JP2010037477A - Material for forming insulating layer, and electronic component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a material for forming an insulating layer, which has a large aspect ratio, can be pattern processed by photolithography and further has an excellent insulation property. <P>SOLUTION: The material for forming the insulating layer, which is in the form of paste or uncured sheet, including: (A) barium sulfate particles having the average particle diameter of at least 1 nm to at most 40 nm; and (B) a compound having a polymerizable group and a carboxyl group or a phosphate ester compound having a polymerizable group. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a paste for forming an insulating layer in which inorganic particles are dispersed in an organic material, an uncured sheet, and an electronic component using the same.

  With the downsizing and high performance of electronic components, there is a demand for materials that can be patterned with a high aspect ratio and that have excellent insulation reliability. In response to such demands, for example, a technique is known in which inorganic particles are dispersed in an organic substance such as a resin to produce a photosensitive resin composition, a patterned cured product is produced, and used as a permanent resist. (For example, refer to Patent Documents 1 to 3). However, such a material has a problem that pattern processing at a high aspect ratio by photolithography is difficult. In addition, since the insulating material is in contact with the wiring made of metal, there is a problem that the insulating material is peeled off or cracked due to the difference in linear expansion coefficient between the metal and the insulating material, thereby impairing the reliability of the electronic component.

On the other hand, a technique is known in which barium sulfate particles having a diameter of 40 nm or less are dispersed to produce a photosensitive resin composition, and pattern processing is performed to obtain an optical wiring material that exhibits athermal properties (for example, Patent Document 4). reference).
JP 2007-11321 A (Claims, Examples) JP 2008-39863 A (Claims, Examples) JP 2007-156404 A (Claims, Examples) WO08 / 056639 pamphlet

  An object of the present invention is to provide an insulating layer forming material that can be patterned with a large aspect ratio by photolithography and that is excellent in insulation.

  The present invention relates to an insulating layer forming material comprising (A) barium sulfate particles having an average particle diameter of 1 nm to 40 nm and (B) a compound having a polymerizable group and a carboxyl group, or a phosphate ester compound having a polymerizable group. It is.

  When the insulating layer forming material of the present invention is used, an insulating layer that is finely processed with a high aspect ratio and that has a linear expansion coefficient after curing that is close to that of a metal and that has excellent insulating properties can be obtained. This feature is advantageous for obtaining a large Q value when forming the inductor. In addition, since the coefficient of linear expansion of the insulating layer is close to that of metal, the stress generated between the insulating layer and the metal wiring due to temperature changes can be reduced, and the reliability of components formed from these can be increased. Can do.

  The insulating layer forming material of the present invention comprises (A) barium sulfate particles having an average particle diameter of 1 nm to 40 nm and (B) a compound having a polymerizable group and a carboxyl group, or a phosphate ester compound having a polymerizable group. It is a material that contains. As long as these materials contain these components, the shape is not limited, and may be, for example, a paste or an uncured sheet. Hereinafter, unless otherwise specified, the paste material is “paste A”, the uncured sheet material is “uncured sheet A”, the compound having a polymerizable group and a carboxyl group, or the phosphate ester compound having a polymerizable group. The case where “compound A” is used and the material of the present invention is in the form of a paste and an uncured sheet will be described.

  The material of the present invention can be finely processed at a high aspect ratio, and the linear expansion coefficient after curing is close to that of a metal. Therefore, it is a very suitable material for forming an insulating layer of an electronic component. The high-aspect-ratio microfabrication referred to in the present invention means that the processed pattern has a shape whose height is larger than the width (the aspect ratio is greater than 1).

  If an insulating layer having a high aspect ratio can be formed, even if the wiring width is narrow, the wiring thickness can be increased and the cross-sectional area can be increased, so that the conductor wiring can be formed three-dimensionally and a three-dimensional electronic component can be formed. it can. For this reason, when mounting such an electronic component on a board | substrate, there exists an advantage that a mounting area can be made small. In addition, since the structure is three-dimensional, the distance from the center to the end is shorter than that with strong two-dimensionality, so the absolute value of expansion due to temperature change at the end of the electronic component is reduced, and the heat There is an advantage that the generation of stress due to the volume change due to fluctuation is reduced, and the reliability as an electronic component is increased.

  For example, taking an inductor as an example of an electronic component, the inductor can be manufactured by removing the insulating layer formed on the substrate in a spiral shape by pattern processing and filling the removed portion with a conductive material such as a metal such as copper. When such an inductor is formed, a conductive layer is formed on a substrate in advance, an uncured film is formed thereon using the material of the present invention, and an insulating layer is formed by performing pattern processing. By doing so, it is possible to easily form a spiral circuit made of a metal material in a portion where the insulating layer is removed by electrolytic plating. If the material of the present invention is used, the pattern processing aspect ratio of the insulating layer can be increased. Therefore, by forming a conductive material formation region deeply in the thickness direction of the insulating layer, the in-plane of the spiral is formed. The cross-sectional area of the spiral circuit can be increased without increasing the direction spread. As a result, the wiring resistance of the spiral circuit can be reduced, and the Q value of the inductor can be increased, which is preferable.

