JP2019185033A - Photosensitive film laminate and cured product of the same, and electronic component - Google Patents

Abstract

To provide a photosensitive film laminate suitable for forming a hollow structure in an electronic component having a hollow structure such as a SAW filter, in which peeling of a plating film or the like near the hollow structure can be suppressed.SOLUTION: The photosensitive film laminate includes a support film, a photosensitive film formed of a photosensitive composition, and a protective film, successively in this order. After the protective film is peeled from the photosensitive film laminate to expose the photosensitive film surface and the laminate is left to stand in an environment at 23°C and 42% relative humidity for 1 minute, an arithmetic average surface roughness Ra1 of the photosensitive film surface is determined; after the protective film is peeled from the photosensitive film laminate to expose the photosensitive film surface and the laminate is left to stand in an environment at 23°C and 42% relative humidity for 180 minutes, an arithmetic average surface roughness Ra2 of the photosensitive film surface is determined: and Ra1 and Ra2 satisfy Ra1≥0.10 μm and 0.40≤Ra2/Ra1<1.00.SELECTED DRAWING: Figure 1

Description

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

  In recent years, there has been an increasing demand for downsizing and high functionality of electronic devices, and electronic parts used there are further required to be downsized, thinned, and combined functions. Among these, image sensors represented by CMOS and CCD sensors, and gyro sensors using MEMS (Micro Electro Mechanical Systems) technology that integrates mechanical elements and electronic circuit elements on a single substrate by means of semiconductor microfabrication technology. The development of microelectronic components such as device packages that exhibit specific electrical functions by forming electrode patterns and microstructures on the surface of single crystal wafers, such as surface acoustic wave (SAW) filters, has attracted attention. . In these fine electronic components, a hollow structure is formed in order to prevent other objects from coming into contact with the active surface (movable part) of the sensor element and to protect the sensor element from moisture, dust, etc. Etc. are arranged.

  The electronic parts as described above have conventionally formed a hollow structure by processing and joining inorganic materials. However, there is a need for a reduction in manufacturing cost and further miniaturization, and a method of forming a hollow structure with a photosensitive resin or the like instead of an inorganic material has been studied. For example, a permanent resist is laminated, and a photolithography technology It has been proposed that a hollow portion is formed by forming a wall portion (wall surface) or a lid portion (for example, Patent Document 1).

Table 2009/151050

  By the way, the electronic component having a hollow structure such as the SAW filter described above is manufactured as a package structure having external terminals and external electrodes that are electrically connected to the wiring electrodes of the piezoelectric substrate in order to be mounted on the mounting substrate. The At that time, in order to obtain the connection reliability with the external wiring at the wall portion and the lid portion forming the hollow structure, an internal conductor is formed by plating or the like. Further, in order to improve the handleability as well as the protection of the element, the hollow structure and the proximity portion are resin-sealed by a transfer molding method or the like.

  However, in the case where the hollow structure is formed with a permanent resist, it has been confirmed that peeling such as plating occurs when the inner conductor is formed in the proximity portion.

  Therefore, the present invention provides a photosensitive film laminate suitable for forming a hollow structure, which can suppress peeling of plating or the like in a proximity part of the hollow structure in an electronic component having a hollow structure such as a SAW filter. For the purpose. Another object of the present invention is to provide a cured product formed using the photosensitive film laminate and an electronic component having a hollow structure.

  As a method of forming the above hollow structure by using a resin, several layers of photosensitive films are laminated, a wall portion is formed by exposure and development, and another photosensitive film is placed on the upper end of the wall portion. Then, a hollow structure can be formed by exposing and developing to a predetermined shape to form a lid portion and thermally curing the photosensitive resin. When the present inventors diligently studied the above-mentioned problems, when a hollow structure was formed using a photosensitive film as described above, it was used in a developing step on a wall portion or a lid portion constituting the hollow structure. It has been found that a slight amount of the developer remains, and the developer oozes out from the interface, whereby the adhesion with the plating or the like is hindered and easily peeled off. As a result of further investigation, in the photosensitive film laminate provided with the protective film, the photosensitive film whose change with time of the surface form after peeling the protective film and exposing the surface of the photosensitive film is in a specific range It has been found that by using the laminate for forming a hollow structure, it is possible to suppress inhibition of adhesion with plating and the like and to manufacture an electronic component having a high-quality hollow structure.

That is, the photosensitive film laminate of the present invention is a photosensitive film laminate comprising a support film, a photosensitive film formed of a photosensitive composition, and a protective film in order,
The protective film is peeled off from the photosensitive film laminate to expose the surface of the photosensitive film, and the arithmetic average surface roughness of the surface of the photosensitive film after being left for 1 minute in an environment of 23 ° C. and 42% relative humidity. Ra1,
The protective film is peeled off from the photosensitive film laminate to expose the surface of the photosensitive film, and after being left in an environment of 23 ° C. and 42% relative humidity for 180 minutes, the arithmetic average surface roughness of the surface of the photosensitive film. Ra2
If the following formula:
Ra1 ≧ 0.10 μm and 0.40 ≦ Ra2 / Ra1 <1.00
It is characterized by satisfying.

In an embodiment of the present invention, the protective film is peeled off from the photosensitive film laminate to expose the surface of the photosensitive film, and the photosensitive film is allowed to stand for 1 minute in an environment of 23 ° C. and a relative humidity of 42%. The maximum height of the surface is Ry1,
The protective film is peeled off 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 set. Ry2,
If the following formula:
Ry1 ≧ 1.00 μm and 0.30 ≦ Ry2 / Ry1 <1.00
It is preferable to satisfy.

  Moreover, in the embodiment of this invention, it is preferable that the said photosensitive composition contains a photocurable compound.

  In the embodiment of the present invention, it is preferable that the photosensitive composition further contains a photopolymerization initiator.

  In the embodiment of the present invention, the photosensitive film laminate is preferably used for forming a lid portion or a wall portion constituting the hollow structure in an electronic component having a hollow structure.

  Moreover, the hardened | cured material by another aspect of this invention is obtained by hardening the photosensitive film of the said photosensitive film laminated body, It is characterized by the above-mentioned.

  Moreover, the electronic component by another aspect of this invention has the said hardened | cured material, It is characterized by the above-mentioned.

  Moreover, it is preferable that the electronic component by another aspect of this invention has a hollow structure which consists of a wall part and a cover part, and either or both of the said wall part and a cover part consist of said hardened | cured material.

  ADVANTAGE OF THE INVENTION 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 proximity | contact part of a hollow structure, can be provided. . Moreover, according to another aspect of this invention, the hardened | cured material and electronic component which were formed using the said photosensitive film laminated body can be provided.

6 is a schematic cross-sectional view showing a procedure for producing test substrates produced in Example 4 and Example 5. FIG. 6 is a schematic cross-sectional view showing a procedure for producing test substrates produced in Example 4 and Example 5. FIG. 6 is a schematic cross-sectional view showing a procedure for producing test substrates produced in Example 4 and Example 5. FIG. 6 is a schematic cross-sectional view showing a procedure for producing test substrates produced in Example 4 and Example 5. FIG.

<Photosensitive film laminate>
The photosensitive film laminated body by this invention is equipped with the support film, the photosensitive film formed with the photosensitive composition, and the protective film in order. Hereinafter, each component which comprises the photosensitive film laminated body of this invention is demonstrated. Unless otherwise specified, in this specification, a numerical range represented using the symbol “to” includes a range including upper and lower limits (that is, a range not less than the lower limit and not more than the upper limit). Means.

[Support film]
The support film constituting the photosensitive film laminate according to the present invention supports the photosensitive film, and can be used without particular limitation as long as it can achieve the function, for example, polyethylene terephthalate or A film made of a thermoplastic resin such as a polyester film such as polyethylene naphthalate, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film can be suitably used. When the thermoplastic resin film is used, a filler is added (kneading treatment) to the resin when the film is formed, mat coating (coating treatment), or the film surface is subjected to sandblast treatment. It may be subjected to a blast treatment, or a treatment such as hairline processing or chemical etching. Among these, a polyester film can be preferably used from the viewpoints of heat resistance, mechanical strength, handleability, and the like. The support film may be a single layer, or two or more layers may be laminated.

  As the above-described thermoplastic resin film, it is preferable to use a film stretched in a uniaxial direction or a biaxial direction for the purpose of improving strength.

  The thickness of the support film is not particularly limited, but is appropriately selected depending on the intended use within a range of about 10 μm to 3,000 μm.

[Photosensitive film]
The photosensitive film which comprises the photosensitive film laminated body by this invention is formed with 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 dry and form. The photosensitive film becomes a cured product by curing the photosensitive composition after making it into a predetermined shape by exposure and development. Therefore, in the state where the protective film is peeled off from the photosensitive film laminate and the surface of the photosensitive film is exposed, the photosensitive composition is in an uncured state, so the surface morphology of the photosensitive film changes over time. To do. In the present invention, it has been found that there is some relationship between the change over time of the surface form of the photosensitive film and peeling such as plating, and a photosensitive film laminate that satisfies the following conditions: Thus, if the hollow structure of the electronic component is formed using the photosensitive film laminate, the electronic component having a high-quality hollow structure can be realized by suppressing the inhibition of adhesion with plating and the like. Is.

