TW201303501A - Photosensitive resin composition, photosensitive film, forming method for rib pattern, forming method for hollow structure, and electronic component - Google Patents

Abstract

A photosensitive resin composition, comprising a photopolymerisable initiator (B) and a photopolymerisable compound (A) containing a urethane compound (A1) having at least one type of an acryloyl group and a methacryloyl group, has excellent heat and moisture resistance, has high elasticity in a cured product, also has excellent hollow-structure maintainability, and is suitable as a material used as a rib material and/or a lid material that form the hollow structure in an electronic component having a hollow structure.

Description

Photosensitive resin composition, photosensitive film, rib pattern forming method, hollow structure forming method, and electronic part

The present invention relates to a photosensitive resin composition, a photosensitive film formed using the composition, a method of forming a rib pattern, a method of forming a hollow structure, and an electronic component.

In recent years, due to the development of high integration and miniaturization of semiconductor devices, rapid capacity increase and cost reduction have been achieved. A package that exhibits a specific electrical function by forming an electrode pattern or a fine structure on the surface of a single crystal wafer, which is represented by a surface acoustic wave (SAW) filter, and causes a characteristic change on the surface of the functional portion coated with a resin or the like. For this reason, it is necessary to have a hollow structure in such a manner that the surface of the element, particularly the portion important for the function, does not come into contact with other objects. In addition, an image sensor represented by a CMOS or CCD sensor has a hollow structure in which a light-receiving portion is covered with a glass cover in order to protect the device from moisture or dust that hinders imaging, and does not shield light from the outside. Other MEMS (Micro Electro Mechanical System), such as a gyroscope or a milliwave rader, have a hollow structure for protecting a movable portion.

In an element which has such a hollow structure, conventionally, a hollow structure is formed by processing/joining of an inorganic material. However, in order to reduce the cost of parts and the amount of work, and to reduce the size and structure of the structure, it is necessary to have a frame portion and/or a cover portion formed of a resin. The hollow structure and its formation method are discussed. In particular, the use of the photosensitive resin material makes it easy to form the shape of the hollow structure by the lithography technique and the opening for forming the electrode portion, and a very large cost reduction effect is obtained.

In the electronic components having a hollow structure, it is described that a photosensitive polyimide, a photosensitive epoxy resin, or the like is used as a peripheral wall portion for forming a hollow portion. Photosensitive resin material for the frame edge portion and/or the patio portion (cover portion).

In addition, an electronic component having a hollow structure such as a surface acoustic wave device (SAW device) can be manufactured by mounting the mounted substrate so as to have an external terminal or an external electrode that is electrically connected to the wiring electrode of the piezoelectric substrate. The packaging structure. In this case, the frame edge portion of the hollow portion and the periphery of the lid portion are formed, and the resin is sealed by, for example, transfer molding or the like in order to improve the protection and operability of the element (see, for example, Patent Documents 4 to 7).

Further, the surface acoustic wave device is an electronic component that is mounted on the same substrate and integrated with a plurality of components such as an IC, in terms of an electronic device such as a mobile phone terminal device. In order to protect the components mounted on the same substrate, the modular electronic components are vacuum-layered or vacuum-pressed by using a semiconductor sealing material or by using a photosensitive epoxy resin. In the method, the element is sealed with a resin (for example, Patent Documents 8 to 9).

The resin is sealed by a transfer molding method, and usually molded at a high temperature and high pressure (150 to 200 ° C, 50 to 150 kg/cm ² ), and a high voltage can be applied to an element mounted on the substrate. As a result, the frame edge portion and the lid portion forming the hollow portion are deformed, and problems such as contact with the wiring electrode of the piezoelectric substrate or large strain in the vibration space occur. Therefore, in Patent Documents 4 to 8, That is, various methods for solving the problem of deformation of such a hollow structure have been proposed.

Further, in the above-described Patent Document 9, it is disclosed that the first sealing portion forming the cavity (hollow) reduces the elastic modulus of the second sealing portion provided around the first sealing portion to prevent hollowness The method of constructing the deformation.

Further, a structure in which a frame portion and/or a lid portion of a hollow structure are formed by using a photosensitive resin is known, and it is known that a single substrate can be used to manufacture a method similar to wafer level packaging of an electronic component such as a surface acoustic wave device. Reference is made to the aforementioned Patent Documents 2, 6 to 8). The package manufactured by the substrate can greatly reduce the manufacturing cost, and the structure and manufacturing method are also disclosed in Patent Documents 10 to 12.

[Previous Technical Literature] [Japanese Patent Literature]

[Patent Document 1] JP-A-2010-10812

[Patent Document 2] Japanese Patent Publication No. 2003-523082

[Patent Document 3] JP-A-2008-250200

[Patent Document 4] JP-A-2007-142770

[Patent Document 5] JP-A-2001-185976

[Patent Document 6] JP-A-2009-200996

[Patent Document 7] JP-A-2009-212760

[Patent Document 8] International Publication No. 2009/057699

[Patent Document 9] JP-A-2007-208665

[Patent Document 10] JP-A-2009-117730

[Patent Document 11] International Publication No. 2008/018452

[Patent Document 12] International Publication No. 2010/061821

However, the above-mentioned Patent Documents 1 to 12 disclose that the epoxy resin or the polyimide resin as the photosensitive resin is a general-purpose material used in the field of conventional lithography, but whether it can be used to form The material of the fine and sturdy hollow structure alone, whether the resin can be used as a material capable of sufficiently ensuring the shape retention of the hollow structure at a high temperature and various reliability as an electronic component, has no specific report and is hardly related. Review.

In general, the photosensitive resin is more resistant to heat and moisture resistance or to the substrate, and is more thermosetting than the thermosetting resin which is cured only by heat. Resin is difficult. In other words, in the case of the photosensitive epoxy resin, the moisture absorption rate or the moisture permeability ratio tends to be higher than that of the thermosetting epoxy resin, and sufficient moist heat resistance cannot be obtained, and the hollow structure cannot be secured. The problem of reliability that the device expects.

Further, in the above patent documents, there is no specific review of the elastic modulus of the photosensitive epoxy resin after photocuring. Therefore, when the photosensitive epoxy resin described in these patent documents is used, deformation, undercut, or depression of the resin may occur during or during use, and the hollow structure retention property may be impaired. Suffered a lot of damage. In particular, in order to ensure reliability or modularization with other devices, when the hollow structure device is subjected to molding by a sealing resin in a subsequent step, when a pressure is applied to the hollow structure under high temperature and high pressure conditions, The hollow structure is likely to collapse, and thus it is unstable in the maintenance of shape and electrical characteristics, and becomes a big problem.

In addition, in the high-temperature repetitive process of solder reflow which is performed on the substrate, the photosensitive epoxy resin is not only deformed but also has a high possibility of occurrence of cracking or peeling. problem. Further, in the lithography using a photosensitive epoxy resin, a pattern is generally formed in an opening diameter of 100 μm or more. In the above-mentioned patent documents, the formation of fine patterns below the conditions is not disclosed, and it is not clear whether or not a fine pattern can be formed by a photosensitive epoxy resin.

Further, the above-mentioned patent document discloses a photosensitive polyimide resin having a photosensitive resin having high heat resistance and high reliability, and generally has a problem that it is difficult to form a film having a thickness of 10 μm or more. Therefore, when a photosensitive polyimide resin is used, it is difficult to form a sufficient thickness required for rib formation of a hollow structure. In the miniaturization or high-precision of the hollow structure device, the rib formation which is thick film and has a fine pattern is indispensable, but the material selection range of the photosensitive polyimide resin is small, and it is difficult to sufficiently conform to this. Claim.

Further, as described above, the photosensitive polyimide resin is difficult to form a thick film, and when the resin is applied to a lid portion having a hollow structure, it is difficult to form a lid portion having a sufficient thickness and a thin film shape. Poor durability under high temperature and high pressure conditions. Although it can be used together as a material with high rigidity as a reinforcing material, New problems such as cost or workload increase.

Further, the photosensitive polyimide resin must be cured at 250 ° C or higher in order to achieve desired physical properties or characteristics. When heating at such a high temperature, it is difficult to apply to a SAW FILTER device or the like which may cause stress generation or damage to the substrate.

As described above, in the conventional photosensitive polyimide resin, it is necessary to greatly improve the structure, physical properties, and properties of the material itself while forming the ridge portion and the lid portion of the hollow structure, while the application range is limited.

Further, in the above-mentioned Patent Documents 8, 10 to 12, a photosensitive acrylate-based resin other than a photosensitive epoxy resin or a photosensitive polyimide resin is exemplified. The photosensitive acrylate-based resin exemplified is known to have physical properties or characteristics depending on the combination with various materials. However, similarly to the photosensitive epoxy resin or the photosensitive polyimide resin, there has not been sufficient review for preventing the deformation of the hollow structure and improving the reliability such as moist heat resistance. Therefore, in the above-mentioned patent documents, the specific kind and structure of the resin which can satisfy these characteristics at the same time are completely unknown. Therefore, it is necessary to design an optimum material for the type or structure of the material constituting the resin and the combination thereof.

In order to solve the above-mentioned problems, the present invention provides a photosensitive resin composition which is excellent in formability of a fine pattern, has a high elastic modulus, is excellent in moist heat resistance, and is excellent in hollow structure retention. A photosensitive film and an electronic component formed by using the composition, and a rib pattern forming method and a method of forming a hollow structure formed using the photosensitive resin composition or the photosensitive film are used.

In order to achieve the above object, the inventors of the present invention have evaluated the reliability of the improvement, the high modulus of elasticity, and the thickness of the composition of the photosensitive resin composition which is applied to the lid portion and/or the rib portion for the hollow structure. Film formability and pattern formation.

As a result, it has been found that the combination of the constituent components of the photosensitive resin composition is carried out, and the urethane-based compound having an acrylonitrile group and/or a methacryl oxime group is focused on photopolymerization. The compound was used to achieve the above object, and thus the present invention was completed.

That is, the present invention relates to the following (1) to (13).

(1) A photosensitive resin composition containing the photopolymerizable compound (A) and a photopolymerization initiator (B), wherein the photopolymerizable compound (A) contains at least one Acryl sulfhydryl group and methacryl oxime group urethane compound (A1).

(2) The photosensitive resin composition according to the above (1), wherein the urethane-based compound (A1) is a total of 2 to 15 propylene groups and methacryl groups in one molecule. The weight average molecular weight is 950~25000.

(3) The photosensitive resin composition according to (1), wherein the urethane-based compound (A1) is a total of 2 to 15 propylene groups and methacryl groups in one molecule. The weight average molecular weight is 950~15000.

(4) The photosensitive resin according to any one of (1) to (3) The composition further contains an inorganic filler (C).

(5) The photosensitive resin composition according to any one of the above-mentioned, wherein the cured product of the photosensitive resin composition has an elastic modulus at 150 ° C of 0.2 GPa or more.

(6) The photosensitive resin composition according to any one of (1) to (5), which is an electronic component having a hollow structure, and can be used as one of a ridge portion and a lid portion forming the hollow structure. Or both materials to use.

(7) A photosensitive film obtained by molding the photosensitive resin composition according to any one of (1) to (6) into a film shape.

(8) A method of forming a pattern, comprising: forming a photosensitive resin composition according to any one of (1) to (6) or a photosensitive film according to (7) on a substrate; And a step of laminating the photosensitive resin layer, an exposure step of irradiating the active light with a predetermined portion of the photosensitive resin layer to lightly cure the exposed portion, and a portion other than the exposed portion of the photosensitive resin layer. A developing step of removing the developing liquid, and a thermal curing step of thermally curing the exposed portion of the photosensitive resin layer to form a cured resin.

(9) A method of forming a hollow structure, comprising the step of forming any one of layers (1) to (6) on a rib pattern for forming a hollow structure on a substrate. a step of laminating a photosensitive resin layer formed of the photosensitive resin composition or the photosensitive film described in (7), and an exposure step of irradiating the predetermined portion of the photosensitive resin layer with the active light to photoharden the exposed portion, and The exposure portion of the photosensitive resin layer is thermally cured to form a heat-curing step of the cured resin.

(10) The method for forming a hollow structure according to (9), comprising the step of removing a portion other than the exposed portion of the photosensitive resin layer after the exposure step and before the thermosetting step ,.

(11) The method for forming a hollow structure according to (9) or (10), wherein the rib pattern is formed by the method described in (8).

(12) An electronic component having a hollow structure, wherein the hollow structure is formed by using the photosensitive resin composition according to any one of (1) to (6) or the photosensitive film described in (7) The ridge portion and/or the lid portion of the hollow structure are formed.