  Furthermore, an insulating layer manufactured from the insulating layer forming material of the present invention or other insulating layers and wiring layers can be combined in multiple layers to form a more complicated circuit.

  In the paste A and the uncured sheet A of the present invention, the compound A has a function of dispersing barium sulfate particles. The compound A covers the surface of the barium sulfate particles by the interaction of the carboxyl group or the phosphate ester binding site in the compound A with the barium sulfate particles. The polymerizable group of the compound A covering the surface of the barium sulfate particles is directed to the outside of the barium sulfate particles, and the barium sulfate particles are stably dispersed in affinity with other compounds in the paste A and the uncured sheet A. It is thought to let you.

  The polymerizable group in the compound A is an organic group that can be polymerized by light or heat by a polyaddition reaction or a radical reaction. In the paste A and the uncured sheet A of the present invention, since the compound A is involved in the polymerization, the curing proceeds promptly and reliably.

  In the present invention, compound A itself is polymerized by light or heat to become a matrix resin in the cured product. Therefore, the compound A used in the present invention has both a function as a dispersant for barium sulfate particles and a function as a matrix resin. When barium sulfate is dispersed in a resin having a polymerizable group for forming a matrix with a dispersant having no polymerizable group, when the matrix resin is polymerized, the barium sulfate particles move and gather, It is conceivable that the dispersibility decreases. On the other hand, in the paste A and the uncured sheet A of the present invention, since the compound A is polymerized in a state where the barium sulfate particles are captured, the dispersibility of the barium sulfate particles can be kept good even in the cured product. . For this reason, the mechanical strength of the cured product becomes uniform and the surface flatness becomes good.

  Furthermore, pattern processing by a photolithography method can be performed by curing the paste A and the compound A of the uncured sheet A with light. In this case, since compound A is polymerized in the state where the barium sulfate particles are captured in the exposed area, a strong network is formed starting from the barium sulfate particles, and the swelling and dissolution of the exposed area during development can be suppressed. Can be realized.

  The polymerizable group of the compound A is preferably one having good affinity with other compounds contained in the uncured sheet A for the purpose of favorably dispersing the barium sulfate particles. These include vinyl groups, acrylate groups, methacrylate groups, epoxy acrylate groups, epoxy methacrylate groups, epoxy groups, and the like.

  Compound A has a carboxyl group together with the polymerizable group. When the carboxyl group of the compound A interacts with the barium sulfate particles, the compound A covers the surface of the barium sulfate particles, and the barium sulfate particles can be dispersed. Further, when the paste A of the present invention and the compound A in the uncured sheet A are cured by light and pattern processing is performed by a photolithography method, the compound A has a highly polar carboxyl group, so that elution into the developer is caused. It is quick and can reduce the residue at the time of development in the unexposed area.

  The compound A used in the present invention is preferably one represented by the following general formula (1).

In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a divalent group represented by any one of the following general formulas (2) to (4).

  In general formula (2)-(4), n and m are the integers of 1-3, respectively.

The polymerizable group in the general formula (1) is an acrylate group when R ¹ is a hydrogen atom, and is a methacrylate group when R ¹ is a methyl group. An acrylate group or a methacrylate group has an unsaturated bond and can be radically polymerized by light irradiation or heating. When radical polymerization is performed by light, a wiring pattern or the like can be formed by applying a photolithography method in which light is irradiated through a photomask. An acrylate group in which R ¹ is a hydrogen atom is preferred because the polymerizability is better.

  When n and m in the general formulas (2) to (4) are small, the number of polymerizable groups and carboxyl groups per unit weight increases, so that the polymerizability becomes better and the barium sulfate particles Dispersibility is improved. On the other hand, when the number of n and m is large, the effect of causing steric hindrance when the compound A is coordinated to the barium sulfate particles is increased, so that dispersibility is improved. Therefore, n and m are preferably ethylene groups having 2 carbon atoms.

Among the compounds represented by the general formula (1), a compound in which R ¹ is a hydrogen atom and R ² is a divalent group represented by the general formula (4) is preferable. Is more preferably 2. When this compound is used, the polymerizability and developability become better. Moreover, the dispersibility of the barium sulfate particles becomes better, and the average particle diameter of the dispersed barium sulfate can be further reduced. For this reason, light irradiated at the time of exposure to a film or uncured sheet coated and dried with a paste composition reaches a deep part in the film thickness direction with almost no irregular reflection or scattering, enabling high aspect ratio pattern processing. It becomes.

Specific examples of the compound A represented by the general formula (1) used in the present invention include “HOA-MS” (trade name, R ¹ in the general formula (1) is a hydrogen atom, manufactured by Kyoeisha Chemical Co., Ltd. There are those ^{wherein R 2} is represented by the general formula (2), n, m are both 2.), "HOA-HH " R 1 is a hydrogen atom in the (trade name, the general formula (1) R ² is represented by the general formula (3), and n is 2.), “HOA-MPL” (trade name, R ¹ in the general formula (1) is a hydrogen atom, R ² is represented by the general formula (4), and n is 2.).