In the present invention, the protective film is peeled from the photosensitive film laminate to expose the surface of the photosensitive film, and the surface of the photosensitive film is left to stand in an environment of 23 ° C. and 42% relative humidity for 1 minute. Ra1 as the average surface roughness
The protective film is peeled from the photosensitive film laminate to expose the surface of the photosensitive film, and after being left for 180 minutes in an environment of 20 ° C. and 42% relative humidity, the arithmetic average surface roughness of the surface of the photosensitive film is obtained. Ra2
If the following formula:
Ra1 ≧ 0.10 μm and 0.40 ≦ Ra2 / Ra1 <1.00
It is important to meet. When the photosensitive film when the protective film is peeled has an uneven surface with a predetermined arithmetic average surface roughness, the uneven surface tends to gradually become flat, and the surface form changes over time. In the present invention, paying attention to the temporal change of the surface form and using a photosensitive film that remains in a specific surface form change, it is possible to suppress peeling of plating or the like in the proximity part of the hollow structure.

  In the present invention, the arithmetic average surface roughness Ra1 of the photosensitive film on the surface in contact with the protective film after peeling off the protective film is 0.10 μm or more, preferably 0.15 μm or more, and 0.20 μm or more. It is more preferable. Moreover, when providing an upper limit, below 1.00 micrometer is preferable, 0.80 micrometer or less is more preferable, and 0.60 micrometer or less is further more preferable. Ra1 is defined as a value measured by peeling the protective film to expose the surface of the photosensitive film and leaving it in an environment of 23 ° C. and 42% relative humidity for 1 minute.

  Further, from the viewpoint of further suppressing peeling such as plating, the maximum height Ry1 of the photosensitive film on the surface in contact with the protective film after peeling off the protective film is preferably 1.00 or more, and 1.20 μm. The above is more preferable, and 1.40 μm or more is more preferable. Moreover, when providing 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 further more preferable. Ry1 is defined as a value measured by peeling the protective film to expose the surface of the photosensitive film and leaving it in an environment of 23 ° C. and 42% relative humidity for 1 minute.

  The change in the shape of the photosensitive film surface over time can be evaluated by the ratio of the arithmetic average surface roughness after elapse of a predetermined time to the arithmetic average surface roughness (that is, Ra1) immediately after the protective film is peeled off. In the present invention, the protective film is peeled off from the photosensitive film laminate to expose the surface of the photosensitive film and left in an environment of 23 ° C. and 42% relative humidity for 180 minutes, which is in contact with the protective film. Assuming that the arithmetic average surface roughness of the photosensitive film is Ra2, if the photosensitive film laminate satisfies 0.40 ≦ Ra2 / Ra1 <1.00, peeling such as plating in the adjacent portion of the hollow structure may occur. Can be suppressed. The reason for this is not clear, but is considered as follows. That is, in the photosensitive film laminate provided with the protective film, the surface form having a certain roughness after peeling the protective film and exposing the photosensitive film surface gradually changes over time, and the When the rate of change is constant, in the case of wall materials, the degree of close contact between the base material and the cover material is more appropriate, and the remaining developer used during development is in the periphery of the hollow structure. As a result, it is presumed that it was possible to prevent peeling of plating and the like due to the remaining developer. However, this is only an estimation area and is not necessarily limited to this. In the present invention, the place where the protective film is peeled off and the surface of the photosensitive film is exposed for 180 minutes is under a yellow lamp.

  The change in the shape of the photosensitive film over time is preferably 0.50 ≦ Ra2 / Ra1 ≦ 0.95, and 0.60 ≦ Ra2 / Ra1 ≦ 0.90 from the viewpoint of further suppressing peeling from an appropriate shape change. Is more preferable.

  Also, the protective film is peeled from the photosensitive film laminate to expose the surface of the photosensitive film, and the photosensitive film on the surface in contact with the protective film after being left for 180 minutes in an environment of 23 ° C. and 42% relative humidity. When the maximum height of Ry2 is Ry2, if the photosensitive film laminate satisfies 0.30 ≦ Ry2 / Ry1 <1.00, peeling such as plating can be further suppressed. In the present invention, the place where the protective film is peeled off and the surface of the photosensitive film is exposed for 180 minutes is under a yellow lamp.

  The shape change over time of the photosensitive film surface is preferably 0.35 ≦ Ry2 / Ry1 ≦ 0.80 from the viewpoint of further suppressing peeling from an appropriate shape change, and 0.40 ≦ Ry2 / Ry1 ≦ 0.70. Is more preferable.

  Further, the arithmetic surface roughness Ra ″ and the maximum height Ry ″ of the surface in contact with the support film in the photosensitive film are also in the same range and change as the arithmetic surface roughness Ra and the maximum height Ry of the surface in contact with the protective film. It is preferable to be in the ratio. This is particularly effective in the case of a photosensitive film laminate having no protective film and sequentially comprising a support film and a photosensitive film formed of a photosensitive composition. In such a case, the support film is preferably made of the same material and thickness as a protective film as described later.

  In the present invention, the above-mentioned “arithmetic average surface roughness Ra” and “maximum height Ry” mean values measured by a measuring device based on JIS B0601-1994. Hereinafter, a specific measurement method will be described. The arithmetic average surface roughness Ra and the maximum height Ry can be measured using a shape measurement laser microscope (for example, VK-X100 manufactured by Keyence Corporation). Sample (photosensitive film) to be measured on xy stage after starting shape measurement laser microscope (VK-X100) main body (control unit) and VK observation application (VK-H1VX manufactured by Keyence Corporation) Is placed. Turn the lens revolver of the microscope section (VK-X110 manufactured by Keyence Corporation) to select an objective lens with a magnification of 10x, and adjust the focus and brightness roughly in the image observation mode of the VK observation application (same VK-H1VX). To do. The xy stage is operated so that the part to be measured on the sample surface is adjusted to the center of the screen. The objective lens with a magnification of 10 times is changed to a magnification of 50 times, and the surface of the sample is focused with the autofocus function in the image observation mode of the VK observation application (VK-H1VX). By selecting the simple mode of the shape measurement tab of the VK observation application (same VK-H1VX) and pressing the measurement start button, the surface shape of the sample can be measured to obtain a surface image file. After starting the VK analysis application (VK-H1XA manufactured by Keyence Corporation) and displaying the obtained surface image file, tilt correction is performed. The observation measurement range (horizontal) in measuring the surface shape of the sample is 270 μm. Display the line roughness window, select JIS B0601-1994 in the parameter setting area, select the horizontal line from the measurement line button, display the horizontal line at an arbitrary location in the surface image, and press the OK button. The numerical values of the arithmetic average surface roughness Ra and the maximum height Ry are obtained. Further, horizontal lines are displayed at four different locations in the surface image, and numerical values of the arithmetic average surface roughness Ra and the maximum height Ry are obtained. The average values of the obtained five numerical values are respectively calculated and set as the arithmetic average surface roughness Ra and the maximum height Ry value of the sample surface. In the measurement of the arithmetic average surface roughness Ra and the maximum height Ry described above, a photosensitive film in a state before the curing step by exposure or the like is 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 the lamination to a base material shall be used. In this case, the “arithmetic average surface roughness Ra” and the “maximum height Ry” of the sample surface are measured immediately after peeling the protective film and exposing the photosensitive film (1 minute) and after 180 minutes. . The measurement environment in the present invention is a temperature of 23 ° C. and a relative humidity of 42%.

  In order to make the surface form of the photosensitive film within the range of the specific arithmetic average surface roughness Ra and the maximum height Ry described above, known and commonly used techniques can be applied. From the viewpoint of ease of formation, a photosensitive film can be formed using a protective film having an arithmetic average surface roughness Ra and a maximum height Ry adjusted as described later. Moreover, after sticking the protective film which has specific arithmetic mean surface roughness Ra and maximum height Ry, the said protective film is peeled, Then, another protective film which has different arithmetic mean surface roughness Ra and maximum height Ry May be adhered to the surface of the photosensitive film to adjust the roughness of the surface of the photosensitive film.

  Moreover, the time-dependent change of the surface form of the photosensitive film after peeling off a protective film can be adjusted with the kind and compounding quantity of the component contained in the photosensitive composition before the hardening which comprises a photosensitive film. For example, it can be adjusted by blending materials having different solubility parameters (SP values), using an appropriate material having a glass transition temperature (Tg) or a weight average molecular weight, or appropriately using a filler. It is not limited. In the present invention, the photosensitive composition forming the photosensitive film is not particularly limited in its composition, but may contain a photocurable compound, a photopolymerization initiator, a thermal crosslinking material, an inorganic filler, and the like. Hereinafter, each component constituting the photosensitive composition will be described.