(13) The electronic component according to (12), wherein the electronic component is a surface acoustic wave filter.

The photosensitive resin composition of the present invention has excellent photocurability and photo-resolution, and can form a fine pattern not only in a thick film, but also a cured product of the photosensitive resin composition can exhibit high elastic modulus or high adhesion to a substrate. Sex. Therefore, the electronic device having a hollow structure to which the photosensitive resin composition of the present invention is applied has high modulus of elasticity, excellent heat and humidity resistance, and excellent hollow structure retention. Further, in the high temperature, since the film can maintain high adhesion to the substrate, even if it is a thick film, it has a great effect on the improvement of the resistance to reflow cracking.

[Formation of the Invention]

Hereinafter, the preferred embodiments of the present invention will be described in detail with reference to the drawings. In the following description, the same or equivalent portions are denoted by the same reference numerals to omit the repeated description. Further, the dimensional ratio of the drawings is not limited to the ratio shown.

In the following description of the present specification, for example, the phrase "(meth) acrylate compound" means a term used for one or both of "acrylate compound" and "methacrylate compound", and "( The term "methyl) acrylonitrile" means the term used for "one or both of" "acryloyl" and "methacryl". Also, other similar terms are the same.

In the present specification, the photopolymerizable compound (A) containing at least one urethane-based compound (A1) having an acryloyl group and a methacryl fluorenyl group is referred to as "(A) component. Or the "photopolymerizable compound (A)", the at least one urethane-based compound (A1) having an acryloyl group and a methacrylic acid group is referred to as "(A1) component" or "amine group" The formate compound (A1)", the (B) photopolymerization initiator are referred to as "(B) component", and the (C) inorganic filler is referred to as "(C) component".

In the present specification, the rib portion means a rim body that can constitute a side peripheral wall of the hollow structure. The frame body is not particularly limited as long as it can form a side peripheral wall of the hollow structure, and the outer shape of the frame may be a triangle, a quadrangle, or a pentagon or more, or may be a true circle, a circle, or the like. Round. Moreover, the frame body may also be a frame body lacking one of the parts. For the lack of a part of the frame body, for example, the shape of the letter type, the English alphabet C shape and so on. Further, the rib pattern refers to a ridge pattern formed by lithography.

When the photosensitive resin which is a material of the ridge portion and the lid portion of the hollow structure is formed by exposure, it is preferable that the light-transmissive property and the fine pattern property are excellent even in a thick film. Further, in order to improve the heat resistance and moisture resistance, the photosensitive resin is preferably one having a high heat resistance of the cured resin and having low hygroscopicity and low moisture permeability. As described above, conventional photosensitive epoxy resins or photosensitive polyimide resins for lithography are difficult to meet this requirement.

The present inventors have found that at least one urethane-based compound (A1) having an acryloyl group and a methacryloyl group has high photopolymerization reactivity, and is sensitive to thick film formation and pattern formation. Excellent characteristics. In addition, the present inventors have found that a chemical structure contributing to the improvement of the heat resistance of the cured resin is easily introduced into the molecule of the component (A1), and specifically, it is easy to introduce an increase in the glass transition temperature and a low absorption. The chemical structure that contributes to the moisture rate. Furthermore, the present inventors have found that the total number and weight average molecular weight of the propylene sulfhydryl group and the methacryl fluorenyl group in one molecule of the component (A1) are optimized, and it is determined that heat resistance/rigidity and highness can be achieved. The resin structure of the urethane-based compound is more preferable.

The photosensitive resin composition of the present invention contains a photopolymerizable compound (A) having the urethane-based compound (A1), and has a large selection range as a low-viscosity material to form a rib or a lid portion. In this case, it is easy to arbitrarily adjust the viscosity of the photosensitive resin composition applied to the substrate. Although a solvent can be used for the low viscosity of the photosensitive resin composition to be applied, at least when the photopolymerizable compound (A) is used, the tree after hardening can be reduced. The amount of solvent that adversely affects the properties or reliability of the lipid composition.

In addition, when the inorganic filler (C) is contained in the photosensitive resin composition, for example, even if the content of the inorganic filler (C) is large, the workability or film formability of the photosensitive resin composition can be maintained.

Next, the photosensitive resin composition, the photosensitive film, the pattern forming method, the hollow structure forming method, and the electronic component of the present invention will be described in order.

[Photosensitive Resin Composition]

The photosensitive resin composition of the present invention contains a photopolymerizable compound (A) and a photopolymerization initiator (B), wherein the photopolymerizable compound (A) has at least one of an acrylonitrile group and a methacryl group. A urethane-based compound (A1).

<(A) component>

In the present invention, the component (A) contains at least one urethane-based compound (A1) having a propylene group and a methacryl group. Further, the component (A) may contain a photopolymerizable compound (A2) other than the component (A1).

In the following, the component (A1) will be described, and then the polymerizable compound (A2) other than the component (A1) (hereinafter referred to as "component (A2)") will be described.

((A1) component)

In the present invention, the urethane-based compound (A1) having at least one of an acryloyl group and a methacryloyl group may, for example, be a (meth)acrylic monomer having an OH group at the β-position. Addition reaction of diisocyanate compound; EO modified urethane di(meth) acrylate; PO modified urethane di(meth) acrylate; carboxyl group containing urethane (Meth) acrylate; a diol compound, a reaction of a bifunctional epoxy (meth) acrylate and a polyisocyanate, and the like.

Among the above, the (meth)acrylic monomer having an OH group at the β-position includes 2-hydroxyethyl (meth) acrylate, dipentaerythritol penta (meth) acrylate, and pentaerythritol tri (methyl). ) Acrylate and the like. Further, in the above, as the diisocyanate compound, isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, 1,6-hexamethylene diisocyanate or the like. Among the above, the bifunctional epoxy (meth) acrylate may be one having two hydroxyl groups and two (meth) acrylonitrile groups in the molecule.

In the above (A1) component of the present invention, the total number of the acryloyl group and the methacrylic acid group as the functional group is preferably in the range of 2 to 15 in one molecule.

When the total number of the acryl-based group and the methacrylic fluorenyl group is two or more in one molecule, the heat resistance is extremely high, and the rigidity of the resin at a high temperature can be improved. In addition, when the total number of the acrylonitrile group and the methacrylic acid group is 15 or less, in addition to the high heat resistance and rigidity of the resin, the resin can be prevented from being weakened, and the adhesion can be improved to improve the reliability. Further, if the total number is 15 or less, the urethane is reduced by the weight average molecular weight. The viscosity of the compound (A1) makes it easy to coat the photosensitive resin composition. In addition, when the total amount is 15 or less, when the light-irradiated resin composition is applied, the functional group is not excessively applied, and only the surface portion is rapidly photocured, and the photocuring can be sufficiently performed. As far as the interior is concerned, the resolution will increase and the desired pattern will be formed. If the number of acryloyl fluorenyl groups or methacryl fluorenyl groups is too large, the unreacted acrylonitrile group and methacryl oxime group tend to remain even after photohardening and/or thermal hardening, and the physical properties or characteristics of the resin tend to occur. Changes. In the present invention, the number of the acryloyl fluorenyl group or the methacryl fluorenyl group is not more than 15 in a single molecule, and the above problems are not caused. However, the coating property and the resolution are improved, and the light is cured. The physical properties or characteristics of the photosensitive resin composition are stabilized, and it is preferably 10 or less. Therefore, the total number of molecules in one of the acryloyl group and the methacryloyl group is preferably 2 to 15, more preferably 2 to 10, still more preferably 2 to 8, and even more preferably 2 to 2 Six.

The component (A1) of the present invention is preferably a weight average molecular weight of 950 to 25,000.

Further, the weight average molecular weight can be measured by a colloidal permeation chromatography (GPC) method using a developing solvent such as tetrahydrofuran or toluene. The weight average molecular weight of the other components can also be measured in the same manner.

When the weight average molecular weight is 950 or more, undercoating of the coating liquid applied on the substrate can be prevented, and workability can be improved. Further, since the volume shrinkage of the urethane compound in the photocuring is small, the formation of a thick film can be performed, and the resin stress due to the hardening shrinkage is suppressed, and the reliability is improved. Moreover, if the weight average molecular weight is 25,000 or less, the photosensitive resin group The viscosity of the coating liquid of the product is lowered to improve the workability. Further, since the solvent content for lowering the viscosity is reduced, not only the formation of a thick film is easy, but also the solubility of the developing solution is improved, and the resolution is also improved. Further, since the molecular movement is fast, the proximity of the functional groups in the photopolymerization reaction becomes easy to be sufficiently reacted. Thereby, not only the photopolymerizability is improved, but also the thick film formability and the pattern formability are improved, and the light energy can be reduced and the irradiation time can be shortened at the time of light irradiation, and the hollow structure can be formed more efficiently. In the present invention, in order to improve the physical properties and properties of the photosensitive resin composition after photocuring, the coating property and the resolution are further improved, and the weight average molecular weight is preferably in the range of 950 to 15,000. Furthermore, from the viewpoint of imaging or compatibility, it is particularly preferable in the range of 950 to 11,000.

In the present invention, the component (A1) (the urethane-based compound (A1)) is compatible with the urethane-based compound in order to respond to the workability, the pattern formation property, and the physical properties or properties of the resin after curing. The photopolymerizable compound (A2) other than the compound (A1) is used in combination.

In the present invention, the urethane-based compound (A1) is an essential component for improving the physical properties or properties of the photosensitive resin composition, and the content of the urethane-based compound (A1) is determined by the resin cured product. The total amount of the photosensitive resin composition is 10% by mass or more, preferably 30% by mass or more, and more preferably 50% by weight or more based on the physical properties and properties. When the content of the urethane-based compound (A1) is 10% by mass or more, the physical properties or characteristics of the cured product of the resin due to the blending of the urethane-based compound (A1) are improved. When the content of the urethane-based compound (A1) is 30% by mass or more, the coating property, the pattern formation property, and the resin after curing Among the physical properties or characteristics, all the characteristics required to exert the effects of the present invention can be simultaneously satisfied. In addition, when the content of the urethane-based compound (A1) is 50% by mass or more, a hollow structure having excellent resistance to moisture and heat resistance over a long period of time can be obtained even in an environment that is too severe. Electronic parts.

(Photopolymerizable compound (A2) other than (A1) component)

In the present invention, the photopolymerizable compound (A2) other than the component (A1) used in combination with the component (A1) may be a polymerizable compound having at least one ethylenically unsaturated group. The polymerizable compound having at least one ethylenically unsaturated group may, for example, be a compound obtained by reacting an α,β-unsaturated carboxylic acid with a polyhydric alcohol, having a guanamine bond and two or more ethylenically unsaturated groups. a polymerizable compound, a compound having two phenolic hydroxyl groups in one molecule, a compound obtained by reacting an α,β-unsaturated carboxylic acid with a glycidyl group-containing compound, and a copolymer of an alkyl (meth)acrylate. A compound obtained by introducing an ethylenically unsaturated group or the like. These may be used alone or in combination of two or more.

[Compound obtained by reacting an α,β-unsaturated carboxylic acid with a polyol]

The compound obtained by reacting the α,β-unsaturated carboxylic acid with a polyhydric alcohol may, for example, be a polyethylene glycol di(meth)acrylate having a number of ethylene groups of 2 to 14 and a number of stretching propyl groups. Polypropylene glycol di(meth)acrylate of 2~14, polyethylene/polypropylene glycol di(meth)acrylate and trishydroxyl group with a number of 2 to 14 and a propyl group of 2 to 14 base Propane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide (EO) modified trimethylolpropane tri(meth)acrylate, propylene oxide (PO) modified three Hydroxymethylpropane tri(meth)acrylate, EO, PO modified trimethylolpropane tri(meth)acrylate, tetramethylol methane tri(meth)acrylate, tetramethylol methane tetra ( Methyl) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. These may be used alone or in combination of two or more.

[Polymerizable compound having a guanamine bond and two or more ethylenically unsaturated groups]

The polymer compound represented by the following general formula (1) is preferable from the viewpoint of the resolution and the adhesion property of the polymerizable compound having a guanamine bond and two or more ethylenically unsaturated groups.

In the general formula (1), R ₃₁ , R ₃₂ and R ₃₃ each independently represent a divalent organic group, R ₃₄ represents a hydrogen atom or a methyl group, and R ₃₅ and R ₃₆ each independently represent a hydrogen atom and have a carbon number of 1 to 2; 4 alkyl or phenyl.