  On the other hand, a compound A represented by the following general formula (5) is also preferably used.

In the general formula (5), R ^{3 to} R ⁵ represent a monovalent group or a hydrogen atom represented by any of the following general formulas (6) to (10), and R ^{3 to} R ⁵ are the same or different. May be. However, all of R ^{3 to} R ⁵ are not hydrogen atoms.

In General Formulas (6) to (10), R ^{6 to} R ⁹ represent a hydrogen atom or a methyl group. R ^{10 to} R ¹¹ are a divalent group having 1 to 10 carbon atoms, preferably a divalent hydrocarbon group having 1 to 10 carbon atoms, and more preferably an alkyl group having 2 carbon atoms. R ¹² is a divalent group having 1 to 10 carbon atoms having a hydroxyl group, preferably an organic group represented by the following general formulas (13) to (15).

In the general formula (5) Compound A represented by, any two of R ³ to R ⁵ is phosphoric acid monoester is a hydrogen atom, a phosphodiester any one of R ³ to R ⁵ is a hydrogen atom Rather than disperse the barium sulfate particles. Also, diester phosphate, than phosphoric acid triester both free of hydrogen atoms of R ³ to R ^5, since improving the dispersibility of the barium sulfate particles preferred.

The monovalent groups represented by the general formulas (6) to (9) have an acrylate group or a methacrylate group, and can be radically polymerized by light irradiation or heating. Moreover, the monovalent group represented by the general formula (10) can be ionically polymerized by light irradiation or heating. An acrylate group in which R ^{6 to} R ⁹ are hydrogen atoms is preferred because the polymerizability becomes better.

Since the number of carbon atoms in R ^{10 to} R ¹² in the general formulas (8) to (10) is small, the number of polymerizable groups and phosphate ester bonding sites per unit weight increases, so that the polymerizability is better. And the dispersibility of the barium sulfate particles is improved. Moreover, since the effect of R ¹⁰ to R ¹² Compound A and a larger number of carbon atoms in it is sterically hindered when coordinated to barium sulfate particles increases, thereby improving the dispersibility. ^Therefore, the number of carbon atoms in R 10 ^{to R 12} is preferably 1-4.

In particular, among the compounds represented by the general formula (5), it is preferable that at least one of R ^{3 to} R ⁵ is a monovalent group represented by the general formula (8), in which case R ¹⁰ is carbon. It is more preferably a divalent hydrocarbon group having 1 to 3 numbers. Further, at least one of R ^{3 to} R ^{5 in} the general formula (5) is a monovalent group represented by the general formula (9), and R ^{12 in the} general formula (9) has 2 to 2 carbon atoms having a hydroxyl group. 3 is preferably a divalent hydrocarbon group.

  Specific examples of the compound A represented by the general formula (5) used in the present invention include “Light acrylate P-1A” (trade name, phosphate monoester having an acrylate group) manufactured by Kyoeisha Chemical Co., Ltd., Kyoeisha “Light Ester P-1M” (trade name, phosphate monoester having a methacrylate group), “Light Ester P-2M” (trade name, phosphate diester having a methacrylate group) manufactured by Kagaku Co., Ltd., Daicel Cytec RDX63182 (a phosphoric diester having an epoxy acrylate group) manufactured by Co., Ltd. may be mentioned. The compound A used in the present invention may be one type or a plurality of types.

  The dispersant in the cured product may increase the linear expansion coefficient of the cured product. For this reason, it was considered preferable to make the dispersant content as small as possible. In the present invention, the compound A itself, which also contributes to the dispersibility of the barium sulfate particles, is polymerized and cured, or is involved in the polymerization with the resin described later, so that it is possible to suppress an increase in the coefficient of linear expansion.

  As described above, the paste A and the uncured sheet A of the present invention form a matrix in the cured product by polymerization of the compound A, but may further contain a resin that forms a matrix. Resins used at this time include polyamic acid, vinyl resin, norbornene resin, epoxy resin, acrylate resin, methacrylate resin, epoxy acrylate resin, epoxy methacrylate resin, cyanate resin, bismaleimide-triazine resin, benzocyclobutene resin, siloxane resin, etc. And thermosetting or UV curable resins having a polymerizable group. Moreover, thermoplastic resins, such as an aramid resin, a polystyrene, polyetherimide, polyphenylene ether, thermoplastic polyimide, are mentioned. These resins may be used singly or plural kinds may be used in an appropriate ratio.

  In applications where heat resistance is required in the process, among the above resins, resins having a polymerizable group such as thermosetting resins and UV curable resins are preferable. Moreover, when using the hardened | cured material obtained from the paste A and the unhardened sheet | seat A for the use as which a light transmittance is requested | required, an epoxy resin, an acrylate resin, a methacrylate resin, an epoxy acrylate resin, an epoxy methacrylate resin, a siloxane resin, etc. are suitable. Used for.