[Photocurable compound]
The photosensitive composition used in the photosensitive film laminate of the present invention includes a component that is cured by irradiation with ionizing radiation such as ultraviolet rays, and examples thereof include a photocurable compound. The photocurable compound is a compound having an ethylenically unsaturated double bond, and the compound includes any of resin, oligomer and monomer. Examples of such a photocurable compound include alkyl (meth) acrylates such as 2-ethylhexyl (meth) acrylate and cyclohexyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) Hydroxyalkyl (meth) acrylates such as acrylates; mono- or di (meth) acrylates of alkylene oxide derivatives such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol; hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane Polyhydric alcohols such as dipentaerythritol and trishydroxyethyl isocyanurate or ethylene oxide or propylene oxide thereof Polyhydric (meth) acrylates of additives; (meth) acrylates of ethylene oxide or propylene oxide adducts of phenols such as phenoxyethyl (meth) acrylate and polyethoxydi (meth) acrylate of bisphenol A; glycerin diglycidyl ether, And (meth) acrylates of glycidyl ethers such as trimethylolpropane triglycidyl ether and triglycidyl isocyanurate; and melamine (meth) acrylate. In addition, in this specification, (meth) acrylate is a term which generically refers to acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.

  In addition to the above, there may be mentioned urethane monomers or urethane oligomers such as polymerizable compounds having an amide bond and at least one ethylenically unsaturated group, and (meth) acrylate compounds having a urethane bond.

  Furthermore, the photocurable compound can be made into a carboxyl group-containing photosensitive resin by reacting an unsaturated carboxylic acid such as acrylic acid or methacrylic acid with an epoxy resin or a phenol resin. Such a carboxyl group-containing photosensitive resin is preferable in that it can be cured by polymerization or cross-linking by light irradiation, and further, by including a carboxyl group, not only solvent development but also alkali developability can be achieved. . In particular, it is preferable from the viewpoint of being able to achieve excellent developability even for a weakly alkaline developer, specifically, a developer having a pH of 7.0 or more and 12.0 or less.

Specific examples of the carboxyl group-containing photosensitive resin include the compounds listed below (which may be either oligomers or polymers).
(1) A bifunctional or higher polyfunctional (solid) epoxy resin is reacted with (meth) acrylic acid, and the hydroxyl group present in the side chain has two bases such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. A carboxyl group-containing photosensitive resin to which an acid anhydride is added,
(2) A polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin is reacted with (meth) acrylic acid, and a dibasic acid anhydride is added to the resulting hydroxyl group. Carboxyl group-containing photosensitive resin,
(3) An epoxy compound having two or more epoxy groups in one molecule is combined with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, and (meth) acrylic acid or the like. Polybasic, such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid, etc., with respect to the alcoholic hydroxyl group of the reaction product obtained by reacting with a saturated carboxylic acid containing monocarboxylic acid A carboxyl group-containing photosensitive resin obtained by reacting an acid anhydride,
(4) Two or more per molecule such as bisphenol A, bisphenol F, bisphenol S, novolac type phenol resin, poly-p-hydroxystyrene, condensate of naphthol and aldehydes, condensate of dihydroxynaphthalene and aldehydes Obtained by reacting an unsaturated group-containing monocarboxylic acid such as (meth) acrylic acid with a reaction product obtained by reacting a compound having a phenolic hydroxyl group with an alkylene oxide such as ethylene oxide or propylene oxide. A carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a polybasic acid anhydride,
(5) A reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate is reacted with an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing photosensitive resin obtained by reacting the resulting reaction product with a polybasic acid anhydride,
(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 A type A terminal urethane group-containing photosensitive urethane resin obtained by reacting an acid anhydride with a terminal of a urethane resin by a polyaddition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group,
(7) During synthesis of a carboxyl group-containing urethane resin by a polyaddition reaction between a diisocyanate, a carboxyl group-containing dialcohol compound such as dimethylolpropionic acid or dimethylolbutyric acid, and a diol compound, a molecule such as hydroxyalkyl (meth) acrylate A carboxyl group-containing photosensitive urethane resin in which a compound having one hydroxyl group and one or more (meth) acryloyl groups is added and terminal (meth) acrylated,
(8) During synthesis of a carboxyl group-containing urethane resin by polyaddition reaction of a diisocyanate, a carboxyl group-containing dialcohol compound, and a diol compound, an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate, etc. A carboxyl group-containing photosensitive urethane resin obtained by adding a compound having two isocyanate groups and one or more (meth) acryloyl groups, and terminal (meth) acrylated,
(9) A carboxyl group-containing polyester resin obtained by reacting a polyfunctional oxetane resin with a dicarboxylic acid such as adipic acid, phthalic acid or hexahydrophthalic acid and adding a dibasic acid anhydride to the primary hydroxyl group produced. Further, a carboxyl group-containing photosensitive resin obtained by adding a compound having one epoxy group and one or more (meth) acryloyl groups in one molecule, such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate. ,
(10) A carboxyl group-containing photosensitive resin obtained by adding a compound having a cyclic ether group and a (meth) acryloyl group in one molecule to the carboxyl group-containing photosensitive resin of any one of (1) to (9) described above. ,
(11) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene. On the other hand, a carboxyl group-containing photosensitive resin obtained by reacting a compound having a cyclic ether group and a (meth) acryloyl group in one molecule such as 3,4-epoxycyclohexyl methacrylate can be used. Here, (meth) acrylate is a generic term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

  The weight average molecular weight of the above-described photocurable compound varies depending on the resin skeleton, but is generally preferably 2,000 to 200,000. When the weight average molecular weight is 2,000 or more, tack-free performance and resolution can be improved. Furthermore, the state change with time of the coating film surface becomes appropriate, and the adhesion to the base can be further improved. Further, when the weight average molecular weight is 200,000 or less, developability and storage stability can be improved. A more preferred weight average molecular weight is 4,000 to 150,000, and even more preferably 5,000 to 100,000. The weight average molecular weight can be measured by gel permeation chromatography (GPC) method (polystyrene standard).

  The compounding amount of the photocurable compound is 50 to 50 when the total amount of the photocurable compound and the thermal crosslinking material is 100 parts by mass in terms of solid content when the composition also contains a thermal crosslinking material to be described later. It is preferably 90 parts by mass. By setting the blending amount of the photocurable compound within the above range, a stronger hollow structure can be formed. Moreover, the state change with time of the coating film surface becomes appropriate, and the adhesion to the ground can be further improved.

[Thermal crosslinking material]
It can be expected that the heat resistance of the photosensitive film is improved by adding a thermal crosslinking material. A thermal crosslinking material can be used individually by 1 type or in combination of 2 or more types. Any known thermal crosslinking material can be used. For example, amino resins such as melamine resin, benzoguanamine resin, melamine derivative, benzoguanamine derivative, isocyanate compound, block isocyanate compound, cyclocarbonate compound, epoxy compound, oxetane compound, episulfide resin, bismaleimide, carbodiimide resin, melamine resin, urea resin, Known thermosetting components such as novolak resins such as polyimide resin, phenol novolak, and cresol novolak can be used. Among these, from the viewpoint of adhesion between the cured product of the photosensitive composition and the substrate, an epoxy resin, a melamine resin, and a urea resin are preferable, and an epoxy resin is more preferable.

  When the composition includes the photocurable compound described above in the composition, it is 10 to 10 when the total amount of the photocurable compound and the heat crosslinkable material is 100 parts by mass in terms of solid content. It is preferable that it is 40 mass parts. By setting the blending amount of the thermal crosslinking material in the above range, a stronger hollow structure can be formed. Moreover, since the ratio of a photocurable compound increases because the compounding quantity of a thermal crosslinking material shall be 40 mass parts or less, the resolution improves more.

  When an epoxy resin or the like is used as the thermal crosslinking material, a curing agent for further curing the epoxy resin may be included. Examples of the curing agent include amines, imidazoles, polyfunctional phenols, acid anhydrides, isocyanates, and polymers containing these functional groups, and a plurality of these may be used as necessary.

[Photopolymerization initiator]
Specific examples of the photopolymerization initiator include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, 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-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2, 4,6-trimethylbenzoyl) -phenylphosphine Bisacylphosphine oxides such as oxide; 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2-methyl Monoacylphosphine oxides such as benzoyldiphenylphosphine oxide, pivaloylphenylphosphinic acid isopropyl ester, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; phenyl (2,4,6-trimethylbenzoyl) phosphinic acid Ethyl, 1-hydroxy-cyclohexyl phenyl ketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, 2-hydroxy-2-methyl-1-phenyl Hydroxyacetophenones such as propan-1-one; benzoins such as benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether; benzoin alkyl ethers; benzophenone, p -Benzophenones such as methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone; acetophenone, 2,2-dimethoxy-2-phenylacetate Phenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl) -1- [4- (4- Morpholinyl) phenyl] -1-butanone, acetophenones such as N, N-dimethylaminoacetophenone; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chloro Thioxanthone, 2,4-diisopropylthio Thioxanthones such as Sandton; anthraquinones such as anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone; acetophenone dimethyl ketal Ketals such as benzyldimethyl 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-carbazol-3-yl]-, 1- (O- Acetyl Oxime esters such as bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium, bis (cyclo Titanocenes such as pentadienyl) -bis [2,6-difluoro-3- (2- (1-pyr-1-yl) ethyl) phenyl] titanium; phenyl disulfide 2-nitrofluorene, butyroin, anisoin ethyl ether Azobisisobutyronitrile, tetramethylthiuram disulfide and the like.

