating. . Next, 0.46 parts of methylhydroquinone as a polymerization inhibitor and 1.38 parts of triphenylphosphine were added as a reaction catalyst. This mixture was heated to 95-105 degreeC, 72 parts (1 equivalent) of acrylic acid was dripped gradually, and it was made to react for 16 hours. The obtained reaction product (hydroxyl group: 1 equivalent) was cooled to 80-90 degreeC, 50 parts (0.5 equivalent) of succinic anhydride was added, it was made to react for 8 hours, and it extracted after cooling. Thus, the carboxyl group-containing photosensitive resin varnish 4 of 65% of non volatile matter, the acid value of 89 mgKOH / g of solid, and 65.0% of solid content was obtained.

<Production of Photosensitive Composition>

It mix | blended in the content and ratio (mass part) shown in following Table 1, and knead | mixed so that each component might become uniform, and manufactured the photosensitive compositions 1-5. In addition, * 1-* 22 in Table 1 represent the following components.

* 1 Methylated melamine resin, manufactured by Sanwa Chemical Co., Ltd.

* 2 Fluorene frame | skeleton containing epoxy resin, the product made by Osaka Gas Chemical Co., Ltd.

* 3 bisphenol A epoxy resin (made by DIC Corporation)

* 4 biphenyl aralkyl type epoxy resin (made by Nippon Kayaku Co., Ltd.)

* 5 phenol novolak type epoxy resin (made by DIC Corporation)

* 6 dicyclopentadiene type epoxy resin (made by DIC Corporation)

* 7 Synthesis Example 1 (mixture amount is solid amount)

* 8 Synthesis Example 2 (mixture amount is solid amount)

* 9 Synthesis Example 3 (mixture amount is solid amount)

* 10 Synthesis Example 4 (Formulation amount is solid amount)

* 11 Alkali-soluble photosensitive resin which has an amideimide structure (20% of solid content, Nippon Kogyo Kogyo KK make)

* 12 Dipentaerythritol acrylate, manufactured by Kyoeisha Chemical Co., Ltd.

* 13 ε-caprolactone modified dipentaerythritol acrylate, manufactured by Kyoeisha Chemical Co., Ltd.

* 14 tricyclodecane dimethanol diacrylate, made by Shin-Nakamura Kagaku Kogyo Co., Ltd.

* 15 Oxime ester system photoinitiator (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime)), BASF Japan Kabushi Kaisha

* 16 diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (manufactured by IMG Resins)

* 17 2-ethyl-4-methylimidazole (made by Shikoku Kasei Kogyo Co., Ltd.)

* 18 spherical silica, made by Admatex

* 19 Spherical silica particle with average particle diameter of 100 nm

* 20 C. I. Pigment Blue 15: 3

* 21 C. I. Pigment Yellow 147

* 22 Paliogen Red K3580 (product of BASF Japan Corporation)

<Production of protective film>

Production Example 1

Polypropylene resin pellets having a weight average molecular weight (Mw) of 3.0 × 10 ⁵ , a molecular weight distribution (Mw / Mn) of 5.0, and an isotactic component fraction of 95.0% were fed to an extruder, melted at a temperature of 250 ° C., and subjected to T die. The film was wound around a metal drum kept at a surface temperature of 150 ° C. to form a cast fabric sheet having a thickness of about 225 μm. Subsequently, the unstretched cast fabric sheet was stretched five times in the flow direction at a temperature of 120 ° C., immediately cooled to room temperature, and then stretched 10 times in the transverse direction at a temperature of 160 ° C. with a tenter, and was 12 µm thick. The biaxially stretched polypropylene film 1 was obtained. This biaxially stretched polypropylene film 1 is called protective film 1.

Production Example 2

Polypropylene resin pellets having a weight average molecular weight (Mw) of 3.1 × 10 ⁵ , a molecular weight distribution (Mw / Mn) of 5.5, and an isotactic component fraction of 93.0% were fed to an extruder, and melted at a temperature of a resin temperature of 250 ° C., T It extruded with the die, it wound around the metal drum which kept the surface temperature at 150 degreeC, and formed into a film, and produced the cast fabric sheet of about 225 micrometers in thickness. Subsequently, the unstretched cast fabric sheet was stretched five times in the flow direction at a temperature of 200 ° C., immediately cooled to room temperature, and then stretched ten times in the transverse direction at a temperature of 160 ° C. with a tenter to obtain a thickness of 15 μm. The biaxially stretched polypropylene film 2 was obtained. This biaxially stretched polypropylene film 2 is called protective film 2.