Examples of the organic group of the divalent group include a phenyl group, a pyridyl group, an alkyl group having a linear or branched chain of 1 to 10 carbon atoms, and an alicyclic ring having a carbon number of 1 to 10. The basis of the structure, etc. Further, these groups may be substituted with a substituent such as a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an aryl group.

The polymerizable compound represented by the above general formula (1) is a guanamine-bonded bis (methyl group) obtained by reacting a compound containing an oxazoline group with a compound containing a carboxyl group and/or a compound having a phenolic hydroxyl group. Acrylate is preferred. By using this compound, a cured product of a resin having high elasticity and high heat resistance can be easily obtained.

The polymerizable compound represented by the above general formula (1) can be, for example, a bisoxazoline represented by the following general formula (2), a compound having two phenolic hydroxyl groups in one molecule, and (meth) Acrylic reaction derived.

In the general formula (2), Y ⁴ represents a divalent organic group, but a stretchable phenyl group which may have a substituent, a pyridyl group which may have a substituent, and a linear chain having a substituent of 1 to 10 carbon atoms It is preferred that the alkyl group of the branched chain or the substituent having a carbon number of 1 to 10 and having an alicyclic structure is preferred. Among them, the phenylene-extended and pyridine-producing genes are preferably heat-resistant, and the alkylene group is preferred because it imparts improved moisture resistance.

Further, R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group.

The bisoxazoline aspect represented by the above general formula (2) may, for example, be mentioned. 2,2'-(1,3-phenylene)bis-2-oxazoline, 2,6-bis(4-isopropyl-2-oxazolin-2-yl)pyridine, 2-2' - isopropylidene bis(4-phenyl-2-oxazoline), 2-2'-isopropylidene bis(4-tert-butyl-2-oxazoline), and the like. These may be used alone or in combination of two or more.

[a compound having two phenolic hydroxyl groups in one molecule]

In the case of a compound having two phenolic hydroxyl groups in one molecule, biphenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxydimethylnaphthalene, bis(4-hydroxyphenyl)ketone, Bis(4-hydroxy-3,5-dimethylphenyl)one, bis(4-hydroxy-3,5-dichlorophenyl)one, bis(4-hydroxyphenyl)anthracene, bis(4-hydroxyl) -3,5-dimethylphenyl)anthracene, bis(4-hydroxy-3,5-dichlorophenyl)anthracene, bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxy-3, 5-dimethylphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dichlorophenyl)hexafluoropropane, bis(4-hydroxyphenyl)dimethyloxane, bis(4-hydroxy- 3,5-Dimethylphenyl)dimethyloxane, bis(4-hydroxy-3,5-dichlorophenyl)dimethyloxane, bis(4-hydroxyphenyl)methane, bis(4-hydroxyl -3,5-dichlorophenyl)methane, bis(4-hydroxy-3,5-dibromophenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-dual (4 -hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-methyl Phenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, bis(4-hydroxyphenyl)ether, bis(4-hydroxy-3,5-dimethylphenyl)ether Double (4-hydroxyl -3,5-dichlorophenyl)ether, 9,9-bis(4-hydroxyphenyl)anthracene, 9,9-bis(4-hydroxy-3-methylphenyl)anthracene, 9,9-double (4-hydroxy-3-chlorophenyl)indole, 9,9-bis(4-hydroxy-3-bromophenyl)anthracene, 9,9- Bis(4-hydroxy-3-fluorophenyl)anthracene, 9,9-bis(4-hydroxy-3-methoxyphenyl)anthracene, 9,9-bis(4-hydroxy-3,5-dimethyl Phenyl) ruthenium, 9,9-bis(4-hydroxy-3,5-dichlorophenyl)anthracene, 9,9-bis(4-hydroxy-3,5-dibromophenyl)anthracene, and the like. Among these, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane is particularly preferred. These may be used alone or in combination of two or more.

The reaction of the compound containing a phenolic hydroxyl group and/or the compound containing a carboxyl group and the compound containing an oxazoline group is preferably carried out at a reaction temperature of 50 to 200 °C. When the reaction temperature is 50 ° C or higher, the reaction becomes extremely rapid, and if the reaction temperature is 200 ° C or lower, the side reaction can be sufficiently suppressed. Further, the reaction can be carried out in a polar organic solvent such as dimethylformamide, dimethylacetamide or dimethylhydrazine as needed.

[Compound obtained by reacting an α,β-unsaturated carboxylic acid with a compound containing a glycidyl group]

Examples of the compound obtained by reacting an α,β-unsaturated carboxylic acid with a compound containing a glycidyl group include a novolac type epoxy resin, a bisphenol type epoxy resin, and an o-hydroxybenzaldehyde type epoxy resin. An epoxy acrylate compound obtained by reacting an epoxy resin with (meth)acrylic acid or the like. Further, an acid-modified epoxy acrylate compound obtained by reacting an acid anhydride such as tetrahydrophthalic anhydride with an OH group of the above epoxy acrylate compound may also be used. In the case of such an acid-modified epoxy acrylate compound, for example, EA-6340 (manufactured by Shin-Nakamura Chemical Co., Ltd.) shown in the following general formula (3) is commercially available.

In the general formula (3), the ratio of m to n is 100/0 to 0/100.

[Compound for the introduction of an ethylenically unsaturated group into a copolymer of an alkyl (meth) acrylate]

Examples of the compound obtained by introducing an ethylenically unsaturated group into a copolymer of an alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, and (methyl). A copolymer of butyl acrylate or 2-ethylhexyl (meth) acrylate is introduced into a compound obtained by introducing an ethylenically unsaturated group such as a (meth) acrylonitrile group.

The photopolymerizable compound (A2) other than the above-mentioned (A1) component may be used alone or in combination of two or more.

(content of component (A))

The content of the component (A) is preferably from 80 to 99.9% by mass based on the total amount of the solid component after removing the inorganic filler in the photosensitive resin composition (that is, the amount of the component after removing the inorganic filler and the solvent). (A) When the content of the component is 80 to 99.9% by mass, the rib pattern or the shape of the lid portion can be formed, and sufficient resin strength can be obtained to make the hollow structure less likely to collapse. From this point of view, the content of the component (A) is preferably from 90 to 99.5% by mass, more preferably from 95 to 99% by mass.

<Photopolymerization initiator (B)>

The photopolymerization initiator (B) which can be contained together with the component (A) is not particularly limited as long as it can generate free radicals by active light, and examples thereof include oxidation of an aromatic ketone and a mercaptophosphine. , oxime esters, anthraquinones, benzoin ether compounds, benzyl derivatives, 2,4,5-triarylimidazole dimers, acridine derivatives, N-phenylglycine, N-phenylgan Amino acid derivative, coumarin compound.

The aromatic ketone may, for example, be benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (meaning, it is a ketone), N, N'-tetraethyl 4--4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl)-butan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propan-1-one.

The mercaptophosphine oxide may, for example, be bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide or 2,4,6-trimethylbenzylidene-diphenyl. - a phosphine oxide.

The oxime ester may, for example, be 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzhydrylhydrazine)].

Examples of the terpenoids include 2-ethyl hydrazine, phenanthrenequinone, 2-tert-butyl hydrazine, octamethyl hydrazine, 1,2-benzoquinone, 2,3-benzoquinone, and 2- Phenylhydrazine Bismuth, 2,3-diphenylanthracene, 1-chloroindole, 2-methylindole, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl-1,4-naphthoquinone 2,3-dimethylhydrazine.

Examples of the benzoin ether compound include benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether.

Examples of the benzyl derivative include a benzoin compound such as benzoin, methyl benzoin, and ethyl benzoin, and benzyl dimethyl ketal.

The 2,4,5-triaryl imidazole dimer may, for example, be 2-(2-chlorophenyl)-1-[2-(2-chlorophenyl)-4,5-diphenyl-1. 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl), etc., 3-oxazol-2-yl]-4,5-diphenylimidazole -4,5-bis(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxybenzene 4-)-5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer.

The acridine derivative may, for example, be 9-phenylacridine or 1,7-bis(9,9'-acridinyl)heptane.

The photopolymerization initiator (B) can be synthesized by a usual method, and is also commercially available. Examples of the photopolymerization initiator (B) which can be obtained include, for example, IRGACURE-369, IRGACURE-907, IRGACURE-651, and IRGACURE-819 (all of which are manufactured by BASF Corporation, trade names), and compounds having an oxime ester bond. Wait.

Among the above photopolymerization initiators (B), in particular, from the viewpoint of improvement in photocurability or high sensitivity, a compound having an oxime ester bond is preferred. In the case of the compound having a oxime ester bond, more specifically, 1,2-octanedione-1-[4-(phenylthio)phenyl]- represented by the following formula (4) 2-(O-benzhydrylhydrazine) (trade name: OXE-01, manufactured by BASF Corporation), 1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazole- 3-yl]ethanone 1-(O-acetamidine) (trade name: OXE-02, manufactured by BASF Corporation), 1-phenyl-1,2-propanedione-2-[O-(ethoxyl) Carbonyl) 肟] (trade name: Quantacure-PDO, manufactured by Nippon Kayaku Co., Ltd.).

The photopolymerization initiator (B) may be used alone or in combination of two or more.

The content of the photopolymerization initiator (B) is preferably 0.1 to 20% by mass based on the total solid content of the photosensitive resin composition. When the content of the photopolymerization initiator (B) is from 0.1 to 20% by mass, the sensitivity of the photosensitive resin composition can be improved, and the deterioration of the shape of the resist can be prevented. From this point of view, the content of the photopolymerization initiator (B) is preferably from 0.5 to 10% by mass, more preferably from 1 to 5% by mass. In the same manner, the content of the photopolymerization initiator (B) is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the photopolymerizable compound (A). More preferably 1 to 5 parts by mass.

<Inorganic filler (C)>

In addition to the photopolymerizable compound (A) and the photopolymerization initiator (B), the photosensitive resin composition of the present invention may further contain an inorganic filler (C) (hereinafter referred to as "(C) component").

In the photosensitive resin composition of the present invention, by containing an inorganic filler, it is possible to obtain not only a high modulus of elasticity but also a cured resin having excellent rigidity, even under more severe high-temperature and high-pressure conditions. High hollow structural retention can be achieved. Further, since the photosensitive resin composition of the present invention has a low thermal expansion or a low moisture absorption rate of the imageable cured product by containing an inorganic filler, it is possible to form a highly reliable ridge portion and a cover in the hollow structure device. unit.

As the inorganic filler, it is preferred to use cerium oxide, aluminum oxide, titanium oxide, zirconium oxide, ceramic fine powder, talc, mica, boron nitride, kaolin or barium sulfate having a volume average particle diameter in the range of 10 nm to 50 μm. When the particle diameter is 10 nm or more, the inorganic filler in the photosensitive resin composition is less likely to aggregate, and it is easy to uniformly disperse, and the fine pattern formation property is greatly improved, and the difference in physical properties or characteristics of the cured product is small. In addition, when the particle diameter is 50 μm or less, the scattering of the irradiation light due to the inorganic filler is small, and the thick film formation property or the fine pattern formation property is improved.

Here, the volume average particle diameter of the inorganic filler is obtained by a laser refractive particle size distribution meter (for example, Nikkiso, trade name: MICROTRAC MT3000), and is obtained by MV value (Mean Volume Diamete).

The shape of the inorganic filler (C) may be any of a spherical shape, a crushed shape, a needle shape, or a plate shape, and a desired shape may be selected depending on the particle diameter. For example, an inorganic filler having a volume average particle diameter in the range of 10 nm to 1 μm and having a small particle diameter close to a spherical shape or a spherical shape not only improves the elastic modulus of the photosensitive resin composition, but also enhances the mechanical strength of the cured product. At the same time, it has an effect of imparting thixotropy to the photosensitive resin composition before curing to improve coatability. Therefore, the inorganic filler having a small particle diameter is used for improving the physical properties or properties of the photosensitive resin composition of the present invention even if it is slightly affected by light transmission or light absorbing properties. In addition, the large particle diameter inorganic filler having a volume average particle diameter in the range of 1 μm to 50 μm can greatly improve the elastic modulus of the photosensitive resin composition, and therefore has a large effect on the shape maintainability of the hollow structure. Further, in terms of shape, the plate-shaped inorganic filler can greatly reduce the moisture absorption rate or moisture permeability of the cured product of the photosensitive resin composition. As described above, the photosensitive resin composition of the present invention which is applied to the rib portion or the lid portion of the hollow structure is preferably an inorganic filler having a large particle diameter in the form of a plate.