  The compounding quantity of a photoinitiator is 0.1-10 mass parts in conversion of solid content with respect to 100 mass parts of photocurable compounds, when the photocurable compound mentioned above is contained in a composition. Is preferred. The resolution improves more by making the compounding quantity of a photoinitiator into said range.

  A photoinitiator or sensitizer may be used in combination with the above-described photopolymerization initiator. Examples of the photoinitiation assistant or sensitizer include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds. These compounds may be used as a photopolymerization initiator in some cases, but are preferably used in combination with a photopolymerization initiator. Moreover, a photoinitiator auxiliary or a sensitizer may be used individually by 1 type, and may use 2 or more types together.

  In addition, since these photopolymerization initiators, photoinitiator assistants, and sensitizers absorb a specific wavelength, in some cases, the sensitivity is lowered, and the photopolymerization initiator, photoinitiator assistant, and sensitizer may function as an ultraviolet absorber. However, they are not used only for the purpose of improving the sensitivity of the composition. If necessary, light of a specific wavelength can be absorbed to increase the photoreactivity of the surface, and the shape accuracy when exposed and developed can be improved.

[Filler]
By mix | blending a filler with a photosensitive composition, while being able to raise the hardness of a coating film, heat resistance, etc., 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 filler include barium sulfate, silica, mica, hydrotalcite, talc, metal oxide, metal hydroxide such as aluminum hydroxide, and the like. Of these, silica and mica are preferable. Examples of the silica include spherical silica and amorphous silica.

  If necessary, other resins other than those described above, a thermal radical generator, a polymerization inhibitor, an adhesion aid, an organic solvent, and the like may be added to the photosensitive composition.

  For example, heat resistance can be improved by mix | blending other resin. Examples of other resins include polyimides, polyoxazoles and their precursors, novolak resins such as phenol novolac and cresol novolac, polyamideimide, polyamide, phenoxy resin, and polyethersulfone. These may be used alone or in combination of two or more.

  The polyimide resin may be alkali-soluble. Specifically, it has an alkali-soluble group such as a carboxyl group or an acid anhydride group in addition to the imide group. For introducing the alkali-soluble group, a known and commonly used method can be used. Examples thereof include a resin obtained by reacting a carboxylic anhydride component with at least one of an amine component and an isocyanate component. The imidization may be performed by thermal imidization or chemical imidization, and these can be used in combination.

  Moreover, a photocurable compound can be hardened in a short time at low temperature by mix | blending a thermal radical generator. Examples of the thermal radical generator include peroxides and azo compounds.

  Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, phenothiazine and the like. Examples of the adhesion assistant include silane coupling agents such as γ-glycidoxysilane, aminosilane, and γ-ureidosilane.

  The photosensitive film can be formed by applying the photosensitive composition described above to one side of the support film and drying it. In consideration of the applicability of the photosensitive composition, the photosensitive composition is diluted with an organic solvent and adjusted to an appropriate viscosity. A comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, and a transfer roll. Apply a uniform thickness to one side of the support film with a coater, gravure coater, spray coater, bar coater, roll coater, comma coater, slit die coater, spin coater, etc., and volatilize the organic solvent by drying. A free coating film can be obtained. Although there is no restriction | limiting in particular about a coating film thickness, Generally, it is a film thickness after drying, and is suitably selected in the range of 0.5-500 micrometers. From the viewpoint of using it as a material for forming the wall or lid of the hollow structure, it is preferably in the range of 1 to 300 μm.

  The organic solvent that can be used is not particularly limited, and examples thereof include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. be able to. 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, Glycol ethers such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol Monomethyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol Esters such as chill 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, and solvent naphtha And N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone and the like. Such an organic solvent may be used individually by 1 type, and may be used as a 2 or more types of mixture.

  Volatile drying of organic solvents supports hot air circulation drying furnaces, IR furnaces, hot plates, convection ovens, etc. (methods using counter-contact with hot air in the dryer using a steam-heated heat source and nozzle support Can be performed using a method of spraying on the body). As volatile drying conditions, the temperature is appropriately selected in the range of 60 to 120 ° C. and the time in the range of 1 to 60 minutes.

[Protective film]
The photosensitive film laminate according to the present invention is for the purpose of preventing dust and the like from adhering to the surface of the above-described photosensitive film and improving the handleability, and further, the arithmetic average surface roughness Ra of the photosensitive film surface. For the purpose of adjusting the thickness, a protective film is provided on the surface of the photosensitive film opposite to the support film.

  As the protective film, for example, a polyester film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper or the like can be used, and a polypropylene film is particularly preferable. In addition, it is preferable to select a material in which the adhesive force between the protective film and the photosensitive film is smaller than the adhesive force with the photosensitive film. Moreover, in order to make it easy to peel a protective film at the time of use of a photosensitive film laminated body, you may give a mold release process as mentioned above to the surface which contacts the photosensitive film of a protective film.

  The thickness of the protective film is not particularly limited, but is appropriately selected depending on the application in the range of about 10 to 200 μm.

  In the present invention, it is preferable to use a protective film having an arithmetic average surface roughness Ra ′ of 0.10 μm or more on the surface of the protective film on the side in contact with the photosensitive film. Further, it is more preferable to use a protective film having an arithmetic average surface roughness Ry ′ of 1.00 μm or more on the surface of the protective film on the side in contact with the photosensitive film. By using the protective film having such a surface form, it becomes easy to form a photosensitive film having an arithmetic average surface roughness Ra of 0.10 μm or more, and further, an arithmetic average surface roughness Ry of 1.00 μm or more. It becomes easy to form the photosensitive film which has this. The arithmetic average surface roughness Ra ′ of the protective film is more preferably 0.15 μm or more, and further preferably 0.20 μm or more. Moreover, when providing an upper limit, it is preferable that it is 1.00 micrometer or less, it is more preferable that it is 0.80 micrometer or less, and it is more preferable that it is 0.60 micrometer or less.

  Further, the maximum height Ry ′ of the protective film on the side in contact with the photosensitive film is more preferably 1.20 μm or more, and further preferably 1.40 μm or more. Moreover, when providing 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 meaning of each of the arithmetic average surface roughness Ra ′ and the maximum height Ry ′ and the specific measurement method thereof will be described in the above-mentioned “Photosensitive film”. The arithmetic average surface roughness Ra ′ of the protective film, the arithmetic average surface roughness Ra of the photosensitive film, the maximum height Ry ′ of the protective film, and the maximum height Ry of the photosensitive film are not necessarily the same. By appropriately adjusting, the arithmetic average surface roughness Ra and the maximum height Ry of the photosensitive film can be set within the specific ranges as described above.

  The method for adjusting the protective film having the arithmetic average 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 filler However, the surface of the protective film can be brought into a predetermined form by blasting or by hairline processing, mat coating, chemical etching, or the like.

<Hardened product>
A cured product is formed using the photosensitive film laminate of the present invention. As an example of such a cured product, a method for forming a hollow structure having a wall portion and a lid portion using the photosensitive film laminate of the present invention will be described.

[Method for forming wall]
First, a wall part is formed using a photosensitive film laminated body. Specifically, the protective film is peeled from the photosensitive film laminate, and the photosensitive film is laminated on an adherend such as a substrate, and a predetermined portion of the photosensitive film is irradiated with light through a mask. The exposure process for photocuring the exposed portion, the development process for removing the portion other than the photocured portion of the photosensitive film using a developer, and the photocured portion of the photosensitive film is cured by light or heat. A desired wall portion can be formed through a main curing step for forming an object. Hereinafter, each step will be described.

  In the lamination step, the protective film is peeled off from the photosensitive film laminate, and the exposed photosensitive film surface side is laminated on the substrate. Lamination can be performed by adhesion or the like by thermocompression bonding. Examples of the substrate that is an adherend include a silicon wafer, a glass substrate, a ceramic substrate, an aluminum base substrate, a stainless steel substrate, a glass epoxy substrate, a polyester substrate, and a polyimide substrate. Examples of the thermocompression bonding method include hot pressing, roll laminating, vacuum roll laminating, vacuum pressing, diaphragm vacuum laminating, and the like. The thermocompression bonding temperature is 20 to 150 ° C. from the viewpoint of adhesion to the substrate, embedding property, and maintaining good resolution without curing the photosensitive composition during thermocompression bonding. Preferably, it is 35-100 degreeC, More preferably, it is 40-85 degreeC. The laminating pressure is preferably 0.005 to 10 MPa, more preferably 0.005 to 3 MPa.

  Next, an exposure process is performed. The exposure includes a negative type and a positive type, but the negative type is preferable. In the case of the negative type, the photosensitive film laminate laminated on the substrate is irradiated with light through a negative mask having a desired pattern that becomes the shape of the wall, and the exposed portion of the photosensitive film is photocured. Here, examples of the actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, and X-rays. Among these, ultraviolet rays and visible rays are particularly preferable. Further, mask exposure using i-line (365 nm), h-line (405 nm), and g-line (436 nm) of an ultrahigh pressure mercury lamp through a photomask is preferable. Moreover, the method of directly drawing on a photosensitive film masklessly using the laser of wavelength 405nm is also mentioned. At this process, the support film which comprises a photosensitive film laminated body may peel before exposure, and may peel after exposure. Moreover, 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 a support film or peeling before exposure. Moreover, you may heat-process for 5 second-60 minutes at the temperature of 40-150 degreeC using an oven or a hotplate after peeling, without peeling a support film or without peeling.