  In the present invention, the polymerizable groups of the thermosetting resin or the UV curable resin may be polymerized, or the polymerizable group of these resins and the polymerizable group of the compound A may be polymerized. . The polymer formed in the cured product of the present invention has various forms such as (a) a polymer comprising Compound A, (b) a polymer comprising Compound A and a resin, or (c) a polymer comprising only a resin. And has barium sulfate particles present in a dispersed state in these polymers. Unless otherwise specified, each of the polymers (a) to (c) present in the cured product obtained from the paste A and the uncured sheet A is simply referred to as “polymer”.

  Depending on the composition of compound A, resin, polymerization accelerator, etc. contained in paste A and uncured sheet A, the polymer in the cured product obtained from paste A and uncured sheet A is the above (a) to (c ) Or a mixture of these.

  For example, when the polymerizable group of the compound A is an acrylate group and the polymerizable group of the resin is also an acrylate group, a large amount of the compound A exists in the vicinity of the barium sulfate particles. In the region away from the barium sulfate particles, the polymer (c) is abundant, and the polymer (b) is present in the middle region. As another example, from the paste A and the uncured sheet A containing the compound A in which the polymerizable group is an acrylate group and the resin in which the polymerizable group is an epoxy group, the polymer (a), and (c) The hardened | cured material which consists of a polymer of this can be manufactured. Further, when a plurality of resins are used, for example, using a compound A in which the polymerizable group is an acrylate group, a resin in which the polymerizable group is an epoxy acrylate group, and a resin in which the polymerizable group is an epoxy group, These three components can be copolymerized to obtain the polymer (b).

    The refractive index of the compound A exemplified above is 1.46 for “HOA-MS”, 1.48 for “HOA-HH”, and 1.52 for “HOA-MPL”. Further, “light acrylate P-1A” is 1.47, “light ester P-1M” is 1.47, “light ester P-2M” is 1.47, and RDX63182 is 1.54. Use of “HOA-MPL” or RDX63182, which has a refractive index close to that of barium sulfate, is preferable because the light transmittance of the paste A and the uncured sheet A tends to be good, and photolithography processing at a high aspect ratio can be easily performed.

  When the cured product obtained from the paste A of the present invention and the uncured sheet A is used for applications requiring heat resistance and light transmittance, the polymerizable group possessed by the thermosetting resin or the UV curable resin is an epoxy. A group, an acrylate group, a methacrylate group, an epoxy acrylate group, an epoxy methacrylate group, and the like are preferable. However, when an epoxy resin or the like is cationically polymerized, the cationically active species may be adsorbed on the barium sulfate particles, and the polymerization reaction may be slowed. Accordingly, acrylate resins, methacrylate resins, epoxy acrylate resins, and epoxy methacrylate resins suitable for radical polymerization are preferred. When used as an optical material, those having a refractive index close to that of the barium sulfate particles as described above are preferable. For example, an acrylate resin represented by the following formula (11) (refractive index: 1.55), or the following formula: And an epoxy acrylate resin represented by (12) (refractive index: 1.56). In the case of performing pattern processing by photolithography using the paste A and the uncured sheet A, if a resin represented by the following formula (11) is selected as the resin, the residue in the unexposed area during development can be reduced. This is preferable. On the other hand, when a resin represented by the following formula (12) is selected as the resin, the temperature dependence and the linear expansion coefficient of the refractive index of the cured product obtained from the paste A and the uncured sheet A can be reduced.

  In the paste A and the uncured sheet A of the present invention, the content of the compound A is preferably 5 parts by weight or more and 20 parts by weight or less with respect to 100 parts by weight of the barium sulfate particles. When the content of the compound A with respect to the barium sulfate particles is 5 parts by weight or more, the dispersibility of the barium sulfate particles can be increased, and the dispersed particle diameter of the barium sulfate particles can be reduced. High-aspect ratio pattern processing becomes easy. On the other hand, considering the refractive index difference between compound A and barium sulfate, if the content of compound A with respect to barium sulfate particles is 20 parts by weight or less, light enters deeply in the film thickness direction during exposure, and a pattern with a high aspect ratio Processing becomes easy.

  Further, in the paste A and the uncured sheet A of the present invention, the preferable content of the compound A with respect to the entire paste A and the uncured sheet A is such that the polymer obtained by curing comprises only the compound A, It depends on the case of resin. For example, when the polymer in the cured product is only the embodiment of (a) in which compound A is polymerized and cured alone, the content of compound A is not particularly limited, but the solid component in paste A and uncured sheet A The content is preferably 20% by weight or more and 70% by weight or less. When the content of the compound A is 20% by weight or more with respect to the solid component in the paste A and the uncured sheet A, the crack resistance of the obtained cured product and the adhesion to the substrate are improved, and the cohesive failure is prevented. Also increases resistance. When the content of the compound A is 30% by weight or more with respect to the solid components in the paste A and the uncured sheet A, these effects are further enhanced and further preferable. When the content of Compound A is 70% by weight or less with respect to the solid component in the paste A and the uncured sheet A, the refractive index change rate and the linear expansion coefficient due to the temperature of the obtained cured product can be further reduced. it can. It is more preferable that the content of the compound A is 50% by weight or less with respect to the solid component in the paste A and the uncured sheet A because these effects are further increased.