The present invention has a main purpose of providing a photosensitive resin composition having high reliability against moisture and heat while ensuring the retention of the hollow portion under high temperature and high pressure. Therefore, the average aspect ratio of the inorganic filler (C) is preferably from 30 to 100, more preferably from 40 to 90, and particularly preferably from 50 to 80. Further, the volume average particle diameter is preferably 5 to 50 μm, preferably 8 to 40 μm, and particularly preferably 10 to 30 μm. By using an inorganic filler having such an aspect ratio and a volume average particle diameter, the cured resin can exhibit low hygroscopicity and water permeability and excellent rigidity, for example, a sealing resin capable of withstanding high temperature resistance can be obtained. The hollow portion of the pressure is retained. Further, when the photosensitive resin composition contains the inorganic filler (C), it is a thick film which is a necessary photosensitive property of the present invention. Although the formability and the fine pattern formation property tend to be lowered, the shape and the particle diameter of the inorganic filler are set to the above-described aspect ratio and volume average particle diameter, and the decrease can be suppressed.

In the present invention, the aspect ratio is defined by the ratio of the thickness of the inorganic filler (C) to the long diameter (long diameter/thickness), and does not mean the (long diameter/short diameter) in the plane of the inorganic filler. The shape of the inorganic filler is preferably a shape called a plate (including a flat plate shape, a disk shape, a flat shape, or a scaly shape), and is preferably a scaly shape.

The aspect ratio of the inorganic filler can be determined by using a scanning electron microscope or a transmission electron microscope. That is, here, the measurement of the average aspect ratio is performed by observation by a scanning electron microscope (SEM). First, the inorganic filler is fixed on the SEM sample table, and the magnification is observed by the maximum magnification of one particle in the field of view, and the shape is observed. The surface with the largest observation area of the particle (that is, the smooth and broad comparison) The face, such as the mica face of the mica, is taken in the direction of the X face) (photographing). Next, the secondary sample stage rotates, and unlike this, the surface having the smallest observation area from the particle (that is, if the particle is a plate shape, the surface of the thickness of the plate can be observed, for example, a layer of mica or the like. Take a picture (photographing) in the direction of the section (broken section); From the image (photograph) thus obtained, first, the smallest circle inscribed with the particle is set for the particle image of the X surface, and the diameter is measured, and is defined as the "long diameter" of the particle, and the particle image of the Y surface is Two parallel lines are drawn in such a manner that the particles are closest to each other, and the interval between the parallel lines is defined as "thickness", and the long diameter is divided by the thickness to obtain the aspect ratio of each particle. For any pumping The 100 inorganic filler particles were subjected to this operation, and the average value was calculated to be an average aspect ratio. In the present invention, when the average aspect ratio is 30 or more, the effect of reducing moisture absorption or moisture permeability of the photosensitive resin is high. On the other hand, the effect of high elastic modulus is also increased. For example, it is possible to obtain a hollow portion retaining property capable of blocking the resin molding pressure at a high temperature. When the average aspect ratio is 100 or less, the photosensitive properties such as thick film formation property and fine pattern formation property are improved.

In the present invention, the average particle diameter of the inorganic filler (C) is obtained by a laser refractive particle size distribution meter (for example, Nikkiso, trade name: MICROTRAC MT3000) with an MV value (Mean Volume Diamete). . The inorganic filler can be measured and analyzed by dispersing it in water using a phosphonate as a dispersing agent. In the present invention, when the volume average particle diameter of the inorganic filler is 5 μm or more, the effect of reducing the moisture absorption or moisture permeability of the photosensitive resin is sufficient, and the effect of high elastic modulus is also the same as when the aspect ratio is large. Will get bigger. When the volume average particle diameter is 50 μm or less, the photosensitive properties such as thick film formation property and fine pattern formation property are good.

The present invention is preferably such that the average aspect ratio and the volume average particle diameter of the inorganic filler (C) are each in the range of 30 to 100 and 5 to 50 μm. When the average aspect ratio is in the range of 30 to 100 and the volume average particle diameter is 5 μm or more and 50 μm or less, the photosensitive property such as thick film formation property or fine pattern formation property and the heat resistance and high heat resistance of the cured resin can be obtained. Both the elasticity rate and the two are combined. The inorganic filler (C) is preferably such that the average aspect ratio and the volume average particle diameter are in the range of 30 to 100 and 5 to 50 μm, and more preferably set to be better than the above. (40~90 Or 8~40μm), or a particularly good range (50~80 or 10~30μm).

The focus of the present invention is particularly focused on the improvement of shape maintenance and reliability in manufacturing and in use in a hollow structural device. Therefore, of course, the inorganic filler can more effectively exert the effects of the present invention when the average aspect ratio and the volume average particle diameter are in the range of 30 to 100 and 5 to 50 μm, respectively, but if the average aspect ratio is set to more than 50 and 100 In the following, it is particularly preferable because the above-described shape maintenance and reliability can be greatly improved without greatly reducing the photosensitive characteristics. In this case, when the volume average particle diameter of the inorganic filler is in the range of 5 to 50 μm, the effect of the present invention is exerted, and no problem occurs.

In the photosensitive resin composition of the present invention, specific particles of the inorganic filler having an average aspect ratio of 30 to 100 and a volume average particle diameter of 5 to 50 μm include talc, mica, boron nitride, kaolin, barium sulfate, and the like. Among them, scaly-like mica is preferred. Mica can increase the aspect ratio and has a high uniformity of shape. In addition to reducing the water permeability of the photosensitive resin composition and improving the moldability of the high modulus, it is also more capable than other inorganic fillers. The effect of reducing the photosensitive characteristics is suppressed. In addition, mica has synthetic mica, etc., which can be less harmful than other natural inorganic fillers, and can reduce the resistance to photohardenability. Further, since the deterioration of the moisture resistance due to the impurities contained in the inorganic filler can be suppressed, the effect of greatly improving the reliability of the hollow structure device can be obtained.

In the present invention, in order to allow the inorganic filler to have the above-described average aspect ratio and volume average particle diameter, a commercially available product having the above characteristics can be purchased and used as it is. A plurality of commercially available products may be mixed and processed, or may be processed by sieving a commercial product. For example, in the case of commercial products of mica, various mica made by the company Yamaguchi Mica Industries can be used. For specific examples, A-51S (average aspect ratio 85, volume average particle diameter 52 μm), SYA-31RS can be used directly. (average aspect ratio 90, volume average particle diameter 40 μm), SYA-21RS (average aspect ratio 90, volume average particle diameter 27 μm), SJ-005 (average aspect ratio 30, volume average particle diameter 5 μm), or the like, or use of these Processed products.

In the present invention, when the photosensitive resin composition of the present invention is applied to the material of the lid portion of the hollow structural device, the content of the inorganic filler is generally not required to be precise pattern accuracy, and the physical properties and thick film of the cured resin can be used. It is determined by the balance of the photosensitive characteristics such as the formation property or the fine pattern formation property. However, when it is applied to the material of the ridge portion of the hollow structure device, the fine pattern accuracy is usually required. Therefore, the content of the inorganic filler is 0.5 to 50% by mass based on the total solid content of the photosensitive resin composition. Preferably, 2 to 50% by mass is better, 5 to 45% by mass is better, and 10 to 40% by mass is particularly good. When the content of the inorganic filler is from 0.5 to 50% by mass, the thick film formation or pattern shape of the photosensitive resin composition is good, and sufficient resin strength can be obtained, and at the same time, even if a small amount, the physical properties or characteristics of the cured resin can be obtained. Can be improved. When the photosensitive resin composition of the present invention is applied to a material of a lid portion, the content of the inorganic filler is preferably 0.5 to 60% by mass, and the amount of 2 to 50% by mass is more preferably 5 to 40% by mass. Especially good.

In the photosensitive resin composition of the present invention, an inorganic filler (C) having an average aspect ratio of 30 to 100 and a volume average particle diameter of 5 to 50 μm is contained. When the photosensitive resin composition is applied to the rib portion, the content of the inorganic filler is preferably from 5 to 50% by mass, preferably from 10 to 50% by mass based on the total solid content of the photosensitive resin composition. 15 to 45 mass% are better, and 20 to 40% by mass are particularly good. The content of the inorganic filler having an average aspect ratio and a volume average particle diameter in the above range is 5 to 50% by mass, and the thick film formation property or pattern formation property of the photosensitive resin composition is not adversely affected. A sufficient resin strength and a high modulus of elasticity can be obtained, and physical properties or characteristics desired as a cured resin of low hygroscopicity or low moisture permeability can be obtained. In the present invention, when a photosensitive resin composition containing an inorganic filler having an average aspect ratio of 30 to 100 and a volume average particle diameter of 5 to 50 μm is applied to the lid portion, the content of the inorganic filler is set to 5 to 60 mass. % is better, 20 to 50% by mass is better, and 20 to 40% by mass is particularly good.

<sensitizer (D)>

Further, in the photosensitive resin composition of the present invention, a sensitizer (D) (hereinafter referred to as "(D) component") may be further added. Examples of the sensitizer (D) include pyrazolines, anthraquinones, coumarins, ketones, oxazoles, benzoxazoles, thiazoles, benzothiazoles, and triazoles. Tertiary styrenes, triazines, thiophenes, naphthoquinone imines, and the like. These sensitizers (D) may be used alone or in combination of two or more.

The content of the sensitizer (D) is preferably 0.1 to 1% by mass based on the total amount of the solid content of the photosensitive resin composition. When the content of the sensitizer (D) is in the above range, the sensitivity of the photosensitive resin composition will be Improve, compatibility with solvents is also good.

<Heat resistant polymer (E)>

Further, a heat-resistant polymer (E) (hereinafter referred to as "(E) component") may be further added to the photosensitive resin composition. Examples of the heat resistant polymer (E) include, for example, polyimidazole having high heat resistance, polyoxazole, and novolak resins such as these precursors, phenol novolacs, cresol novolacs, and polyamidofluorenes. Amine, polyamine, and the like are preferred from the viewpoint of workability. These may be used alone or in combination of two or more.

The content of the heat-resistant polymer (E) is preferably from 1 to 50% by mass based on the total solid content of the photosensitive resin composition. When the content of the heat resistant polymer (E) is within the above range, the heat resistance and resin strength of the photosensitive resin composition are good, and the developability is also good.

<Hot crosslinked material (F)>

Further, in the above-mentioned photosensitive resin composition, a thermally crosslinked material (F) (hereinafter referred to as "(F) component") may be further added. Examples of the heat crosslinked material (F) include an epoxy resin, a phenol resin in which the α-position is substituted with a methylol group or an alkoxymethyl group, and a N-position substituted with a methylol group and/or an alkoxymethyl group. The melamine resin, the urea resin and the like are preferred from the viewpoint of the strength of the resin after curing. These may be used alone or in combination of two or more.

The content of the thermally crosslinked material (F) is preferably from 1 to 20% by mass based on the total solid content of the photosensitive resin composition. If the content of the heat crosslinked material (F) is in the above range, the photosensitive resin composition is resistant. The heat or resin is good in strength and good in imageability.

<Thermal acid generator (G)>

Further, a thermal acid generator (G) (hereinafter referred to as "(G) component") may be further added to the photosensitive resin composition described above. Examples of the thermal acid generator (G) include a salt formed of a strong acid such as a phosphonium salt and a base, or a quinone imide sulfonate. The onium salt is a di(alkyl) group such as an aryldiazonium salt, a diphenylsulfonium salt, a diarylsulfonium salt, a diarylsulfonium salt or a di(t-butylphenyl)phosphonium salt. An aryl) sulfonium salt, a trialkylsulfonium salt like a trimethylsulfonium salt, a dialkyl monoarylsulfonium salt like a dimethylphenylsulfonium salt, and a diphenylmethylsulfonium salt Diaryl monoalkyl phosphonium salts and triarylsulfonium salts.

The content of the thermal acid generator (G) is preferably 0.1 to 30 parts by mass, more preferably 0.2 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the component (A).

<Thermal free radical generator (H)>

Further, in the above-mentioned photosensitive resin composition, a thermal radical generating agent (H) (hereinafter referred to as "(H) component") may be further added. The thermal radical generating agent (H) may, for example, be t-butyl cumyl peroxide (PERBUTYL® C) or n-butyl 4,4-di-(t-butylperoxy) pentane. Peroxides such as PERHEXA® V and dicumyl peroxide (PERCUMYL® D).