  Next, a portion of the photosensitive film other than the photocured portion (unexposed portion) is removed using an organic solvent-based or alkaline aqueous solution-based developer to form a wall pattern.

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

  Examples of the developing method include spraying a developer on a photosensitive film, immersing in a developer, or applying ultrasonic waves while immersing.

  Further, after development, it is preferable to rinse with water, alcohol such as methanol, ethanol or isopropyl alcohol, n-butyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether acetate or the like, if necessary. Examples of the rinsing method include spraying a developer on the surface of the photosensitive film, immersing in the developer, or applying ultrasonic waves while immersing.

  Next, the photocured portion (exposed portion) of the photosensitive film is cured by light or heat to form a wall portion. Curing after curing (curing) is preferably carried out for 1 to 2 hours while gradually increasing the temperature by selecting the temperature when cured by heat. The temperature of thermosetting is appropriately selected within the range of 120 to 400 ° C. and the time of 60 to 120 minutes. The temperature may be fixed at a constant temperature or a stepwise temperature increase. At the time of curing, it is preferable to perform a heat treatment in an inert gas such as nitrogen or argon. The final heating temperature is preferably 150 to 350 ° C. Further, photocuring may be performed before or after thermal curing or instead of thermal curing.

  The film thickness of the photosensitive film for forming the wall is preferably 1 to 3000 μm, more preferably 5 to 1,000 μm, further preferably 10 to 500 μm, particularly preferably 20 to 200 μm, most preferably 20 to 100 μm. preferable. If 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 during molding. Moreover, if thickness is 3000 micrometers or less, the light transmittance of the photosensitive film at the time of exposure will be hard to be inhibited. In addition, you may increase the thickness of a wall part by repeating the lamination process which piles up a photosensitive film. The final film thickness of the wall formed through the curing step is also preferably 1 to 3,000 μm, more preferably 5 to 500 μm, and further preferably 10 to 200 μm.

[Formation of lid]
The wall portion made of a cured product of the photosensitive film formed by the above-described forming method has a sufficient film thickness, and a ceramic substrate, Si substrate, glass substrate, metal substrate, or the like is used as a lid on the upper end of the wall portion. Although a hollow structure can be formed by covering, a lid part may be formed using a photosensitive film laminate. Hereinafter, a method for forming the lid using the photosensitive film laminate will be described.

  The photosensitive film laminate from which the protective film is peeled off is laminated on the upper end of the wall portion formed as described above, and the cover is obtained by curing the photocured photosensitive film by performing exposure and developing as necessary. The part can be formed to form a hollow structure. When forming the lid using the photosensitive film laminate, it is not always necessary to go through a development step. For example, when simultaneously manufacturing a plurality of hollow structure devices at the same time, it corresponds to the lid of the hollow device. After exposing only the size through a mask, the peripheral unexposed portions can be developed to be divided into individual pieces.

  Lamination, exposure, development, and curing of the photosensitive film laminate can be performed in the same manner as the formation of the wall portion described above. Here, adhesion at the time of lamination of the laminated body forming the wall portion and the lid portion can be performed by thermocompression bonding. Examples of the thermocompression bonding method include hot pressing, roll laminating, vacuum roll laminating, vacuum pressing, diaphragm vacuum laminating, etc. Among them, roll laminating is preferable. The thermocompression bonding temperature is preferably 20 ° C. or higher from the viewpoint of adhesion to the adherend and embedding property. In addition, the thermocompression bonding temperature is preferably 150 ° C. or less from the viewpoint of preventing the photosensitive resin component from being cured during thermocompression bonding and deteriorating the resolution of pattern formation in exposure and development. That is, the thermocompression bonding temperature is 20 to 150 ° C. from the viewpoint of adhesion to the substrate, embedding property, and maintaining good resolution without curing the photosensitive composition during thermocompression bonding. Preferably, it is 35-100 degreeC, More preferably, it is 40-85 degreeC. The laminating pressure is preferably 0.005 to 10 MPa, more preferably 0.005 to 3 MPa.

  The support film constituting the photosensitive film laminate may be peeled off before exposure, may be peeled off after exposure, or may be peeled off after the photosensitive film is cured. Peeling after exposure and peeling after curing are preferred from the viewpoint of stability because the cured product of the film is supported only by the wall. Moreover, you may heat-process for 5 second-60 minutes at the temperature of 40-150 degreeC using an oven or a hotplate, without peeling a support film or without peeling before exposure. Further, after the exposure, the support film may be peeled off or may be heat-treated at a temperature of 40 to 150 ° C. for 5 seconds to 60 minutes using an oven or a hot plate. Further, the development and curing may be performed collectively for the wall portion and the lid portion. The tensile modulus of the cured film forming the lid is preferably 2.0 GPa or more.

  The film thickness of the photosensitive film for forming the lid is preferably 1 to 3,000 μm, more preferably 5 to 1,000 μm, further preferably 10 to 500 μm, particularly preferably 20 to 200 μm, most preferably 20 to 100 μm. preferable. The final film thickness of the lid formed through the curing step is preferably 10 μm to 3,000 μm. 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 during molding. Moreover, if it is 3,000 micrometers or less, the light transmittance of the photosensitive film at the time of exposure will not be inhibited easily. In addition, you may increase the thickness of a cover part by repeating the lamination process which piles up a photosensitive film.

  In the present invention, the wall portion can be formed without using the photosensitive film laminate of the present invention, and only the lid portion can be formed using the photosensitive film laminate of the present invention. When both the pattern and the lid portion use the photosensitive film laminate of the present invention, the adhesiveness between them is more excellent, and peeling such as plating at the proximity portion of the hollow structure can be suppressed.

  According to the present invention, in an electronic component having a hollow structure such as a SAW filter, the wall portion and the lid portion are formed by using the photosensitive film laminate of the present invention, so that plating or the like is peeled off at the adjacent portion of the hollow structure. Can be suppressed. In addition, since the hollow structure is moisture-proof by the wall and lid, and the hollow structure is maintained even at high temperatures, it can be applied to electronic parts that require a hollow structure such as SAW filters, CMOS / CCD sensors, and MEMS. Therefore, it is useful for reducing the size, height and functionality of electronic components. The photosensitive film laminate of the present invention is particularly suitable for forming a wall or lid of a hollow structure of a SAW filter, and a highly reliable electronic component that suppresses peeling such as plating at the adjacent portion of the hollow structure is obtained. It is particularly suitable in that it can be used. Moreover, you may use this invention for printed wiring board uses, such as a soldering resist, a plating resist, an etching resist, and an interlayer insulation material.

<SAW filter and manufacturing method thereof>
The method of forming a hollow structure having a wall and a lid using the photosensitive film laminate of the present invention has been described. As an example of an electronic component having a hollow structure, a surface acoustic wave (SAW) filter and its The manufacturing method will be described below.

  First, the protective film is peeled off from the photosensitive film laminate of the present invention and the photosensitive film surface is laminated on the substrate on which the comb-shaped electrode is formed. 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.

  Next, after laminating the photosensitive film laminate, light exposure is performed on a predetermined portion of the photosensitive film through a negative mask having a desired pattern as necessary, and the exposed portion is photocured. For the exposure, a method similar to the method described in the above-described method for forming the wall portion can be used.

  Subsequently, after forming a desired pattern by removing a portion other than the exposed portion of the photosensitive film, that is, an unexposed portion using a developing solution, the exposed portion of the photosensitive film is cured by light or heat and cured. Form a wall made of objects. In addition, each process of exposure, image development, and hardening can use the method similar to the formation method of the wall part mentioned above.

  In addition, when using the photosensitive film laminated body of this invention for formation of the cover part of the hollow structure of a SAW filter so that it may mention later, a wall part is formed by methods other than the method of using the photosensitive film laminated body of this invention. It may be.

  A lid is provided on the upper end of the wall portion formed as described above to form a hollow structure. Here, the cover part peels off the protective film from the photosensitive film laminate of the present invention, and after the photosensitive film surface is attached to the upper end of the wall part, exposure, development and curing are performed to form the cover part. be able to. The lid and the wall can be bonded by, for example, bonding by thermocompression using a roll laminator.

  The lid may be made of a material other than the photosensitive film laminate of the present invention, for example, a known permanent resist or a sealing substrate such as ceramic. However, it is preferable that the lid portion is made of a material having excellent moisture and heat resistance and a low water absorption rate. In this case, at least a wall portion formed using the photosensitive film laminate of the present invention is used as a wall portion for forming a SAW filter hollow structure.

  After forming the wall portion and the lid portion as described above, in order to make an electrical connection between the electrode and the conductor wired on the inside of the substrate and the opposite surface of the electrode, the formation of the plating and the metal ball May be mounted.