  On the other hand, when the polymer in the cured product includes the embodiment of (b) or (c), the sum of the content of the compound A and the resin is 20% by weight with respect to the solid components in the paste A and the uncured sheet A. The above is preferable, and 30 wt% or more is more preferable. Moreover, 70 weight% or less is preferable with respect to the solid component in the paste A and the uncured sheet A, and 50 weight% or less is more preferable. The reason why it is preferable to be in this range is the same as the reason in the embodiment (a). The mixing ratio of the compound A and the resin can be arbitrarily set in accordance with the composition ratio of the polymer of the compound A and the resin to be manufactured. However, the content of the compound A is 1 weight with respect to the barium sulfate particles. % Or more is preferable because the dispersibility of the barium sulfate particles can be improved.

  Moreover, when using resin which has a polymeric group, it is preferable to set these mixing ratios in consideration of the polymerization characteristic of the compound A and resin. That is, when (b1) the compound A and the resin having a polymerizable group are each independently polymerized, and (b2) when the resin having a polymerizable group is polymerized in a chain form starting from one compound A, (b3) When the compound A and the resin having a polymerizable group are alternately polymerized, the mixing ratio of the compound A and the resin having a polymerizable group is different. For example, in the case of alternately polymerizing the compound A and the epoxy resin in which the polymerizable group is an epoxy acrylate group, which is an example of the above-described embodiment (b3), it is preferable that the number of both polymerizable groups is the same.

  The paste A and the uncured sheet A of the present invention may contain a polymerization accelerator that generates active species such as radicals, cations, and anions in order to accelerate the polymerization of the compound A and the resin. Some polymerization accelerators are activated by light irradiation or heat treatment, and can be used properly according to the application. When patterning the paste A and the uncured sheet A by photolithography, a polymerization accelerator that is activated by light irradiation is used. Examples of the polymerization accelerator that generates radicals by UV light irradiation include oxime, benzophenone, triazine, and benzotriazole. Examples of the polymerization accelerator that generates cations by UV light irradiation include phosphonium-based, sulfonium-based, and iodonium-based materials.

  The paste A and the uncured sheet A of the present invention contain barium sulfate having an average particle diameter of 1 nm to 40 nm. In addition, the average particle diameter in this invention refers to a number average particle diameter. The barium sulfate particles in the paste A and the uncured sheet A are in a state of primary particles in which aggregation is completely loosened and in a state in which a plurality of primary particles are aggregated. Here, the particle diameter of the barium sulfate particles in the paste A and the uncured sheet A is the particle diameter of the primary particles that are not aggregated, and the aggregated primary particles are the particles of the aggregates. Is the diameter. In order to produce the paste A and the uncured sheet A in which the average particle diameter of the dispersed barium sulfate particles is 40 nm or less, the average particle diameter of the primary particles of the barium sulfate particles to be used needs to be 40 nm or less. As what satisfies this, for example, BF-40 (average primary particle diameter: 10 nm) manufactured by Sakai Chemical Industry Co., Ltd. can be mentioned. As a method of measuring the average particle diameter of the barium sulfate particles in the paste A and the uncured sheet A, the particles are directly observed by SEM (scanning electron microscope) or TEM (transmission electron microscope), and the number average of the particle diameters The method of calculating is mentioned. At this time, it is preferable to observe the paste A and the uncured sheet A after producing a cured product by heat treatment or light irradiation. In this curing process, since the number average particle diameter of the barium sulfate particles in the paste A and the uncured sheet A does not change, the number average particle diameter of the barium sulfate particles in the cured product is the same as that in the paste A and the uncured sheet A. It is equal to the number average particle diameter of the barium sulfate particles.

  When the average particle diameter of the barium sulfate particles in the paste A and the uncured sheet A is 40 nm or less, the homogeneity is improved in each form of the paste A, the uncured sheet A and the cured product, and electrical properties such as dielectric constant The spots will disappear. When the average particle diameter of the barium sulfate particles in the paste A and the uncured sheet A is 40 nm or more, light used for exposure at the time of exposure is easily scattered in the film, making it difficult to process a high aspect ratio, It may happen that the processing margin of the conditions and the development conditions linked thereto is very narrow. Furthermore, when the average particle diameter of the barium sulfate particles in the paste A and the uncured sheet A is 30 nm or less, the light irradiated at the time of exposure reaches almost a deeper position in the film thickness direction without being scattered. Pattern processing with a large ratio becomes possible.

  On the other hand, when the particle diameter of the barium sulfate particles is 1 nm or more, the specific surface area with respect to the volume of the particles becomes small, so that the dispersibility of the particles becomes good. This effect is further increased when the number average particle diameter of the barium sulfate particles is 5 nm or more.