The content of the above-mentioned thermal radical generating agent (H) is preferably 0.1 to 30 parts by mass, and 0.2 to 20 parts by mass based on 100 parts by mass of the component (A). More preferably, 0.5 to 10 parts by mass is better.

<Solvent>

In the photosensitive resin composition of the present embodiment, the photopolymerizable compounds (A) and (B) photopolymerization initiators may optionally contain an inorganic filler (C) and other materials such as a sensitizer. (D), a heat resistant polymer (E), a thermal crosslinked material (F), a thermal acid generator (G), and a thermal radical generating agent (H) are mixed together with a solvent.

The solvent to be used at this time is not particularly limited, and examples thereof include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, and propylene glycol. A solvent such as a polar solvent as a main component such as monomethyl ether acetate or a solvent such as γ-butyrolactone. These solvents may be used singly or in combination of two or more.

<Subsequent adjuvant>

Further, in the photosensitive resin composition, in order to improve the adhesion between the photosensitive resin composition and the substrate, an auxiliary agent may be added. Examples of the auxiliary agent include a decane coupling agent such as γ-glycidoxydecane, amino decane or γ-ureido decane.

These adjunct adjuvants may be used alone or in combination of two or more.

The content of the auxiliary agent is preferably from 0.1 to 10 parts by mass, more preferably from 0.4 to 3 parts by mass based on 100 parts by mass of the component (A), from the viewpoint of improving the adhesion between the photosensitive resin composition and the substrate. Share.

[Photosensitive film]

The photosensitive film of the present invention is obtained by molding the photosensitive resin composition into a film shape.

The form of the photosensitive film is not particularly limited.

For example, the photosensitive resin composition of the present invention is dissolved in the solvent as needed, and then coated on a support film made of an organic film such as polyethylene terephthalate by various known methods. After drying, the solvent is removed to form a photosensitive resin layer, which can be used as a two-layer photosensitive film (dry film resist).

Further, a polyethylene terephthalate, a polyethylene film, a polypropylene film or the like may be laminated on the formed photosensitive resin layer as a protective film to form a three-layer photosensitive film.

Further, when the photosensitive resin layer has self-supporting properties, the photosensitive film can be peeled off from the support film to form one layer.

Further, the photosensitive resin composition of the present invention can be heated and melted, and molded into a sheet shape by using an extrusion molding machine or the like.

When the photosensitive film of the present invention is used as a lid portion having a hollow structure, the support film may be subjected to photopolymerization after photoirradiation as described later, or may be used as a lid together with the photosensitive resin composition. The materials used in the department. In the present invention, a transparent or translucent heat-resistant plastic (thermoplastic engineering plastic or thermosetting resin having a three-dimensional mesh structure), glass, ceramics or the like may be used instead of the above-mentioned supporting film. In the case of such a heat-resistant plastic, glass or ceramic, by using a film or a thin plate, the laminated photosensitive resin can be formed in the same manner as the above-mentioned support film. The laminate formed by the object is used as a film or a sheet. Moreover, these heat-resistant plastics, glass or ceramics have the function of enhancing the shape retention or rigidity of the lid portion while reinforcing.

The thickness of the photosensitive film is not particularly limited, and may be appropriately set depending on the application.

For example, when a support film or a support sheet is used, the thickness of the support film or the support sheet is preferably 10 μm to 3 mm. The support film or the support sheet described above can be appropriately determined from the viewpoint of the shape, thickness, and manufacturing of the hollow structure device, and the usable range can be widened.

The thickness of the photosensitive resin layer is preferably from 1 to 500 μm, and the protective film is preferably from 10 to 200 μm.

[Formation method of graphics]

Next, a pattern forming method of the present embodiment will be described.

The pattern forming method of the present embodiment includes a step of laminating a photosensitive resin composition or a photosensitive film of the present invention on a substrate to form a photosensitive resin layer, and irradiating a predetermined portion of the photosensitive resin layer through a mask. The active light is subjected to an exposure step of photocuring the exposed portion, a developing step of removing the portion other than the exposed portion of the photosensitive resin layer by the developing liquid, and thermally curing the exposed portion of the photosensitive resin layer. A heat hardening step of forming a cured resin. Through these steps, a desired pattern such as a rib pattern for forming a hollow structure can be formed.

Hereinafter, each step will be described.

(layering step)

In the laminating step, a photosensitive resin film is formed by laminating and drying the photosensitive resin composition or the photosensitive film on the substrate.

Examples of the support substrate include a glass substrate, a semiconductor, a metal oxide insulator (for example, TiO ₂ or SiO ₂ ), a tantalum nitride, a ceramic piezoelectric substrate, and the like.

Further, the method of applying the photosensitive resin composition may be a method using spin coating, spray coating, dip coating, or roll coating using a spinner, but is not limited thereto. The photosensitive film can be laminated using a laminator or the like.

When the photosensitive resin composition is applied to the substrate, the thickness of the film (photosensitive resin layer) after drying can be appropriately set by the coating means, the solid content concentration and the viscosity of the photosensitive resin composition, and the like. It is 1 to 500 μm, but it is preferably 1 to 300 μm from the viewpoint of improving the resolution.

In order to make the film thickness of the film after drying 1 to 300 μm, the photosensitive resin composition may be dissolved in a solvent to adjust the viscosity to 0.5 to 20 Pa. s is better, adjusted to 1~10Pa. s is better. Further, the solid content concentration of the photosensitive resin composition is preferably from 20 to 80% by mass, more preferably from 30 to 70% by mass. When the film thickness of the obtained film is 300 μm or less in particular, the resolution is good. When a photosensitive film is used, it can be formed in advance so that the film thickness of the photosensitive resin layer is the said film thickness.

After that, it can be equal to 60~120 °C by using a heating plate and an oven. The film was dried for 1 minute to 1 hour to form a photosensitive resin film on the support substrate.

(exposure step)

In the second exposure step, a predetermined portion of the photosensitive resin layer may be irradiated with active light through a mask to photoharden the exposed portion.

Here, examples of the active light used in the exposure include ultraviolet rays, visible rays, electron beams, and X-rays. Among these, ultraviolet rays and visible rays are particularly preferred.

(development step)

In the next development step, a developing liquid is used to remove a portion (unexposed portion) other than the exposed portion of the photosensitive resin layer. As the developing liquid, an organic solvent or an aqueous alkali solution can be used.

As the organic solvent used for the developer, for example, an organic solvent such as N-methylpyrrolidone, ethanol, cyclohexanone, cyclopentanone or propylene glycol methyl ether acetate can be used.

Further, as the aqueous alkali solution for the developing solution, for example, sodium hydroxide, potassium hydroxide, sodium citrate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine or tetramethyl hydroxide can be used. An aqueous solution of a base such as ammonium.

Among these, from the viewpoint of the development speed, it is preferred to use propylene glycol methyl ether acetate.

Further, after development, water, or an alcohol such as methanol, ethanol or isopropyl alcohol, or n-butyl acetate, propylene glycol monomethyl ether acetate or the like may be used as needed. Ethylene glycol dimethyl ether acetate or the like is preferably used for rinsing.

(thermal hardening step)

Further, after the development step, the exposed portion of the photosensitive resin layer is thermally cured to perform a thermal curing step of forming a cured resin.

The heat hardening (maturation) after development is preferably carried out by selecting the temperature for one to two hours while gradually increasing the temperature. The thermosetting is preferably carried out at 120 to 240 °C. When the heating temperature is gradually increased, for example, heat treatment is carried out at 120 ° C and 160 ° C for 10 to 50 minutes (preferably about 30 minutes), and then at 220 ° C, 30 to 100 minutes (preferably about 60 minutes). Heat treatment is preferred.

The pattern formed by the cured resin formed by the above-described forming method has a sufficient film thickness and can cover a ceramic substrate, a Si substrate, a glass substrate, a metal substrate or the like as a lid portion, and has a hollow structure.

(Method of forming hollow structure)

Next, a method of forming the hollow structure of the present invention will be described.

The method for forming a hollow structure according to the present invention includes a step of laminating a photosensitive resin layer formed by laminating the photosensitive resin composition or the photosensitive film described above on a ribbed pattern provided in a hollow structure on a substrate, An exposure step of irradiating the predetermined portion of the photosensitive resin layer with the active light to cure the exposed portion, and a step of thermally hardening the exposed portion of the photosensitive resin layer to form a cured resin. Moreover, after the foregoing exposure step and before the aforementioned thermal hardening step, the aforementioned photosensitivity may be A step of removing the portion of the resin layer other than the exposed portion.

Further, the above rib pattern is preferably formed by the pattern forming method of the present invention described above.

The photosensitive resin composition of the present invention or the photosensitive film formed by thinning the film can be used not only as the hollow structural rib portion but also as a lid portion.

For example, when the photosensitive resin composition is formed into a photosensitive film in advance and attached to the upper portion of the above-mentioned pattern, it is necessary to perform an exposure step and remove a portion other than the exposed portion of the photosensitive resin layer. A development step (removal step), a thermal hardening step to form a hollow structure.

When the photosensitive resin composition or the photosensitive film of the present invention is used as a lid portion, it is not necessary to pass the development step. However, when it is desired to control the shape of the lid portion, it is desirable to simultaneously manufacture a plurality of hollow structure devices, and to expose only the size of the lid portion of the hollow device corresponding to the sheet through the mask. When the exposed portion is imaged and divided into individual pieces, the exposure step is performed by irradiating the active light through the mask to expose the exposed portion, and then passing the photosensitive resin layer. It is preferred that the portion other than the exposed portion is removed by the above-described developing solution.

Further, the lamination step, the exposure step, the removing step, and the thermosetting step in the method for forming a hollow structure of the present invention can be carried out in the same manner as the above-described pattern forming method.

The film thickness of the photosensitive resin layer for forming the lid portion is preferably 5 to 500 μm, more preferably 10 to 400 μm.

The thickness of the final film thickness (the total thickness of the photosensitive resin layer or the film formed by the substrate or the thin plate) of the lid portion formed by the hardening step is preferably 10 μm to 3 mm, more preferably 20 μm to 2 mm. When the photosensitive resin composition of the present invention is used, even if the thickness of the lid portion is 10 μm, the shape can be maintained, and deformation under high temperature and high pressure conditions during molding can be suppressed. Further, when the thickness of the lid portion is 3 mm or less, it is possible to avoid the problem that the device having a hollow structure is too thick and the light transmittance at the time of exposure is lowered.

The thickness of the above-mentioned lid portion is not only the thickness of the photosensitive resin composition or the photosensitive film of the present invention, but can be adjusted as described above by allowing the film or sheet for support to be directly used as a lid portion. The desired thickness.

Further, the lid portion and the rib pattern may be carried out, for example, by a press or a roll laminator or a vacuum laminator. Further, in the present invention, the rib pattern may be formed without using the photosensitive resin composition of the present invention, and the photosensitive resin composition of the present invention may form only the lid portion, but both the rib pattern and the lid portion are When the photosensitive resin composition of the present invention is used, it is preferred because it has excellent adhesion therebetween. In particular, in the case of the photosensitive resin composition for both the rib pattern and the lid portion, it is desirable to further improve the adhesion because the type of the photopolymerizable compound or the content of the inorganic filler is similar.

As described above, according to the method for forming a hollow structure of the present invention, a lenticular pattern of a thick film can be formed by lithography, and a cured product of a film-form photosensitive resin composition can be formed from a rib pattern (or The sealing substrate such as ceramics is sealed as a lid portion to form a hollow structure.

Moreover, the space of the hollow structure can be protected from moisture by the surrounding photosensitive resin composition, and the hollow portion can be maintained at a high temperature, and can be applied to a SAW FILTER, CMOS/CCD sensor. The electronic components of the hollow structure such as MEMS can be effectively used for miniaturization, low-profile, and high-performance of electronic components. The photosensitive resin composition of the present invention is particularly preferably used for forming a rib portion and a lid portion of a hollow structure of SAW FILTER, and is particularly suitable as a member for forming a lid portion from the viewpoint of achieving high reliability.

[electronic parts]

The electronic component of the present invention has a hollow structure in which a rib portion and/or a lid portion of a hollow structure are formed by using the above-described photosensitive resin composition or photosensitive film.

Next, a SAW FILTER (surface acoustic wave filter) will be described as an example of the electronic component of the present invention.

<SAW FILTER and its manufacturing method>

The above SAW FILTER and its manufacturing method will be described. 1(a) to 1(c) are process diagrams showing a preferred embodiment of the SAW FILTER 100 of the present invention and a method of manufacturing the same.