  When forming the wall portion, a hole for forming an internal 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 it exposes through a mask. Since the mask is shielded so that light does not pass through only the part corresponding to the diameter of the hole for forming the internal conductor, the other part forms a light-cured lid. The unexposed portion of the lid portion is subjected to patterning by performing a desmear process or the like after development in order to completely penetrate the hole formed in the wall portion. Moreover, you may use a laser for the patterning of a cover part. As the laser, a known laser such as a YAG laser, carbon dioxide laser, or excimer laser can be used. Exposure or laser irradiation can be appropriately selected and used according to the thickness of the wall, the shape of the internal conductor formed inside the wall, and the shape of the lid surface wiring pattern.

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

  Furthermore, the SAW filter may be sealed with a sealing material. When sealing with a sealing material, it is generally performed in the following steps, but is not limited thereto. First, the SAW filter is set in a molding die. Next, a solid sealing material tablet is set in the pot of the molding machine. Furthermore, the sealing material is melted under conditions of a mold temperature of 150 to 180 ° C., and pressure is applied to the mold (mold). Finally, pressurization is performed for 30 to 120 seconds, the mold is opened after the sealing material is thermally cured, and the molded product is taken out to complete the sealing of the SAW filter.

  Usually, the sealing with the sealing material is performed before the metal ball is mounted, and after the sealing, the metal ball is mounted on the opposite surface of the substrate by reflow. However, after the metal ball is mounted, sealing with a sealing material may be performed. The SAW filter sealed with the sealing material can be manufactured not only in one piece but also in a plurality. In this case, it can be obtained by sealing a plurality of SAW filters formed on one substrate with a sealing material and then cutting them into individual pieces. Specifically, first, a large number of SAW filters are produced on one substrate, and a wall portion and a lid portion are formed using the photosensitive film laminate of the present invention. Thereafter, the SAW filter can be obtained by sealing with a sealing material in a lump and dividing into pieces by a method such as cutting.

  As described above, in the SAW filter manufacturing process, a hollow structure having a wall portion and a lid portion can be formed using the photosensitive film laminate of the present invention. As described above, the photosensitive film laminate of the present invention realizes a SAW filter in which peeling of the adjacent portion of the hollow structure is suppressed because the change of the surface shape with time is within a specific range. be able to. In addition, since the inside of the hollow structure can be moisture-proof by being isolated from the surroundings by the wall portion and the lid portion formed using the photosensitive film laminate of the present invention, corrosion of the aluminum electrode can be suppressed. Moreover, since the hardened | cured material of a 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 pressure at the time of sealing resin molding.

  EXAMPLES Next, although an Example is given and this invention is demonstrated still in detail, this invention is not limited to these Examples. In the following description, “parts” and “%” are based on mass unless otherwise specified, except for% relating to relative humidity. Further, the operations in the following examples were performed at room temperature (23 ° C.), a relative humidity of 42%, and under a yellow lamp.

<Synthesis Example 1>
<Synthesis of carboxyl group-containing resin>
A bifunctional bisphenol-A type epoxy resin (RE-310S, Nippon Kayaku Co., Ltd., epoxy equivalent: 183) as an epoxy compound having two or more epoxy groups in the molecule in a 2 L flask equipped with a stirrer and a reflux tube. 0.5 g / equivalent) is 367.0 parts, acrylic acid (molecular weight: 72.06) is 144.1 parts as a monocarboxylic acid compound having an ethylenically unsaturated group, and hydroquinone monomethyl ether is 1.02 as a thermal polymerization inhibitor. 1.53 parts of triphenylphosphine as a reaction catalyst and a reaction catalyst were allowed to react at a temperature of 98 ° C. until the acid value of the reaction solution became 0.5 mgKOH / g or less, and an epoxycarboxylate compound (theoretical molecular weight: 511. 1) was obtained.
Subsequently, 445.93 parts of carbitol acetate as a reaction solvent, 0.70 part of 2-methylhydroquinone as a thermal polymerization inhibitor, and dimethylolpropionic acid (molecular weight: 134 as a diol compound having a carboxyl group) were added to this reaction solution. .1) was added to 118.8 parts, and the temperature was raised to 60 ° C. To this solution, 209.6 parts of isophorone diisocyanate (molecular weight: 222.29) as a diisocyanate compound was gradually added dropwise so that the reaction temperature did not exceed 65 ° C. After completion of the dropping, the temperature was raised to 80 ° C., and the mixture was reacted for 6 hours until absorption near 2250 cm ⁻¹ disappeared by an infrared absorption spectrum measurement method. To this solution, 36.7 parts of succinic anhydride (molecular weight: 100.1) and 43.0 parts of carbitol acetate were added as polybasic acid anhydrides. After the addition, the temperature was raised to 95 ° C. and reacted for 6 hours to obtain a carboxyl group-containing photosensitive resin varnish 1 containing 65% by weight of a carboxyl group-containing polyester urethane resin having a weight average molecular weight of 10,000. When the acid value was measured, it was 66.61 mg KOH / g (solid content acid value: 102.5 mg KOH / g). The weight average molecular weight was measured by a gel permeation chromatography (GPC) method (polystyrene standard) according to a conventional method.

<Synthesis Example 2>
<Synthesis of carboxyl group-containing resin>
In an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device, and a stirring device, 119.4 g of a novolac-type cresol resin (Shounol CRG951, OH equivalent: 119.4) manufactured by Aika Kogyo Co., Ltd. and potassium hydroxide 1 .19 g and 119.4 g of toluene were charged, the system was purged with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 g of propylene oxide was gradually added dropwise and reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm ² for 16 hours. Thereafter, the reaction solution 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. The nonvolatile content was 62.1% and the hydroxyl value was 182.2 g / eq. A novolak-type cresol resin propylene oxide reaction solution was obtained. The resulting novolac cresol resin had an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl group.
293.0 g of the obtained novolak-type cresol resin alkylene oxide reaction solution, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone and 252.9 g of toluene were mixed with a stirrer and a thermometer. And a reactor equipped with an air blowing tube, air was blown at a rate of 10 ml / min, and the reaction was carried out at 110 ° C. for 12 hours while stirring. As the water produced by the reaction, 12.6 g of water was distilled as an azeotrope with toluene. Thereafter, the mixture was cooled to room temperature, and the resulting reaction solution was neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution and then washed with water. Thereafter, toluene was distilled off while substituting 118.1 g of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak acrylate resin solution. Next, 332.5 g of the obtained novolak acrylate resin solution and 1.22 g of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml / min. While stirring, 62.3 g of tetrahydrophthalic anhydride was gradually added and reacted at 95 to 101 ° C. for 6 hours to obtain a carboxyl group-containing photosensitive resin varnish 2 having an acid value of 88 mgKOH / g and a nonvolatile content of 71%. Obtained.

<Synthesis Example 3>
<Synthesis of carboxyl group-containing resin>
Cresole novolak type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, epoxy equivalent 220 g / eq) 220 parts (1 equivalent), carbitol acetate 140.1 parts, and solvent naphtha 60.3 parts were charged in a flask, 90 Heated and stirred at 0 ° C. to dissolve.
The obtained solution is once cooled to 60 ° C., 72 parts (1 mol) of acrylic acid, 0.5 part of methylhydroquinone and 2 parts of triphenylphosphine are added, heated to 100 ° C., reacted for about 12 hours, A reaction product having a value of 0.2 mgKOH / g was obtained. To this was added 80.6 parts (0.53 mol) of tetrahydrophthalic anhydride, and the mixture was heated to 90 ° C. and reacted for about 6 hours to contain a carboxyl group having a solid content acid value of 85 mgKOH / g and a solid content of 64.9%. A photosensitive resin varnish 3 was obtained.

<Synthesis Example 4>
<Synthesis of carboxyl group-containing resin>
190 parts of a phenol novolac type epoxy resin EPPN-201 (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent = 190) is placed in a four-necked flask equipped with a stirrer and a reflux condenser, and 184 parts of carbitol acetate is added and heated. Dissolved. Next, 0.46 parts of methylhydroquinone as a polymerization inhibitor and 1.38 parts of triphenylphosphine as a reaction catalyst were added. This mixture was heated to 95 to 105 ° C., and 72 parts (1 equivalent) of acrylic acid was gradually added dropwise to react for 16 hours. The obtained reaction product (hydroxyl group: 1 equivalent) was cooled to 80 to 90 ° C., 50 parts (0.5 equivalent) of succinic anhydride was added, allowed to react for 8 hours, cooled and taken out. Thus, a carboxyl group-containing photosensitive resin varnish 4 having a nonvolatile content of 65%, a solid acid value of 89 mgKOH / g, and a solid content of 65.0% was obtained.