  In this invention, it is preferable that content of the barium sulfate particle | grains of the paste A and the unhardened sheet | seat A is 30 to 80 weight% with respect to a solid component. When the content of the barium sulfate particles with respect to the solid components of the paste A and the uncured sheet A is 30% by weight or more, the linear expansion coefficient of the cured product obtained from the paste A and the uncured sheet A is reduced. The content of the barium sulfate particles with respect to the solid components of the paste A and the uncured sheet A is more preferably 50% by weight or more. When the content of the barium sulfate particles relative to the solid components of the paste A and the uncured sheet A is 80% by weight or less, the crack resistance and the adhesion to the substrate are improved, and the resistance to cohesive failure is increased. In addition, when pattern processing is performed by a photolithography method, the residue of unexposed portions at the time of development is reduced. Therefore, the content of barium sulfate particles with respect to the solid components in the paste A and the uncured sheet A is more preferably 70. % By weight or less.

  The paste A and the uncured sheet A of the present invention preferably contain a silane coupling agent. By containing the silane coupling agent, it is possible to reduce the thinning and peeling of the pattern of the exposed portion in the pattern processing by the photolithography method, and to suppress the generation of cracks, thereby realizing a clear pattern shape. Moreover, the residue of an unexposed part can also be reduced more. In general, it is known that a silane coupling agent has an effect of improving the adhesion between an inorganic material and an organic material. Also in the present invention, the adhesion between the resin component in the composition and the inorganic component, and the adhesion between the resin component in the composition and the inorganic substrate such as a silicon wafer are improved, and the exposed portion in pattern processing by a photolithography method is improved. The effect of reducing the thinning and peeling of the pattern and suppressing the occurrence of cracks can be expected. On the other hand, the following reasons can be considered regarding the effect of reducing the residue of the unexposed part in the pattern processing by the photolithography method. When the developer comes into contact with the unexposed area, the resin, the compound A and the like are eluted, and the barium sulfate particles captured by the compound A are also eluted. When the compound A is detached from the barium sulfate particles during development, the barium sulfate particles whose surfaces are exposed aggregate together, and the resin in the vicinity thereof also adheres to form a development residue. However, when a silane coupling agent is present, the silane coupling agent strengthens the binding force between the inorganic component barium sulfate particles and the organic component compound A, so that the dispersibility of the barium sulfate particles during development is maintained. As a result, the composition elutes quickly, and a residue hardly forms.

  Examples of silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, N-2 (amino Ethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane and the like are preferable. Moreover, it is preferable that content of the silane coupling agent of the paste A and the unhardened sheet | seat A is 0.1 to 10 weight% with respect to a solid component. When the content of the silane coupling agent relative to the solid components of the paste A and the uncured sheet A is 0.1% by weight or more, a sufficient effect by the silane coupling agent can be obtained. In addition, the general silane coupling agents including those listed above have a refractive index of 1.45 or less and a large difference in refractive index from the barium sulfate particles. Therefore, it is preferable that the content of the silane coupling agent with respect to the solid component in the paste A and the uncured sheet A is 10% by weight or less because Rayleigh scattering is reduced and light transmittance is improved.

  Moreover, the paste A and the uncured sheet A of the present invention may contain a dispersant other than the compound A. The content of the dispersant other than Compound A is preferably 5 parts by weight or more and 20 parts by weight or less with respect to 100 parts by weight of the barium sulfate particles. If the content of the dispersant other than the compound A is 5 parts by weight or more, the effect of improving the dispersibility of the barium sulfate particles is remarkable, and if it is 20 parts by weight or less, from the paste A and the uncured sheet A. The refractive index change rate and the linear expansion coefficient depending on the temperature of the resulting cured product are reduced.

  A polyethylene terephthalate (PET) film can be used as a carrier for the base material for producing the uncured sheet A of the present invention. As the PET film, the surface thereof is preferably subjected to a release treatment, and the release material is preferably a silicone resin. The thickness of the PET film is not particularly limited, but is preferably in the range of 30 to 80 μm from the viewpoint of workability.

  Moreover, the uncured sheet A of the present invention may have a cover film on the film in order to protect the uncured film. Thereby, the surface of the uncured film can be protected from contaminants such as dust and dust in the atmosphere.

  The uncured sheet A of the present invention preferably has a peel strength between the PET film and the adhesive tape of 74 N / m or more and 114 N / m or less. When the peel strength is 74 N / m or more, when the uncured sheet A is formed on the PET film, a uniform film thickness can be easily obtained and pinholes can be prevented. Moreover, if peeling strength is 114 N / m or less, a PET film can be peeled easily, without impairing the surface state of the paste A and the uncured sheet A. Here, the peel strength can be measured using Tensilon. Adhesive tape (Nitto Denko 31B tape, 25 mm width) is applied to the center part of the joint surface between the PET film and the adhesive tape at a center part and an end part of about 20 mm part using a rubber roller. After bonding, leave for 10-15 minutes (temperature 20 ± 2 ° C, humidity 65 ± 5% RH), then measure the peel strength of the adhesive tape using Tensilon at a peeling speed of 200 mm / min. PET film and adhesive tape And peel strength. A bar coater is used as a coating method on the PET film. Examples of the method for removing the organic solvent include heating with an oven or a hot plate, vacuum drying, heating with an electromagnetic wave such as infrared rays or microwaves, and the like. Here, when the removal of the organic solvent is insufficient, the composition obtained by the subsequent curing treatment may be in an uncured state or may have poor thermomechanical properties.