Production Example 3

Polypropylene resin pellets having a weight average molecular weight (Mw) of 3.0 × 10 ⁵ , a molecular weight distribution (Mw / Mn) of 5.0, and an isotactic component fraction of 95.0% were fed to an extruder, melted at a temperature of 250 ° C., and subjected to T die. The film was rolled around a metal drum held at a surface temperature of 100 ° C. to form a cast fabric sheet having a thickness of about 225 μm. Subsequently, the unstretched cast fabric sheet was stretched five times in the flow direction at a temperature of 120 ° C., and immediately cooled to room temperature, and then stretched ten times in the transverse direction at a temperature of 160 ° C. with a tenter to give a biaxial thickness of 12 μm. Stretched polypropylene film 3 was obtained. This biaxially stretched polypropylene film 3 is called protective film 3.

<Production of support film>

After drying the polyethylene terephthalate and the polyethylene terephthalate masterbatch containing 1.0 mass% of silica with an average primary particle diameter of 1 micrometer, respectively, at 170 degreeC, they were respectively supplied to the twin screw extruder, and it melt | dissolved at 290 degreeC, and T It coextruded from the die and formed into a film, and produced the unstretched film. Subsequently, this unoriented film was biaxially stretched to obtain a support film 1 having a thickness of 40 μm.

<Production of Photosensitive Film Laminate>

Example 1

As a result of measuring the arithmetic mean surface roughness Ra 'and the maximum height Ry' of the protective film 1 obtained as described above as follows, Ra 'was 0.18 µm and the maximum height Ry' was 1.28 µm.

For the measurement of arithmetic mean surface roughness Ra 'and Ry', the shape | measurement laser microscope (VK-X100 by Kyens Co., Ltd.) was used. After activating the shape measurement laser microscope (VK-X100) main body (control unit) and VK observation application (VK-H1VX manufactured by Keyence Co., Ltd.), the protective film (side of contact with the photosensitive film) to be measured on the xy stage. Top)) were loaded. The lens revolver of the microscope unit (VK-X110 manufactured by Keyence Co., Ltd.) was turned to select an objective lens with a magnification of 10 times, and the approximate focus and brightness were adjusted in the image observation mode of the VK observation application (VK-H1VX). By operating the x-y stage, the portion to be measured on the sample surface was adjusted to be in the center of the screen. The objective lens 10 times magnification was changed to 50 times magnification, and the focus was made to the surface of a sample by the autofocus function of the image observation mode of a VK observation application (the same VK-H1VX). The simple mode of the shape measurement tab of a VK observation application (VK-H1VX) was selected, the measurement start button was pressed, the surface shape of a sample was measured, and the surface image file was obtained. After starting the VK analysis application (VK-H1XA manufactured by Keyence Co., Ltd.) to display the obtained surface image file, the tilt correction was performed.

Example 5

In addition, the observation measurement range (width) in the measurement of the surface shape of a sample was 270 micrometers. Display the line roughness window, select JIS B0601-1994 in the parameter setting area, select a horizontal line from the measurement line button, display a horizontal line at any place in the surface image, and press the OK button to select the arithmetic mean surface roughness. Figures for Ra 'and maximum height Ry' were obtained. Further, horizontal lines were displayed at four different places in the surface image to obtain numerical values of the arithmetic mean surface roughness Ra 'and the maximum height Ry'. The average value of five obtained numerical values was computed respectively, and it was set as the arithmetic mean surface roughness Ra 'value and the maximum height Ry' value of a sample surface. In addition, the measurement was performed in the environment of room temperature (23 degreeC), and relative humidity 42% RH.

Subsequently, with respect to 700 parts photosensitive composition 1 obtained as mentioned above, methyl ethyl ketone was added and diluted in the ratio of 300 parts, and it stirred for 15 minutes with the stirrer, and obtained the coating liquid. This coating liquid was apply | coated uniformly on the support film 1 using the slit die coater, it dried at the temperature of 80 degreeC for 15 minutes, and the photosensitive film 1 of thickness 25micrometer after drying was produced. Subsequently, on the photosensitive film 1, the protective film 1 was bonded by a roll laminator so that the measuring surface of arithmetic mean surface roughness Ra 'and the maximum height Ry' of the said protective film 1 contact | connects the said photosensitive film 1 surface, and a support film / The photosensitive film laminated body 1 (25 micrometers in thickness of the photosensitive film) which consists of three layers of the photosensitive film / protective film was produced. In addition, as lamination conditions by the said roll laminator, it adjusted suitably in the range of the roll temperature of 40-60 degreeC, and the roll pressure of 0.2-0.4 MPa.