First, as shown in FIG. 1(a), a photosensitive resin layer 32 for a rib portion formed by using the photosensitive resin composition of the present invention is laminated on a substrate 10 on which the comb-shaped electrode 20 is formed. The lamination method can be the same as the method described in the above-described rib pattern forming method.

The film thickness of the photosensitive resin layer 32 for the edge portion is applied to the photosensitive resin composition of the present invention in the form of usually 1 to 500 μm, preferably 1 to 300 μm, in the same manner as in the pattern forming method.

After the photosensitive resin composition is applied onto the substrate 10, the film is dried to form the photosensitive resin layer 32 for the rib portion. For the drying, an oven, a heating plate, or the like is used, and it is preferably carried out at a temperature of 60 to 120 ° C for 1 minute to 1 hour.

Next, as shown in FIG. 1(a), a predetermined portion of the prismatic photosensitive resin layer 32 may be irradiated with active light rays through a negative mask 60 having a desired pattern as needed to make the exposed portion light. hardening. Here, examples of the active light used in the exposure include ultraviolet rays, visible rays, electron beams, and X-rays. Among these, ultraviolet rays and visible rays are particularly preferred.

Then, as shown in FIG. 1(b), a portion other than the exposed portion of the photosensitive resin layer 32 for the edge portion (unexposed portion) is removed by using an organic solvent-based developing solution to form a pattern. The rib portion is thermally cured by the exposed portion of the photosensitive resin layer 32, and the rib portion 30 formed of the cured resin is formed. These so-called exposure steps, removal steps, and thermal hardening steps can be carried out in the same manner as the above-described rib pattern formation method.

Next, as shown in FIG. 1(c), the lid portion 40 is provided on the ridge portion 30 to form a hollow structure. Here, the lid portion 40 can be produced, for example, by forming a film of the photosensitive resin composition of the present invention into a film beforehand, or by molding it into a photosensitive film in advance. That is, the film may be attached to the upper portion of the rib 30, and then exposed, developed, and thermally cured to form the lid portion 40.

Further, the lid portion 40 and the ridge portion 30 may be carried out, for example, by heat pressing using a roll laminator or the like.

Further, the lid portion 40 may be formed of a material other than the photosensitive resin composition of the present invention. However, it is preferable that the lid portion 40 is made of a material which is excellent in moist heat resistance and has a low water absorption rate. Further, as the cover portion 40, a sealing substrate such as ceramics can also be used. In this case, at least the rib pattern formed by the photosensitive resin composition of the present invention can be used as a rib portion for forming a hollow structure of SAW FILTER.

Further, when the photosensitive resin composition or the photosensitive film of the present invention is used for a lid portion for forming a hollow structure of SAW FILTER, the rib portion can also be formed by a method other than the photosensitive resin composition of the present invention.

After the rib portion and the lid portion are formed by using the photosensitive resin composition or the photosensitive film of the present invention, the wiring is electrically connected to the conductors of the electrode 20 and the inside of the substrate 10 and the opposite side surface of the electrode 20. The SAW FILTER obtained by performing plating formation, mounting of a metal ball, etc. is shown in FIG. The SAW FILTER shown in Fig. 2 is not suitable for the photosensitive resin composition or the photosensitive film which is excellent in shape retention, heat resistance and rigidity according to the present invention, even under high-temperature reflow conditions when the solder ball is mounted. The deformation and the deformation of the characteristics of the hollow structural device occur.

As the substrate 10, a piezoelectric substrate such as a lithium niobate substrate, a lithium niobate substrate, or a gallium germane substrate can be used. For the material of the tooth comb-shaped electrode 20, for example, aluminum or the like can be used. In the case of the material of the wiring formed on the inside of the substrate and the surface, in the case of a metal conductor such as copper or aluminum or a ceramic substrate, a metal conductor such as gold, silver, platinum or palladium can be used. Again, on As the metal ball, for example, a solder material such as tin-silver-copper or lead-tin, gold or a resin ball coated with a metal conductor on the surface can be used.

The manufacturing method of the SAW FILTER shown in Fig. 2 is shown in Fig. 3. In Fig. 3, a method of forming the ridge portion and the lid portion of the present invention by UV exposure and a method of forming the ridge portion and the lid portion of the present invention using both UV exposure and laser aperture are shown. The laser aperture is used for forming the inner conductor of the cover.

In Fig. 3, a method of forming the ridge portion and the lid portion only by UV exposure will be described first. After the steps of (a) to (b) of FIG. 3, a hollow space is formed on the wiring conductor 81 electrically connected to the aluminum comb-shaped electrode 20 on the substrate 10 by the same method as that shown in FIG. The rib 30 is formed. Here, in the inside of the rib portion 30, the opening 35 for forming the inner conductor is formed by a developing step after UV exposure. After that, the photosensitive resin layer 41 for a lid portion formed of the photosensitive resin composition or the photosensitive film of the present invention, which is laminated on a support film, is applied or laminated on the rib portion 30, and is passed through a mask to carry out UV. Exposure ((c) of Figure 3). The above-described mask is shielded so that only a portion corresponding to the diameter of the opening 35 for forming the inner conductor is opaque, and the cover portion 40 which is photohardened at the other places is formed. The unexposed portion of the lid portion 40 is completely penetrated to the opening 35 for forming the inner conductor formed previously, and is subjected to desmear processing or the like after the application of the image (Fig. 3 (d)). Further, the inner conductor 80 is formed inside the opening 35 formed in the ridge portion and the lid portion by a plating method or the like, and wiring is formed on the surface of the lid portion ((e) of FIG. 3). In the present invention, it is formed inside the ridge portion and the lid portion The inside of the opening 35 is formed by a conductor filling method using a metal paste or a metal powder-containing resin paste, not only by plating but also by a metal paste. Through these steps, the conductor 81 of the aluminum comb-shaped electrode 20 wired on the substrate 10 can be electrically connected to the wiring conductor 81 formed on the surface of the lid portion. Finally, the metal ball 70 is mounted on the surface of the lid portion by reflow or the like, and SAW FILTER (Fig. 3 (f)) which is an electronic component having a hollow structure of the present invention is obtained.

Next, in Fig. 3, a method of forming the ridge portion and the lid portion of the present invention using both UV exposure and laser apertures will be described. Basically, the method of forming the ridge portion and the lid portion is the same as that for the case of only UV exposure, but the difference is that when the opening 35 for forming the inner conductor is formed inside the lid portion, UV exposure is not applied. Rather, it is suitable for opening the hole with a laser. In the case of (c) of FIG. 3, after the photosensitive resin layer 41 for the lid portion is laminated on the ridge portion 30, the step of (d) of FIG. 3 is performed by using a photosensitive film. An opening 35 for forming an internal conductor is formed inside the cover portion. The laser aperture method differs from UV exposure in that it is not necessary to perform exposure or development with a mask, and is suitable for the case where any pattern is formed freely and for a short time. For lasers, it is known to use YAG lasers, carbon dioxide lasers, and excimer lasers. The manufacturing method of the SAW FILTER in the present invention is not limited to those shown in Fig. 3.

The UV exposure or the laser irradiation can be appropriately selected depending on the thickness of the ridge portion, the shape of the inner conductor formed inside the ridge portion, and the shape of the wiring pattern on the surface of the lid portion.

In Fig. 3, it is shown that a surface is further formed on the surface of the cover portion. In the method of manufacturing the SAW FILTER of the wire layer, in the present invention, the wiring layer having two or more layers may be provided in a portion corresponding to the lid portion. Fig. 4 shows a wiring forming method of a SAW FILTER having two wiring layers in a portion corresponding to the lid portion. The wiring conductor 81 is formed on the surface of the lid portion 40 of the SAW FILTER in the same manner as the one shown in (a) to (e) of FIG. 3, and then the photosensitive film of the present invention is laminated to form a photosensitive resin for the lid portion. After the layer 41 (Fig. 4 (a)), ultraviolet light exposure is performed by using a mask 60 that is shielded from light in the area corresponding to the diameter of the external connection electrode (Fig. 4 (b)), and the cover portion is formed by solvent development. The uppermost layer of 40 forms an opening for the external connection electrode (Fig. 4 (c)). Then, after the external connection electrode is formed by a plating method, finally, the metal ball 70 is mounted on the surface of the lid portion by reflow or the like, and SAW FILTER which is an electronic component having a hollow structure of the present invention is obtained. (d)). In this case, the metal ball is directly mounted via an anti-oxidation metal film (Ni, Au, etc.) of the electrode for the external electrode (the left side of FIG. 4(d)), or a photoresist may be used equal to the cover portion. After the surface of the wiring layer is formed again, the method of mounting the metal ball (the right diagram of (d) of Fig. 4) is performed.

After the above steps, the hollow structure of the SAW FILTER was completed.

When the SAW FILTER produced as described above is sealed by a sealing material as shown in Fig. 5, it is generally carried out in the following steps, but is not limited thereto.

(1) The SAW FILTER is mounted on a forming mold.

(2) A solid-shaped sealing material tablet is placed in the pot of the molding machine.

(3) Melting the sealing material at a mold temperature of 150 to 180 ° C, and Apply pressure to flow into the mold (mold).

(4) Pressurizing for 30 to 120 seconds After the sealing material is thermally cured, the mold is opened, and the molded product is taken out to terminate the sealing of the SAW FILTER.

Usually, the sealing material is sealed before the metal ball is mounted, and after sealing, the metal ball is mounted by reflowing on the opposing surface of the sealed surface of the substrate. However, after the metal ball is mounted, the sealing material can be sealed. In Fig. 5, although one SAW FILTER 100 sealed by a sealing material is shown, the SAW FILTER of the present invention can also be sealed by sealing a plurality of AW filters formed on one substrate with a sealing material. Broken into pieces.

(a) to (j) of FIG. 6 show a method of manufacturing a SAW FILTER obtained by performing die-cutting (cutting) a plurality of SAW FILTERs formed on one substrate and then separating them into individual pieces. First, a plurality of SAW FILTER having the aluminum comb-shaped electrode 20 and the wiring conductor 81 are formed on one substrate, and then the prism portion and/or the lid portion are formed using the photosensitive resin composition or the photosensitive film of the present invention. 6 (a) ~ (e)). In the manufacturing method, the wiring conductor 81 for electrically connecting to the external connection electrode is disposed on both outer sides of the aluminum comb-shaped electrode 20. Next, in order to form the external connection electrode, the photoresist 50 is applied to the entire substrate, and a mask that can be shielded from light at the diameter of the external connection electrode is used, and ultraviolet exposure is performed to develop the image, and an external connection electrode is provided. The photoresist opening portion 51 for formation ((f) of Fig. 6). Next, after the external connection electrode 82 is formed by a plating method or a conductor filling method, the photoresist 50 is removed by a photoresist stripping solution ((g) of FIG. 6). Furthermore, it can also be taken A washing step in which the photoresist residue existing on the surface of the substrate or the lid portion is completely removed. After that, the hollow structure portion is collectively sealed by the transfer molding method using the resin sealing material 90 ((h) of FIG. 6), and the metal ball 70 is mounted by reflow (FIG. 6 (i)). SAW FILTER 100 (Fig. 6 (j)) is obtained by dividing into pieces by die cutting (cutting) or the like. In the present invention, the mounting of the metal balls 70 can also be carried out in the state in which the sheets are packaged after the die cutting step of the substrate.

At this time, the lid portion 40 and/or the rib portion 30 are required to have mold resistance at a mold temperature of 150 to 180 °C. In other words, when the lid portion 40 and/or the rib portion 30 are formed of a photosensitive resin composition, it is desirable that the lid portion 40 and/or the rib portion 30 are not deformed at a temperature of 150 to 180 ° C, and the characteristics are formed in order to obtain the characteristics. The glass transition temperature of the material (cured material) of the lid portion 40 and/or the rib portion 30 is preferably 80 ° C or higher, more preferably 165 ° C or higher, and even more preferably 180 ° C or higher.

Further, the elastic modulus at 150 ° C of the material (cured material) is preferably 0.2 GPa or more, more preferably 0.5 GPa or more, and particularly preferably 1.5 GPa or more. The upper limit of the elastic modulus at 150 ° C is not particularly limited, and is 10 GPa or less from the viewpoint of practicality. In the present invention, the above elastic modulus is not only required to improve the mold resistance, but also is a necessary physical property value in preventing the lands from collapsing or undercutting or maintaining the flatness of the lid portion. Further, the elastic modulus of the cured resin at 150 ° C or higher tends to be higher as the glass transition temperature is higher, but it is not determined only by the glass transition temperature. If the glass transition temperature becomes too high, there is a case where the adhesion force due to the generation of thermal stress is lowered or the moisture absorption rate is significantly increased. Therefore, in the present invention, In order to prevent deformation of the hollow structure, it is preferred that the predetermined physical property value is based on the elastic modulus at 150 °C.