<Preparation of photosensitive composition>
It mix | blended by the content and ratio (mass part) which are shown in following Table 1, and knead | mixed so that each component might become uniform, and prepared the photosensitive compositions 1-4. In Table 1, * 1 to * 22 represent the following components.
* 1 Methylated melamine resin, manufactured by Sanwa Chemical Co., Ltd. * 2 Fluorene skeleton-containing epoxy resin, manufactured by Osaka Gas Chemical Co., Ltd. * 3 Bisphenol A type epoxy resin (manufactured by DIC Corporation)
* 4 Biphenyl aralkyl epoxy resin (Nippon Kayaku Co., Ltd.)
* 5 Phenol novolac epoxy resin (manufactured by DIC Corporation)
* 6 Dicyclopentadiene type epoxy resin (manufactured by DIC Corporation)
* 7 Synthesis Example 1 (blending amount is solid content)
* 8 Synthesis example 2 (blending amount is solid content)
* 9 Synthesis example 3 (blending amount is solid content)
* 10 Synthesis Example 4 (blending amount is solid content)
* 11 Alkali-available photosensitive resin with an amideimide structure (solid content 20%, manufactured by Nippon Kogyo Paper Industries Co., Ltd.)
* 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, manufactured by Shin-Nakamura Chemical Co., Ltd. * 15 Oxime Ester-based photopolymerization initiator (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime)), manufactured by BASF Japan Ltd. * 16 Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (manufactured by IGM Resins)
* 17 2-Ethyl-4-methylimidazole (manufactured by Shikoku Chemicals Co., Ltd.)
* 18 Spherical silica, manufactured by Admatechs Co., Ltd. * 19 Spherical silica particles with an average particle size of 100 nm * 20 C.I. I. Pigment Blue 15: 3
* 21 C.I. I. Pigment Yellow 147
* 22 Paligen Red K3580 (BASF Japan)

<Preparation 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% are supplied to the extruder, and the resin temperature It was melted at a temperature of 250 ° C., extruded by a T-die, wound around a metal drum having a surface temperature maintained at 150 ° C., and formed into a film, thereby producing a cast raw sheet having a thickness of about 225 μm. Subsequently, this unstretched cast sheet was stretched 5 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. A biaxially stretched polypropylene film 1 having a thickness of 12 μm was obtained. This biaxially stretched polypropylene film 1 is referred to as a protective film 1.

Production Example 2
A polypropylene resin pellet 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% is supplied to an extruder, The resin was melted at a temperature of 250 ° C., extruded through a T-die, wound around a metal drum having a surface temperature maintained at 150 ° C. to form a film, and a cast raw sheet having a thickness of about 225 μm was produced. Subsequently, this unstretched cast sheet was stretched 5 times in the flow direction at a temperature of 200 ° C., immediately cooled to room temperature, and then stretched 10 times in the transverse direction at a temperature of 160 ° C. by a tenter. A biaxially stretched polypropylene film 2 having a thickness of 15 μm was obtained. This biaxially stretched polypropylene film 2 is referred to as a 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% are supplied to the extruder, and the resin temperature It was melted at a temperature of 250 ° C., extruded with a T-die, wound around a metal drum having a surface temperature maintained at 100 ° C., and formed into a film, thereby producing a cast raw sheet having a thickness of about 225 μm. Subsequently, this unstretched cast sheet was stretched 5 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. A biaxially stretched polypropylene film 3 having a thickness of 12 μm was obtained. This biaxially stretched polypropylene film 3 is referred to as a protective film 3.

<Support film>
As the support film 1, a polyethylene terephthalate film (Lumirror T60 manufactured by Toray Industries, Inc.) was used.

<Preparation of photosensitive film laminate>
Example 1
When the arithmetic average surface roughness Ra ′ and the maximum height Ry ′ of the protective film 1 obtained as described above were measured as follows, Ra ′ was 0.18 μm and the maximum height was measured. Ry ′ was 1.28 μm.

  A shape measuring laser microscope (VK-X100 manufactured by Keyence Corporation) was used for the measurement of the arithmetic average surface roughness Ra ′ and Ry ′. Protective film (photosensitive film) for measuring on the xy stage after starting the shape measurement laser microscope (VK-X100) main body (control unit) and VK observation application (VK-H1VX manufactured by Keyence Corporation) The surface that touches the top is the top). Turn the lens revolver of the microscope section (VK-X110 manufactured by Keyence Corporation) to select an objective lens with a magnification of 10x, and adjust the focus and brightness roughly in the image observation mode of the VK observation application (same VK-H1VX). did. The xy stage was operated so that the part of the sample surface to be measured was adjusted to the center of the screen. The objective lens with a magnification of 10 times was changed to a magnification of 50 times, and the surface of the sample was focused with the autofocus function in the image observation mode of the VK observation application (VK-H1VX). The simple mode of the shape measurement tab of the VK observation application (same VK-H1VX) was selected, the measurement start button was pressed, the surface shape of the sample was measured, and a surface image file was obtained. The VK analysis application (Keyence Co., Ltd. VK-H1XA) was started and the obtained surface image file was displayed, and then the tilt correction was performed.

  The observation measurement range (horizontal) in measuring the surface shape of the sample was 270 μm. Display the line roughness window, select JIS B0601-1994 in the parameter setting area, select the horizontal line from the measurement line button, display the horizontal line at an arbitrary location in the surface image, and press the OK button. Numerical values of arithmetic average surface roughness Ra ′ and maximum height Ry ′ were obtained. Further, horizontal lines were displayed at four different positions in the surface image, and numerical values of the arithmetic average surface roughness Ra ′ and the maximum height Ry ′ were obtained. The average values of the obtained five numerical values were respectively calculated and used as the arithmetic average surface roughness Ra ′ value and the maximum height Ry ′ value of the sample surface. The measurement was performed in an environment of room temperature (23 ° C.) and a relative humidity of 42%.

  Subsequently, 700 parts of the photosensitive composition 1 obtained as described above was diluted by adding 300 parts of methyl ethyl ketone, and stirred for 15 minutes with a stirrer to obtain a coating solution. This coating solution was uniformly applied on the support film 1 using a slit die coater and dried at a temperature of 80 ° C. for 15 minutes to prepare a photosensitive film 1 having a dried thickness of 25 μm. Next, the protective film 1 is placed on the photosensitive film 1 with a roll laminator so that the measurement surface of the arithmetic average surface roughness Ra ′ and the maximum height Ry ′ of the protective film 1 is in contact with the surface of the photosensitive film 1. By bonding, a photosensitive film laminate 1 (photosensitive film thickness of 25 μm) composed of three layers of support film / photosensitive film / protective film was produced. In addition, as lamination conditions by the said roll laminator, it adjusted suitably in the range of roll temperature 40-60 degreeC, and roll pressure 0.2-0.4 MPa.

<Production of test substrate>
A test substrate was prepared using the photosensitive film laminate 1 obtained as described above. The procedure for producing the test substrate will be described with reference to the drawings.
First, the protective film is peeled off from the photosensitive film laminate 1 at an angle of 90 ° with respect to the other two layers (support film / photosensitive film) and at a speed of 2.5 seconds / cm to remove the photosensitive film. The exposed surface of the photosensitive film was bonded to the surface of the exposed silicon wafer, and heat lamination was performed using a roll laminator to adhere the silicon wafer and the photosensitive film. The laminating conditions using the roll laminator were a roll temperature of 60 ° C. and a roll pressure of 0.25 MPa.

Next, from the support film in contact with the photosensitive film,
(I) A negative mask having an aperture pattern of 150 μm square and 50 μm square (see FIG. 1), or (ii) a negative mask having an aperture pattern of 150 μm square and 100 μm square (not shown)
For each example and each comparative example, the photosensitive film was exposed with a combination of pattern opening and exposure amount described in Table 2 with a metal halide lamp, and then the support film was peeled to expose the photosensitive film.

Thereafter, the exposed surface of the exposed photosensitive film was immersed in propylene glycol monomethyl ether acetate (PMA) at 23 ° C. for 1 minute for Examples 1-3 and Comparative Examples 1-2, and for Example 4 Was developed with 1 wt% Na ₂ CO ₃ aqueous solution, 30 ° C., 2 MPa, 60 seconds, and Example 5 was developed with 1 wt% Na ₂ CO ₃ aqueous solution, 30 ° C., 2 MPa, 300 seconds. Each test substrate after development was thoroughly washed with water so that no developer remained. As a result of the observation on the pH of 1wt% _Na 2 CO ₃ aqueous solution was 11.6.

Subsequently, each test substrate is heated at 120 ° C. for 30 minutes to cure the photosensitive film, and around the openings that are 150 μm square in a lattice shape,
(I) A cured film pattern corresponding to a 150 μm wide wall having a 50 μm square pattern opening in the center (see FIG. 2), or (ii) corresponding to a 300 μm wide wall having a 100 μm square pattern opening in the center. Curing pattern (not shown)
Got.

  Further, the protective film is peeled off from the photosensitive film laminate 1 to expose the photosensitive film, and the exposed surface of the photosensitive film is bonded onto the cured film pattern corresponding to the wall portion obtained above, and heated lamination Went. Lamination was performed by heating at 80 ° C. for 5 minutes while applying a weight of 1.0 kg on the photosensitive film.