<Production of Test Board>

The test board | substrate was produced using the photosensitive film laminated body 1 obtained by making it above. The manufacturing procedure of a test board | substrate is demonstrated, referring drawings.

First, the protective film is peeled from the photosensitive film laminate 1 at an angle of 90 ° with respect to the other two layers (support film / photosensitive film) at a rate of 2.5 seconds / cm to expose the photosensitive film, and the surface of the prepared silicon wafer The exposed surface of the photosensitive film was bonded together, the heating lamination was performed using the roll laminator, and the silicon wafer and the photosensitive film were closely contacted. In addition, as lamination conditions by the said roll laminator, it was roll temperature 60 degreeC and roll pressure 0.25MPa.

Next, from the support film contacting the photosensitive film,

(i) a negative mask having a lattice size of 150 mu m side and an opening pattern of 50 mu m side (see FIG. 1), or

(ii) Negative mask having an opening pattern of lattice size 150 mu m side and 100 mu m side (not shown)

After exposing the photosensitive film by the combination of the pattern opening and the exposure amount which are shown in Table 2 about each Example and each comparative example through the metal halide lamp, the support film was peeled off and the photosensitive film was exposed.

Thereafter, the exposed surfaces of the exposed photosensitive film were immersed in propylene glycol monomethyl ether acetate (PMA) for 1 minute at 23 ° C. in Examples 1 to 3 and Comparative Examples 1 and 2, and in Example 4 % Na ₂ CO ₃ aqueous solution of 1wt was subjected to 30 ℃, 2MPa, 60 seconds developing example 5 to about 1wt% Na ₂ CO ₃ aqueous solution, 30 ℃, 2MPa, to 300 seconds for each developer. Each test board | substrate after image development fully wash | cleaned with water so that a developing solution might not remain. Furthermore, the 1wt% Na ₂ bar, 11.6 Check the pH of the CO ₃ aqueous solution.

Subsequently, each test board | substrate is heated at 120 degreeC for 30 minutes, hardening a photosensitive film, and around the periphery opened by 150 micrometer side in a lattice form

(i) Cured film pattern (refer FIG. 2) corresponded to the wall part of 150 micrometers width which has a pattern opening of 50 micrometer side in the center, or

(ii) Curing pattern (not shown) which corresponds to a wall portion of 300 mu m width having a pattern opening of 100 mu m side in the center;

Got.

Moreover, the protective film was peeled off from the photosensitive film laminated body 1, the photosensitive film was exposed, the exposure surface of the photosensitive film was bonded together on the cured film pattern corresponded to the wall part obtained above, and the heating lamination was performed. In addition, lamination was performed by heating for 5 minutes at 80 degreeC, weighting on the photosensitive film with the weight of 1.0 kg.

Next, from the support film side of the photosensitive film laminated body bonded on the cured film pattern corresponded to a wall part,

(i) a negative mask having an aperture pattern of 50 µm side lattice size (see FIG. 3), or

(ii) Negative mask having opening pattern of lattice size 100 mu m side (not shown)

After exposing the photosensitive film by the combination of the pattern opening and the exposure amount which are shown in Table 2 about each Example and each comparative example through the metal halide lamp, the support film was peeled off and the photosensitive film was exposed. Furthermore, through the bonded photosensitive film laminated body,

(i) the pattern opening at the 50 μm side of the wall portion and the pattern opening at the 50 μm side of the grid size of the negative mask overlap (see FIG. 3), or

(ii) the pattern openings on the 100 μm side of the wall portion and the pattern openings on the 100 μm side of the grid size of the negative mask overlap (not shown),

The exposure was performed. Thereafter, the exposed surfaces of the exposed photosensitive film were immersed in propylene glycol monomethyl ether acetate (PMA) for 1 minute at 23 ° C. in Examples 1 to 3 and Comparative Examples 1 and 2, and in Example 4 % Na ₂ CO ₃ aqueous solution of 1wt was subjected to 30 ℃, 2MPa, 60 seconds developing example 5 to about 1wt% Na ₂ CO ₃ aqueous solution, 30 ℃, 2MPa, to 300 seconds for each developer. Each test board | substrate after image development fully wash | cleaned with water so that a developing solution might not remain.