  Next, the manufacturing method of the paste A and the uncured sheet A of the present invention will be described in detail. Since the uncured sheet A can be manufactured using the paste A, a method for manufacturing the paste A will be described first.

  First, a method for producing a dispersion in which barium sulfate particles are dispersed in an organic solvent is shown. Barium sulfate particles having an average primary particle size of 40 nm or less (secondary particles, including those in an aggregated state), compound A, organic solvent, and other resins, pH adjusters, polymerization inhibitors, etc. as required Are mixed and stirred. Immediately after mixing, since the air layer covers the surface of the barium sulfate particles, the barium sulfate particles and the organic solvent are not sufficiently wetted, and the viscosity may increase. In that case, it is preferable to stir over time with a rotary blade or the like until the barium sulfate particles and the organic solvent are completely wetted.

  When mixing the barium sulfate particles, the total amount of the resin necessary for producing the desired cured product or a part thereof may be added. Compared with the case where the resin is added after the dispersion treatment, the resin and the barium sulfate particles can be mixed uniformly in the case where the resin is added before the dispersion treatment. On the other hand, the viscosity of the dispersion may increase and the efficiency of the dispersion process may deteriorate, or the storage stability of the dispersion after the dispersion process may deteriorate. Regarding Compound A, the necessary amount may be added before the dispersion treatment, or a part of the necessary amount may be added before the dispersion treatment, and the remaining amount may be added after the dispersion treatment. Further, compound A and other substances can be gradually added while measuring properties such as the viscosity of the dispersion during the dispersion treatment.

  In addition, a polymerization accelerator, an antifoaming agent, an antioxidant, a polymerization inhibitor, a plasticizer, a silane coupling agent and the like necessary for producing the desired cured product may be added. However, it is preferable to add a polymerization accelerator or the like immediately before manufacturing the paste A from the viewpoint of the storage stability of the dispersion.

  After mixing and stirring the barium sulfate particles (including secondary particles and those in an agglomerated state), compound A, an organic solvent, and other necessary substances, the barium sulfate particles are dispersed in a dispersing device.

  Examples of the dispersing device include bead mills such as “Ultra Apex Mill” (trade name) manufactured by Kotobuki Industries Co., Ltd. and “Star Mill” (trade name) manufactured by Ashizawa Finetech Co., Ltd. The average particle diameter of the beads used in the bead mill is preferably 0.01 mm or more and 0.5 mm or less. When the average particle diameter of the beads is 0.5 mm or less, since the frequency of contact between the barium sulfate particles and the beads in the bead mill is high, a sufficient dispersion effect can be obtained. On the other hand, when the average particle diameter of the beads is 0.01 mm or more, since the momentum of each bead is large, sufficient shear stress is obtained to disperse the aggregated barium sulfate particles.

  As the beads, ceramic, glass, metal or the like can be used. Examples of the material of the beads include soda glass, quartz, titania, silicon nitride, silicon carbide, alumina, zirconia, zirconium silicate, steel, and stainless steel. Among these, zirconia beads having particularly high hardness can be preferably used.

  Dispersion by the bead mill may be performed by a single treatment using small beads, or may be performed by changing the size of the beads step by step. For example, the dispersion treatment is first performed using beads having a particle diameter of 0.5 mm until the dispersion particle diameter of the barium sulfate particles is about 100 nm, and then the dispersion treatment is performed using finer beads. Good.

  The time spent for the dispersion treatment is appropriately set according to the type and composition ratio of the substances constituting the dispersion liquid such as barium sulfate particles, compound A, and organic solvent. In addition, sampling the dispersion at regular intervals and measuring the average particle size of the barium sulfate particles in the dispersion allows grasping the change over time in the dispersion state and judging the end of the dispersion process. preferable. As an apparatus for measuring the particle size of the barium sulfate particles in the dispersion, “Zetasizer Nano ZS” (trade name) manufactured by Sysmex Corporation, which is a dynamic light scattering method, can be mentioned. Next, a method for producing the paste A by mixing the dispersion obtained by the above method with a resin or the like will be described. However, when all the substances necessary for producing the desired cured product are mixed during the production of the dispersion, the dispersion obtained by the above method becomes the paste A.