As described above, according to the present invention, in the SAW FILTER manufacturing step, by using a solvent imaging liquid for lithography, a thick film rib pattern can be formed on the piezoelectric substrate together, and then from the above. The cured product (or a sealing substrate such as ceramics) which forms a film-form photosensitive resin composition as a lid portion is sealed to form a hollow structure. Further, in the space of the hollow structure, since the surrounding resin composition can prevent moisture, corrosion of the aluminum electrode can be suppressed. Further, since the resin composition has a high modulus of elasticity, the hollow structure can be maintained even at the temperature and pressure at the time of sealing the resin molding.

[Examples]

Hereinafter, the present invention will be more specifically described based on examples and comparative examples, but the present invention is not limited to the following examples and the like.

In the following description, Mw means the weight average molecular weight of the urethane-based compound, and is obtained by the GPC method using tetrahydrofuran as a solvent.

[Examples 1 to 35 and Comparative Examples 1 to 7]

A photopolymerizable compound (A), a photopolymerization initiator (B), and an inorganic filler (C) containing at least one urethane compound (A1) having an acryloyl group and a methacryl group. The decane coupling agent was mixed with the blending ratio (parts by mass) shown in the following Tables 1 to 5 to obtain a solution of the photosensitive resin compositions of Examples 1 to 35 and Comparative Examples 1 to 7. on The obtained solution was subjected to the evaluation described later. The results are shown in Tables 6 and 7.

Further, the numbers in Tables 1 to 5 indicate the parts by mass of the solid component. In addition, each of the components in Tables 1 to 5 is an urethane-based compound (A1) having at least one of an acryloyl group and a methacrylonitrile group (hereinafter referred to as "amine". The carbamate (meth) acrylate") is represented by a combination of a functional group meaning the number of ethylenically unsaturated groups and a weight average molecular weight. The weight average molecular weight (Mw) was determined by a GPC method using tetrahydrofuran as a solvent. The detailed conditions of the GPC method are as follows.

Device name: HLC-8320GPC made by TOSOH

Column: Gelpack R-420, R-430, R-440 (3 in series)

Detector: RI detector

Column temperature: 40 ° C

Dissolution: tetrahydrofuran

Flow rate: 1ml/min

Reference material: polystyrene

<Material ingredients> ((A1) component)

Among the components (A1) (urethane (meth) acrylate), the trade names are UN-904, UN-952, UN-333, UN-1255, UN-2600, UN-6200, UN-6060PTM The compounds of UN-3320HA, UN-3320HC, UN-9000PEP, UN-9200A, UN-3320HS, and UN-6301 are manufactured by Roots Industrial Co., Ltd.

Among these, UN-6060PTM has a methacryl oxime group and other amines. The carbamate-based compound has an acrylonitrile group.

Further, among the (A1) components, the (A1) component having an acrylonitrile group is TMCH-5R (trade name, manufactured by Hitachi Chemical Co., Ltd.), and has a methacrylic acid group (A2). In terms of the composition, JTX-0309 (trade name, manufactured by Hitachi Chemical Co., Ltd.) and UA-21 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) were used.

A monofunctional urethane-based compound (hereinafter referred to as "monofunctional urethane") is synthesized from phenyl isocyanate and 2-hydroxyethyl acrylate.

((A2) component)

The following compounds are used in the case of a photopolymerizable compound having at least one ethylenically unsaturated group (hereinafter referred to as "other (meth) acrylate").

FA-7220M (trade name, methacrylate-containing methacrylate, manufactured by Hitachi Chemical Co., Ltd.)

EA-6340 (trade name, tetrahydro anhydrous phthalic acid modified vinyl phenol type epoxy resin, manufactured by Nakamura Chemical Industry Co., Ltd.)

A-DPH (trade name, dipentaerythritol, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

M-313 (trade name, iso-cyanuric acid acrylate, manufactured by Toagosei Co., Ltd.)

FA-321M (trade name, ethylene oxide modified bisphenol A acrylate, manufactured by Hitachi Chemical Co., Ltd.)

L-A (trade name, lauryl acrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)

For the other (A2) component, the following compounds were used.

Polyfunctional bisphenol A novolak type epoxy resin (trade name: EPICLON N-865, manufactured by Dainippon Ink and Chemicals Co., Ltd., and "Heering N-865" in the table)

Photosensitive Polyimine (Solvent-based negative photosensitive polyimide UR-3100E series, manufactured by TORAY Co., Ltd., and referred to as "photosensitive polyimine" in the table)

((B) component)

In the case of the component (B), the latter will be used.

I-OXE01 (trade name, 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzhydrylhydrazine), manufactured by BASF Corporation)

Cationic polymerization initiator (diphenyl[4-(phenylthio)phenyl]thioindole trifluoromethylene pentafluoroethylphosphonate)

((C) component)

In the component (C), the following four types of mica A, mica B, cerium oxide A, and cerium oxide B were used.

Mica A (mica, aspect ratio 90, volume average particle diameter 27 μm)

Mica B (mica, aspect ratio 30, volume average particle diameter 5 μm)

Ceria A (mica, spheroidal ceria, volume average particle diameter 0.5 μm)

Ceria B (mica, AEROSIL, volume average particle diameter 16 nm)

(decane coupling agent)

For the decane coupling agent, the latter will be used.

AY43-031 (product name, DOWN CORNING TORAY Co., Ltd.)

<Evaluation of resolution>

The solution of the photosensitive resin composition of the examples and the comparative examples was uniformly applied onto a ruthenium substrate by a spin coater, and dried on a hot plate at 90 ° C for 5 minutes to form a photosensitive resin layer having a film thickness of 30 μm after drying. , manufacturing test substrate. A test substrate on which the photosensitive resin layer was formed, having a spherical diameter of 60 μm The negative-type mask of the opening pattern was exposed to a photosensitive resin layer using a PROXIMITY exposure machine (trade name: UX-1000SM) manufactured by USHIO Electric Co., Ltd. at an exposure amount of 200 mJ/cm ² . This test substrate was immersed in propylene glycol monomethyl ether acetate as an organic solvent-based developing solution for 3 minutes for development. The resist pattern after development was washed with n-butyl acetate, and after drying, it was observed, and as shown in Fig. 7, the solvent resistance was evaluated based on the following criteria. In Fig. 7, reference numeral 11 denotes a ruthenium substrate, and 52 denotes a photosensitive resin layer formed of a photosensitive resin composition. The results are shown in Tables 6 and 7.

A: As shown in Fig. 7 (a), the ball diameter is 60 μm. The opening is open, and the opening is rectangular, and there is no residue after development.

B: As shown in Fig. 7 (b), the ball diameter is 60 μm. Although it is open, the opening has a tapered shape, and an opening having a bottom hem is formed.

B': as shown in Figure 7 (b), the ball diameter is 60μm Although the opening is open, the opening has a tapered shape, and an opening having a bottom hem is formed, and the inclination of the taper is larger than that of the evaluation B.

C: as shown in (c) of Fig. 7, the ball diameter is 60 μm. It is not open and is buried.

<Hollow structure retention>

The solution of the photosensitive resin composition of the examples and the comparative examples was uniformly applied onto a ruthenium substrate by a spin coater, and dried on a hot plate at 90 ° C for 5 minutes to form a photosensitive resin layer having a film thickness of 30 μm after drying. , manufacturing test substrate. The test substrate on which the photosensitive resin layer was formed was passed through a negative mask having an opening pattern of a lattice size of 1 mm square, and a PROXIMITY exposure machine (trade name: UX-1000SM) manufactured by USHIO Electric Co., Ltd. was used to have an exposure amount of 200 mJ/ The exposure of the photosensitive resin layer was performed in cm ² . The test substrate was developed and hardened to obtain a cured film pattern having a lattice shape.

Further, a photosensitive film having a film thickness of 30 μm made of a photosensitive resin composition was formed on a support film made of a polyvinyl phthalate film having a thickness of 50 μm. This photosensitive film was attached to the above-described cured film pattern, and a hollow structure was formed.

Next, the above-mentioned photosensitive film was exposed at a exposure amount of 200 mJ/cm ² using a PROXIMITY exposure machine (trade name: UX-1000SM) manufactured by USHIO Electric Co., Ltd. After the test substrate was cured at 120 ° C for 30 minutes, at 160 ° C for 30 minutes, and at 220 ° C for 60 minutes, the support film was peeled off, and the cross section of the lattice pattern after the hardening was cut by a microscope, and the following reference was made. The hollow structure retention was evaluated. The results are shown in Tables 6 and 7.

A: The hollow portion can be maintained, and there is no undercut at all on the film hardened film.

B: Although the hollow portion can be maintained, the undercut is slightly visible on the film.

B': Although the hollow portion can be maintained, the film can be seen undercut.

C: The film was undercut and the hollow portion collapsed.

<Measurement of elastic modulus and measurement of glass transition temperature>

The solution of the photosensitive resin composition of the examples and the comparative examples was uniformly applied onto a ruthenium substrate by a spin coater, and dried on a hot plate at 90 ° C for 5 minutes to form a photosensitive resin layer having a film thickness of 30 μm after drying. , manufacturing test substrate. In the test substrate on which the photosensitive resin layer was formed, a photosensitive resin layer was exposed to light at a exposure amount of 200 mJ/cm ² using a PROXIMITY exposure machine (trade name: UX-1000SM) manufactured by USHIO Electric Co., Ltd., and the film was cured. The photosensitive resin layer was cured by heating at 120 ° C for 30 minutes, 160 ° C for 30 minutes, and 220 ° C for 60 minutes. The cured film of the obtained photosensitive resin composition was peeled off from the ruthenium substrate, and the elastic modulus and the glass transition temperature at 150 ° C of the cured film which was peeled off were measured by a viscoelasticity tester (trade name: RSA-III, manufactured by TA Instruments Co., Ltd.). To determine. Further, the measurement was carried out under the following conditions. These results are shown in Tables 6 and 7.

Test mode: stretching

Test temperature: room temperature (25 ° C) ~ 300 ° C

Heating rate: 5 ° C / min

Test frequency: 1Hz

Chuck distance: 20mm

<Evaluation of heat and humidity resistance (PCT resistance)>

The solution of the photosensitive resin composition of the examples and the comparative examples was uniformly applied onto a ruthenium substrate by a spin coater, and dried on a hot plate at 90 ° C for 5 minutes to form a photosensitive resin layer having a film thickness of 30 μm after drying. , manufacturing test substrate. In the test substrate on which the photosensitive resin layer was formed, the photosensitive resin layer was exposed to light at a exposure amount of 200 mJ/cm ² using a PROXIMITY exposure machine (trade name: UX-1000SM) manufactured by USHIO Electric Co., Ltd., and the light was cured. Thereafter, the photosensitive resin layer was cured by heating at 120 ° C for 30 minutes, 160 ° C for 30 minutes, and 220 ° C for 60 minutes. The test substrate was placed under conditions of 121 ° C, 100% RH (relative humidity) and 2 atmospheres for 100 hours, and the appearance of the cured film was visually evaluated. The evaluation criteria are as follows. The results are shown in Tables 6 and 7 as PCT resistance.

A: No turbidity, peeling, swelling, or cracking was observed on the cured film.

B: Some of turbidity, peeling, swelling, and cracking were observed on the cured film.

B': Some of turbidity, peeling, swelling, and cracking were observed on the cured film, and the degree was larger than B.

C: The cured film is clearly visible in any of turbidity, peeling, swelling, and cracking.

(resistance to reflow cracking)

The solution of the photosensitive resin composition of the examples and the comparative examples was uniformly applied onto a ruthenium substrate by a spin coater, and dried on a hot plate at 90 ° C for 5 minutes to form a photosensitive resin layer having a film thickness of 30 μm after drying. , manufacturing test substrate. The test substrate on which the photosensitive resin layer was formed was subjected to exposure of a photosensitive resin layer at an exposure amount of 200 mJ/cm ² using a PROXIMITY exposure machine (trade name: UX-1000SM) manufactured by USHIO Electric Co., Ltd., and photohardened. . Thereafter, the photosensitive resin layer was cured by heating at 120 ° C for 30 minutes, 160 ° C for 30 minutes, and 220 ° C for 60 minutes. The test substrate was placed on a hot plate at 260 ° C for 30 seconds, and then returned to room temperature for 30 seconds. This operation was repeated for 5 cycles for one cycle to evaluate the resistance to reflow cracking. The evaluation criteria are as follows. The results are shown in Tables 6 and 7.