Subsequently, each test board | substrate was heated at 200 degreeC for 60 minutes, hardening a photosensitive film, and forming the cured film pattern corresponded to a cover part, and the test board which has a hollow structure containing a wall part and a cover part was produced. Although the obtained test board | substrate does not have a comb-shaped electrode inside, the upper end of a wall part is covered with a cover part, and the junction part of the said cover part and a wall part,

(i) the pattern opening of the 50 micrometer side (refer FIG. 4), or

(ii) pattern opening of 100 micrometer side (not shown)

Had a hollow structure formed.

Example 2

In Example 1, the test board | substrate was produced like Example 1 except having used the photosensitive composition 2 instead of the photosensitive composition 1, and the protective film 2 instead of the protective film 1. In addition, as a result of measuring the arithmetic mean surface roughness Ra 'and the maximum height Ry' of the protective film 2 in the same manner as described above, Ra 'was 0.46 µm and the maximum height Ry' was 1.37 µm. In addition, the protective film 2 was roll shape and the winding inner side was measured.

Example 3

In Example 1, the test board | substrate was produced like Example 1 except having used the protective film 2 instead of the protective film 1.

Example 4

In the second embodiment, propylene glycol monomethyl ether acetate (PMA) 1wt% instead caused by Na ₂ CO ₃ aqueous solution, 30 ℃, except that subjected to 2MPa, 60 seconds Developing, in the same manner as Example 2, Test substrate Was produced.

Example 5

In Example 4, the test substrate was prepared in the same manner as in Example 4, except that the photosensitive composition 3 was used instead of the photosensitive composition 2, and a 1 wt% Na ₂ CO ₃ aqueous solution, 30 ° C., 2 MPa, and 300 seconds development was performed. Produced.

Comparative Example 1

In Example 2, the test board | substrate was produced like Example 2 except having used the photosensitive composition 4 instead of the photosensitive composition 2.

Comparative Example 2

In Example 1, the test board | substrate was produced like Example 1 except having used the protective film 3 instead of the protective film 1. In addition, as a result of measuring the arithmetic mean surface roughness Ra 'and the maximum height Ry' of the protective film 3 in the same manner as described above, Ra 'was 0.07 µm and the maximum height Ry' was 0.98 µm. In addition, the protective film 3 was roll shape and the winding inner side was measured.

<Measurement of Arithmetic Average Surface Roughness Ra and Maximum Height Ry>

On each surface of the photosensitive film laminate (35 mm x 20 mm) used in Examples 1 to 5 and Comparative Examples 1 to 2, the support film side of the glass substrate and the photosensitive film was placed on a clean glass substrate (76 mm x 26 mm x 1.1 mmt) surface. It bonded together using double-sided tape (KZ-12, Nitomsu Corporation make) so that it contacted, and the glass substrate and the photosensitive film laminated body were made to adhere.

Then, the protective film of the photosensitive film laminated body was peeled at the angle of 90 degrees with respect to a glass substrate, and the speed | rate of 2.5 second / cm, and the photosensitive film was exposed. Arithmetic mean surface roughness Ra1 and maximum height Ry1 of the exposed photosensitive film surface immediately after protective film peeling (after 1 minute passed) were measured within 5 minutes immediately after the said protective film peeling. Measurement of Ra1 and Ry1 was performed as follows.

As for "arithmetic mean surface roughness Ra" of the exposed photosensitive film surface, the board | substrate which bonded the exposed photosensitive film to the sample instead of the protective film using the apparatus similar to the measurement of arithmetic mean surface roughness Ra 'of the protective film surface ( The measurement was carried out in the same manner as above, except that the exposed photosensitive film surface was used as the top). In addition, the "maximum height Ry" of the exposed photosensitive film surface also uses the same apparatus as the measurement of the maximum height Ry 'of the support film surface, and the substrate which bonded the exposed photosensitive film instead of the protective film (exposed Measurement was performed similarly to the above except having made photosensitive film surface into the upper part). "Arithmetic mean surface roughness Ra1" and "maximum height Ry1" of each measured photosensitive film surface were as showing in Table 2.

In addition, after leaving each measurement sample for 180 minutes under a yellow lamp in a measurement environment (at room temperature (23 degreeC), relative humidity 42% RH) in the state which exposed the photosensitive film surface with the said protective film, Similarly, the arithmetic mean surface roughness Ra and the maximum height Ry of the exposed photosensitive film surface were measured. "Arithmetic mean surface roughness Ra2" and "maximum height Ry2" of each measured photosensitive film surface were as having shown in Table 2.