Next, from the support film side of the photosensitive film laminate bonded on the cured film pattern corresponding to the wall,
(I) a negative mask having an aperture pattern with a grid size of 50 μm square (see FIG. 3), or (ii) a negative mask having an aperture pattern with a grid size of 100 μm square (not shown).
For each example and each comparative example, the photosensitive film was exposed with a combination of pattern opening and exposure amount described in Table 2 with a metal halide lamp, and then the support film was peeled to expose the photosensitive film. In addition, through the laminated photosensitive film laminate,
(I) The pattern opening of 50 μm square on the wall and the pattern opening of 50 μm square of the negative mask overlap (see FIG. 3), or (ii) the pattern opening of 100 μm square on the wall and the negative mask grid So that the pattern opening of size 100 μm square overlaps (not shown),
Exposure was performed. Thereafter, the exposed surface of the exposed photosensitive film was immersed in propylene glycol monomethyl ether acetate (PMA) at 23 ° C. for 1 minute for Examples 1-3 and Comparative Examples 1-2, and for Example 4 Was developed with 1 wt% Na ₂ CO ₃ aqueous solution, 30 ° C., 2 MPa, 60 seconds, and Example 5 was developed with 1 wt% Na ₂ CO ₃ aqueous solution, 30 ° C., 2 MPa, 300 seconds. Each test substrate after development was thoroughly washed with water so that no developer remained.

Subsequently, each test substrate is heated at 200 ° C. for 60 minutes to cure the photosensitive film, thereby forming a cured film pattern corresponding to the lid portion, thereby having a hollow structure including a wall portion and a lid portion. Was made. The obtained test substrate does not have a comb-shaped electrode inside, but the upper end of the wall is covered with a lid, and the joint of the lid and the wall is
(I) 50 μm square pattern opening (see FIG. 4) or (ii) 100 μm square pattern opening (not shown)
It has a hollow structure formed.

Example 2
A test substrate was produced in the same manner as in Example 1 except that the photosensitive composition 2 was used in place of the photosensitive composition 1 and the protective film 2 was used in place of the protective film 1. . The arithmetic average surface roughness Ra ′ and the maximum height Ry ′ of the protective film 2 were measured in the same manner as described above. As a result, Ra ′ was 0.46 μm and the maximum height Ry ′ was 1.37 μm. It was. In addition, the protective film 2 was roll shape and measured the winding inner surface.

Example 3
A test substrate was produced in the same manner as in Example 1 except that the protective film 2 was used instead of the protective film 1 in Example 1.

Example 4
In Example 2, a test substrate was prepared in the same manner as in Example 2 except that 1 wt% Na ₂ CO ₃ aqueous solution, 30 ° C., 2 MPa, 60 seconds development was performed instead of development with propylene glycol monomethyl ether acetate (PMA). Produced.

Example 5
Example 4 is the same as Example 4 except that the photosensitive composition 3 was used in place of the photosensitive composition 2 and development was performed with a 1 wt% Na ₂ CO ₃ aqueous solution, 30 ° C., 2 MPa, 300 seconds. Thus, a test substrate was produced.

Comparative Example 1
A test substrate was produced in the same manner as in Example 2 except that the photosensitive composition 4 was used in place of the photosensitive composition 2 in Example 2.

Comparative Example 2
A test substrate was produced in the same manner as in Example 1 except that the protective film 3 was used in place of the protective film 1 in Example 1. The arithmetic average surface roughness Ra ′ and the maximum height Ry ′ of the protective film 3 were measured in the same manner as described above. As a result, Ra ′ was 0.07 μm and the maximum height Ry ′ was 0.98 μm. It was. In addition, the protective film 3 is roll shape and measured the winding inner surface.

<Measurement of arithmetic average surface roughness Ra and maximum height Ry>
Each photosensitive film laminate (35 mm × 20 mm) used in Examples 1 to 5 and Comparative Examples 1 and 2 was placed on a clean glass substrate (76 mm × 26 mm × 1.1 mmt) surface, and a glass substrate and a photosensitive film. The glass substrate and the photosensitive film laminate were adhered to each other using a double-sided tape (KZ-12, manufactured by Nitoms Co., Ltd.) so that the support film side was in contact with the glass substrate.
Thereafter, the protective film of the photosensitive film laminate was peeled off at an angle of 90 ° with respect to the glass substrate and at a rate of 2.5 seconds / cm to expose the photosensitive film. The arithmetic average surface roughness Ra1 and maximum height Ry1 of the exposed photosensitive film surface immediately after the protective film peeling (after 1 minute) were measured within 5 minutes immediately after the protective film peeling. Ra1 and Ry1 were measured as follows.

  The “arithmetic average surface roughness Ra” of the exposed photosensitive film surface is the same as the measurement of the arithmetic average surface roughness Ra ′ of the protective film surface, and the exposed photosensitive film is replaced with the protective film. The measurement was performed in the same manner as described above except that the substrate was bonded (the exposed photosensitive film surface is the upper part). In addition, for the “maximum height Ry” of the exposed photosensitive film surface, the same apparatus as the measurement of the maximum height Ry ′ of the support film surface is used, the sample is replaced with a protective film, and the exposed photosensitive film is bonded. The measurement was carried out in the same manner as described above except that the substrate (exposed photosensitive film surface was the top) was used. The “arithmetic average surface roughness Ra1” and “maximum height Ry1” of the measured surface of each photosensitive film were as shown in Table 2.

  In addition, each measurement sample was allowed to stand for 180 minutes under a yellow lamp in a measurement environment (room temperature (23 ° C.), relative humidity 42%) with the surface of the photosensitive film exposed by peeling off the protective film. Thereafter, in the same manner as described above, the arithmetic average surface roughness Ra and the maximum height Ry of the exposed photosensitive film surface were measured. The “arithmetic average surface roughness Ra2” and “maximum height Ry2” of the measured surface of each photosensitive film were as shown in Table 2.

<Plating adhesion evaluation>
Electroless copper plating was performed on the test substrates of Examples 1 to 5 and Comparative Examples 1 and 2 produced as described above. The plating conditions were as follows.
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 on which the electroless plating film was formed was washed with pure water at room temperature for 5 minutes and then dried at 80 ° C. The cross-sectional portion of the boundary between the obtained wall portion of each test substrate and the electroless plating film was observed with an optical microscope and an electron microscope. The evaluation criteria were as follows.
◎: No gap is generated and there is no problem with adhesion. ○: A gap is generated slightly, but there is no problem with adhesion. ×: A gap is generated and there is a problem with adhesion. The evaluation results are as shown in Table 2 below. Met.

As is clear from the results in Table 2, the photosensitive film laminate has an arithmetic average surface roughness Ra1 of 0.1 μm or more and Ra2 / Ra1 of 0.40 or more and less than 1.00. Test boards 1 to 5 (Examples 1 to 5) in which a hollow structure is formed using a body have high adhesion to the plating of the wall and the lid, and an electronic component having a high-quality hollow structure is obtained. I understand.
On the other hand, the test substrate 7 (Comparative Example 2) in which a hollow structure is formed using a photosensitive film laminate in which the arithmetic average surface roughness Ra1 of the photosensitive film surface is less than 0.1 μm has a Ra2 / Ra1 of 0.40. Even if it is less than 1.00 above, it turns out that the adhesiveness with plating of a wall part and a cover part is inadequate.
Moreover, even if arithmetic mean surface roughness Ra1 of the photosensitive film surface is 0.1 μm or more, a hollow structure is formed using a photosensitive film laminate in which Ra2 / Ra1 is not in the range of 0.40 or more and less than 1.00. It can be seen that the formed test substrate 6 (Comparative Example 1) also has insufficient adhesion with the plating of the wall portion and the lid portion.

Claims (8)

A photosensitive film laminate comprising a support film, a photosensitive film formed of a photosensitive composition, and a protective film in order,
The protective film is peeled off from the photosensitive film laminate to expose the surface of the photosensitive film, and the arithmetic average surface roughness of the surface of the photosensitive film after being left for 1 minute in an environment of 23 ° C. and 42% relative humidity. Ra1,
The protective film is peeled off from the photosensitive film laminate to expose the surface of the photosensitive film, and after being left in an environment of 23 ° C. and 42% relative humidity for 180 minutes, the arithmetic average surface roughness of the surface of the photosensitive film. Ra2
If the following formula:
Ra1 ≧ 0.10 μm and 0.40 ≦ Ra2 / Ra1 <1.00
The photosensitive film laminated body characterized by satisfy | filling. The protective film is peeled off from the photosensitive film laminate to expose the surface of the photosensitive film, and the maximum height of the photosensitive film surface after being left for 1 minute in an environment of 23 ° C. and 42% relative humidity is defined as Ry1. ,
The protective film is peeled off 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 set. Ry2,
If the following formula:
Ry1 ≧ 1.00 μm and 0.30 ≦ Ry2 / Ry1 <1.00
The photosensitive film laminated body of Claim 1 which satisfy | fills.   The photosensitive film laminated body of Claim 1 or 2 in which the said photosensitive composition contains a photocurable compound.   The photosensitive film laminated body as described in any one of Claims 1-3 in which the said photosensitive composition contains a photoinitiator further.   The photosensitive film laminated body as described in any one of Claims 1-4 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.   Hardened | cured material obtained by hardening the photosensitive film of the photosensitive film laminated body as described in any one of Claims 1-5.   An electronic component comprising the cured product according to claim 6.   The electronic component according to claim 7, wherein the electronic component has a hollow structure including a wall portion and a lid portion, and either or both of the wall portion and the lid portion are formed of the cured product.