A: There is no abnormal appearance.

B: Cracking and peeling can be seen in a part of the substrate.

C: The substrate is fully visible with cracking and peeling.

As shown in Table 6, the photosensitivity composition of all the examples was evaluated as B' or more (A, B or B'), and exhibited excellent effects (Examples 1 to 35). Among them, a photopolymerizable compound (A) containing a total of 2 to 15 (A1) components having a propylene fluorenyl group and a methacryl fluorenyl group in one molecule and having a weight average molecular weight of 950 to 15,000 is known and photopolymerized. The photosensitive resin composition of the initiator (B) was evaluated as B or higher (A or B) in each characteristic, and exhibited excellent effects (Examples 1 to 32).

The photosensitive resin composition of the example has an elastic modulus at 150 ° C of 0.2 GPa or more, and the higher the elastic modulus, the more the hollow structure retention property is improved. In addition, the hollow structure retention property tends to increase as the glass temperature of the photosensitive resin composition increases, but it is not necessarily determined only by the glass transition temperature. This is known from the evaluation results of Example 23 and the like.

Further, in addition to having a total of 2 to 15 acryl fluorenyl groups and methacryl fluorenyl groups in one molecule, and having a weight average molecular weight of 950 to 15,000 (A1) In addition to the photopolymerizable compound (A) and the photopolymerization initiator (B), the component (C) contains an inorganic filler to increase the modulus of elasticity and greatly improve the hollow structure retention. At this time, the glass transition temperature or the adhesion of the photosensitive resin composition is hardly decreased, and conversely, since the moisture absorption rate is small, the PCT resistance and the reflow-resistant cracking resistance are the same as those of the composition not containing the inorganic filler. Or better than it.

In particular, when mica containing a high aspect ratio and a large particle diameter is contained as the inorganic filler (C), the resolution is not greatly lowered, and the hollow structure retention or PCT resistance can be related to the reliability of the electronic component. The characteristics are greatly improved (Examples 25 to 27, 29, 31 to 32).

In addition, even if cerium dioxide such as spherical cerium oxide having a small particle diameter or cerium oxide such as AEROSIL is used as the inorganic filler (C), the hollow structure can be improved in accordance with the content (Examples 28 and 30). .

The photosensitive resin composition of the present invention is excellent in air structure retention, elastic modulus, and moist heat resistance even if it does not contain the inorganic filler (C), but in order to improve these characteristics, a small particle diameter can be used. Inorganic filler. Further, the cerium oxide B (AEROSIL) described in the example 30 is not only the characteristics shown in Table 6, but also has an effect of improving the shape retainability of the coating property when the photosensitive resin composition is applied.

On the other hand, when a photosensitive epoxy resin was used as the component (A), the PCT resistance, particularly the adhesion, was greatly lowered (Comparative Example 1 shown in Table 7). Further, in order to carry out thick film formation, it is necessary to increase the exposure amount of the resin composition containing the photosensitive polyimide resin (Comparative Example 2). However, at high exposure levels, light at the time of exposure hardly reaches the lower portion of the film (near the base) In the portion of the plate, and in the developing step, it was observed that the portion was excessively developed to make the formed film have an inverted tapered shape, and the pattern formability was drastically lowered.

In addition, the photosensitive resin composition containing the urethane-based compound (A1) as the component (A) cannot be used for forming the ridge portion and/or the lid portion of the hollow structure because it cannot satisfy all the characteristics at the same time. Materials (Comparative Examples 3 to 7).

In Comparative Examples 3 to 5, although the hollow structure retention property was maintained, the reflow resistance crack resistance or the PCT resistance was greatly lowered. This is a (meth) acrylate resin that does not contain a urethane-based compound. In an extremely harsh environment such as high-temperature heating or high-temperature and high-humidity, the toughness of the resin is lowered to cause crack growth and a significant decrease in adhesion. The reason.

Further, in Comparative Example 6, although the modulus of elasticity at 150 ° C was 0.3 GPa, in the thermal curing step performed after exposure of the photosensitive resin composition, the ridge portion and the lid portion were deformed, and the desired condition could not be achieved. Hollow structure retention. This reason may be caused by the fact that the glass transition temperature of the edge portion and the lid portion after the exposure is low, and the heat hardening reaction is slightly slow, and the deformation occurs before the polymerization reaction proceeds further in the heat hardening step, but the detailed reason is unknown.

In Comparative Example 7, since the modulus of elasticity was low, the retention of the hollow structure was greatly reduced. As described above, the present invention not only maintains the shape retention of the hollow structure, but also maintains the reliability of the electronic component in an excessively harsh environment, and the urethane-based compound (A1) is an essential component.

From the comparison of Examples 1 to 32 and Examples 33 to 35, it is apparent that the total number of propylene fluorenyl groups and methacryl fluorenyl groups in one molecule is 2 to 15, and the weight average molecular weight is 950 to 15000 (A1). ) the light of the ingredients The photosensitive resin composition (Examples 1 to 32) composed of the polymerizable compound (A) and the photopolymerization initiator (B) exhibited in resolution, hollow structure retention, PCT resistance, and reflow resistance. Excellent.

That is, in Example 34, since the number of (meth)acryl fluorenyl groups was one as the component (A1), the modulus of elasticity and the glass transition temperature were low, and therefore the evaluation of the hollow structure retention and the PCT resistance were evaluated. The result is B' and is slightly worse. On the other hand, in Examples 1 to 32 in which the number of (meth)acrylonyl groups was two (A1), the evaluation results of the hollow structure retention and the PCT resistance were as good as A or B.

Further, in Example 35, as in Example 34, the number of (meth)acrylonyl groups was one as the component (A1), and the inorganic filler (C) was contained. Although the hollow structure retention was improved by the inorganic filler (C), the total of the four evaluation results of the resolution, the hollow structure retention, the PCT resistance, and the reflow resistance was not able to reach B or more.

Further, in Example 33, the weight average molecular weight of the component (A1) was as high as 33,000, and the evaluation result of the resolution was B' and was slightly inferior. On the other hand, in Examples 1 to 32 in which the weight average molecular weight of the component (A1) was 950 to 15,000, the resolution was excellent as A or B.

In the present invention, when the number of functional groups of the urethane-based compound (A1) is 15, it is necessary to adjust the exposure method of light (Example 24). In the example 24, when the amount of the functional group is large, when the exposure amount (200 mJ/cm ² ) is the same as that of the other examples, it is difficult to obtain the resolution which can exhibit the effect of the present invention, so that the exposure amount is 100 mJ/cm ² and becomes small. . This is because the photohardening of the surface of the coating film of the photosensitive resin composition is accelerated due to the large number of photosensitive cells, that is, in order to avoid a decrease in the photo resolution due to the state of the skin. As described above, when the number of functional groups of the urethane-based compound (A1) is 15, in order to obtain a desired resolution, not only a material but also a step of optimizing the production conditions is required, and the production is slightly complicated. In addition, when the number of functional groups of the urethane-based compound (A1) is 15 or more, not only the decrease in resolution but also the decrease in connectivity or the change in characteristics due to the residual of unreacted functional groups become remarkable. . Therefore, in the present invention, the number of functional groups of the urethane-based compound (A1) is preferably 10 or less.

As described above, in the present invention, the photosensitive resin composition of the present invention contains the photopolymerizable compound (A) and the photopolymerization initiator (B), and the photopolymerizable compound (A) has an amine group. The formate compound (A1) is preferably a urethane compound having a total of 2 to 15 propylene groups and methacryl groups and a weight average molecular weight of 950 to 25,000 in one molecule. (A1) and a photosensitive film formed using the photosensitive resin composition, which is excellent in moist heat resistance, has a high modulus of elasticity, and is excellent in hollow structure retention, and is suitably used as a hollow structure device. Use the ribs and / or cover. Moreover, the above-described hollow structure retainability can be sufficiently maintained even when a high temperature and high pressure mold is used for the semiconductor sealing material.

According to the present invention, a photosensitive resin composition excellent in workability and reliability, that is, a photosensitive film formed using the composition, can be produced by a method for forming a rib pattern and a method for forming a hollow structure. A low-cost and highly reliable hollow structure electronic component, specifically, a SAW FILTER can be produced.

10‧‧‧Substrate

11‧‧‧矽 substrate

20‧‧‧ tooth comb electrode

30‧‧‧Edge

32‧‧‧Photosensitive resin layer for ribs

35‧‧‧Opening

40‧‧‧ 盖部

41‧‧‧Photosensitive resin layer for the cover

50‧‧‧ photoresist

51‧‧‧ photoresist opening

52‧‧‧Photosensitive resin layer

60‧‧‧ mask

70‧‧‧metal ball

80‧‧‧Internal conductor

81‧‧‧Wiring conductor

82‧‧‧External connection electrode

90‧‧‧Closed material

100‧‧‧SAW FILTER

Fig. 1 is a view showing a preferred embodiment of one of the SAW FILTER which is one of the electronic components of the present invention and a method of manufacturing the same.

Fig. 2 is a view showing a mounted metal ball SAW FILTER according to another embodiment of the present invention.

Fig. 3 is a view showing a method of manufacturing a SAW FILTER equipped with a metal ball according to the present invention.

Fig. 4 is a view showing a method of forming a SAW FILTER wiring having two wiring layers, which is one of the electronic components of the present invention.

Fig. 5 is a view showing a SAW FILTER sealed by a sealing material according to another embodiment of the present invention.

Fig. 6 is a view showing a method of manufacturing a SAW FILTER in which a sealing material according to another embodiment of the present invention is sealed.

Fig. 7 is a view showing the evaluation criteria of the resolution of the photosensitive resin composition of the present invention.

Claims (13)

A photosensitive resin composition comprising the photopolymerizable compound (A) and a photopolymerization initiator (B), wherein the photopolymerizable compound (A) contains at least one acryl group and The acrylamide-based urethane-based compound (A1). The photosensitive resin composition according to claim 1, wherein the urethane-based compound (A1) is a total of 2 to 15 propylene groups and methacryl groups in one molecule, and the weight average is The molecular weight is 950~25000. The photosensitive resin composition according to claim 1, wherein the urethane-based compound (A1) is a total of 2 to 15 propylene groups and methacryl groups in one molecule, and the weight average is The molecular weight is 950~15000. The photosensitive resin composition according to any one of claims 1 to 3, further comprising an inorganic filler (C). The photosensitive resin composition as described in any one of Claims 1 to 4, wherein the cured product of the photosensitive resin composition has an elastic modulus at 150 ° C of 0.2 GPa or more. The photosensitive resin composition according to any one of claims 1 to 5, which is incorporated in an electronic component having a hollow structure, and can be used as one or both of a rib portion and a lid portion forming the hollow structure. Materials come to the user. A photosensitive film obtained by molding the photosensitive resin composition according to any one of claims 1 to 6 into a film shape. A method for forming a pattern, which has the following steps, A step of laminating a photosensitive resin layer according to any one of claims 1 to 6 or a photosensitive film according to claim 7 to form a photosensitive resin layer, and a predetermined step of forming the photosensitive resin layer An exposure step of partially irradiating the active light with a mask to photoharden the exposed portion, a developing step of removing a portion of the photosensitive resin layer other than the exposed portion, and a developing step of removing the photosensitive resin layer The exposure portion is thermally hardened to form a thermal curing step of the cured resin. A method for forming a hollow structure, comprising the steps of: forming a lenticular pattern provided on a substrate in a hollow structure, and stacking the photosensitive resin according to any one of claims 1 to 6. a step of forming a photosensitive resin layer by the photosensitive film described in claim 7, and a step of irradiating a predetermined portion of the photosensitive resin layer with an active light to photoharden the exposed portion, and the photosensitive resin layer The exposure portion is thermally cured to form a heat curing step of the cured resin. The method for forming a hollow structure according to claim 9 is the step of removing the portion other than the exposed portion of the photosensitive resin layer after the exposure step and before the thermal curing step. The method of forming a hollow structure according to claim 9 or 10, wherein the rib pattern is shaped by the method described in claim 8. Adult. An electronic component having a hollow structure, wherein the hollow structure is formed by using the photosensitive resin composition according to any one of claims 1 to 6 or the photosensitive film described in claim 7 And / or the cover is formed. The electronic component according to claim 12, wherein the electronic component is a surface acoustic wave filter.