Plating Adhesion Evaluation

Electroless copper plating was performed about each test board | substrate of Examples 1-5 and Comparative Examples 1-2 which were produced as mentioned above. Plating conditions were performed in this way.

Electroless Copper Plating Solution: Melplate CU-390 (Meltex Co., Ltd.)

Plating solution temperature: 80 ℃

Plating time: 1 hour

Plating film thickness: 2.0 μm

PH: 13.0 (room temperature)

After the plating treatment, each test substrate having the electroless plated film formed thereon was washed with pure water at room temperature for 5 minutes and then dried at 80 ° C. The cross-sectional part of the boundary of the wall part of each obtained test board | substrate and the electroless plating film was observed with the optical microscope and the electron microscope. Evaluation criteria were made in this way.

(Double-circle): A gap does not generate | occur | produce and there is no problem in close contact.

(Circle): Although a clearance gap generate | occur | produced, there is no problem in close contact.

×: A gap occurs and there is a problem in adhesion

The evaluation results were as shown in Table 2 below.

As is also apparent from the results in Table 2, the arithmetic mean surface roughness of the photosensitive film surface is a test substrate in which a hollow structure is formed using a photosensitive film laminate having Ra1 of 0.1 µm or more and Ra2 / Ra1 of 0.40 or more and less than 1.00. 1-5 (Examples 1-5) show that the electronic component which has high adhesiveness with the plating of a wall part and a cover part, and has a high quality hollow structure is obtained.

On the other hand, test substrate 7 (Comparative Example 2) in which a hollow structure was formed using a photosensitive film laminate having arithmetic mean surface roughness Ra1 of the photosensitive film surface of less than 0.1 μm, even if Ra2 / Ra1 is 0.40 or more and less than 1.00, has a wall portion and a lid. It turns out that adhesion with negative plating and sealing material is inadequate.

Moreover, even if the arithmetic mean surface roughness Ra1 of the photosensitive film surface is 0.1 micrometer or more, the test substrate 6 (comparative example 1) which formed the hollow structure using the photosensitive film laminated body in which Ra2 / Ra1 is 0.40 or more and less than 1.00 is also the range. It turns out that adhesiveness with the plating of a wall part and a cover part is inadequate.

Claims (8)

As a photosensitive film laminated body provided with the support film, the photosensitive film formed with the photosensitive composition, and a protective film in order,
The protective film is peeled from the photosensitive film laminate to expose the surface of the photosensitive film, and the arithmetic mean surface roughness of the surface of the photosensitive film after being left for 1 minute in an environment of 23 ° C. and 42% relative humidity is set to Ra1,
The protective film is peeled off from the photosensitive film laminate to expose the surface of the photosensitive film, and the arithmetic mean surface roughness of the surface of the photosensitive film after being left for 180 minutes in an environment of 23 ° C. and 42% relative humidity is Ra2.
In one case, the following formula:
Ra1≥0.10μm and also 0.40≤Ra2 / Ra1 <1.00
Photosensitive film laminated body which satisfy | fills. The surface of the photosensitive film is exposed by peeling the protective film from the photosensitive film laminate, and the maximum height of the surface of the photosensitive film after standing for 1 minute in an environment of 23 ° C. and 42% relative humidity is set to Ry1 ,.
The protective film is peeled from the photosensitive film laminate to expose the surface of the photosensitive film, and the maximum height of the surface of the photosensitive film after standing for 180 minutes in an environment of 23 ° C. and 42% relative humidity is Ry2.
In one case, the following formula:
Ry1≥1.00μm and also 0.30≤Ry2 / Ry1 <1.00
Photosensitive film laminated body which satisfy | fills. The photosensitive film laminated body of Claim 1 in which the said photosensitive composition contains a photocurable compound. The photosensitive film laminated body of Claim 1 in which the said photosensitive composition contains a photoinitiator further. The photosensitive film laminated body of Claim 1 used for formation of the cover part or wall part which comprises the said hollow structure in the electronic component which has a hollow structure. The hardened | cured material obtained by hardening | curing the photosensitive film of the photosensitive film laminated body of any one of Claims 1-5. It has the hardened | cured material of Claim 6, The electronic component characterized by the above-mentioned. The electronic component according to claim 7, which has a hollow structure including a wall portion and a cover portion, and either or both of the wall portion and the cover portion include the cured product.

Images