  When the resin is mixed with the dispersion of barium sulfate particles, the type and amount of the resin to be mixed are selected according to the composition of the compound A and the like in the dispersion. When manufacturing an electronic component using the paste composition in which barium sulfate particles obtained in the present invention are dispersed, the refractive index of compound A or resin is close to the refractive index (1.6) of the barium sulfate particles. High aspect ratio photolithography processing is preferable. When mixing the dispersion and the resin, the dispersion may be injected into the resin until a predetermined amount is reached, or the resin may be injected into the dispersion until the predetermined amount is reached. The composition can be adjusted by further adding Compound A during the manufacture of the paste A.

  In order to make the paste composition obtained by mixing a predetermined amount of the dispersion and a resin, etc., more homogeneous, a treatment using a ball mill or a roll mill can be performed. In addition, when bubbles are mixed in the paste composition due to the mixing treatment, it is allowed to stand, put under reduced pressure, or remove bubbles by using a stirring defoaming machine, etc. It is possible to avoid air bubbles from entering the object.

  In order to adjust the viscosity of the paste A, an organic solvent may be further added, or an appropriate amount of the organic solvent may be removed by heating or reduced pressure. Further, the polymerization reaction of Compound A or resin may be appropriately advanced by heat treatment or light irradiation.

  Next, an example of a method for producing an uncured sheet according to the present invention will be described. The paste A produced as described above is applied onto a polyethylene terephthalate (PET) film, the organic solvent is removed, and an uncured sheet is produced. A bar coater is used as a coating method on the PET film. Examples of the method for removing the organic solvent include heating with an oven or a hot plate, vacuum drying, heating with an electromagnetic wave such as infrared rays or microwaves, and the like. Here, when the removal of the organic solvent is insufficient, the composition obtained by the subsequent curing treatment may be in an uncured state or may have poor thermomechanical properties. Moreover, when the solid content concentration of the paste A is low and an uncured sheet having a desired film thickness cannot be produced, two or more uncured sheets after removal of the organic solvent may be bonded together.

  Next, an example of an uncured sheet pasting method and a curing method according to the present invention will be described. First, an uncured sheet is laminated on a substrate. A laminator may be used, or a substrate heated on a hot plate may be manually laminated using a rubber roller. After lamination, the PET film is peeled off after sufficiently cooling.

  Depending on the curing mechanism of the compound A or the resin in the paste A and the uncured sheet A used, the curing reaction of the paste A and the uncured sheet A is advanced by heat treatment or light irradiation. In this case, a plurality of treatments may be combined in order to complete curing such as heat treatment after light irradiation. In addition, when the heat treatment is performed in an environment of 100 ° C. or higher, it is preferable to perform the treatment under an inert atmosphere such as nitrogen because the oxidation of the polymer is suppressed. Also, in the case of curing by light irradiation with a composition using a polymerization accelerator that generates a radical that loses its activity due to oxygen, treatment under an inert atmosphere such as nitrogen is preferable because polymerization is not inhibited.

  When pattern processing is performed by photolithography, the uncured film prepared on the substrate is compatible with the curing wavelength band of the uncured sheet through a mask designed to allow light to pass through only the necessary portions corresponding to the pattern. Irradiate light. Examples of the light source include an ultrahigh pressure mercury lamp, a metal halide lamp, a halogen lamp, a helium-neon laser, and a YAG laser. Examples of the exposure apparatus include an ultrahigh pressure mercury lamp exposure apparatus PEM-6M (manufactured by Union Optics Co., Ltd.). When the curing mechanism of the paste A and the uncured sheet A is radical polymerization, it is preferable to perform an exposure treatment under a nitrogen atmosphere in order to prevent the radical reactive species from being deactivated by oxidation. In order to increase the resolution of the pattern, it is preferable to increase the parallelism of the irradiation light of the exposure apparatus. Further, in order to reduce the influence of the diffracted light by the mask, the mask and the substrate are brought into contact with each other or the mask and the substrate are contacted. It is preferable to reduce the gap.

  The pattern edge may be distorted by scattering the irradiation light inside the paste A and the uncured sheet A during exposure. In this case, if the ultraviolet absorber is added to the paste A and the uncured sheet A, the ultraviolet absorber absorbs the weak light leaking from the exposed portion and suppresses scattering, so that the pattern edge can be kept sharp. It is preferable because it is possible. Scattering inside the paste A and the uncured sheet A is largely due to Rayleigh scattering from the barium sulfate particles, and the shorter the light, the greater the scattering. Therefore, an ultraviolet absorber that selectively absorbs light having a short wavelength can also be preferably used. Further, it is possible to suppress scattering by inserting a filter for cutting short wavelength light between the light source and the mask.

  In order to further advance the curing reaction after exposure, the substrate can be stored at room temperature or subjected to heat treatment for a certain period of time. After the exposure process, the substrate is dipped in a developing solution, an uncured portion of the unexposed film is removed, and the substrate on which the cured product pattern is formed is washed and dried. In order to advance the curing reaction, heat treatment may be further performed.

  An example of an electronic component manufacturing method using the paste A or the uncured sheet A of the present invention will be described. The paste A is applied and dried on a substrate such as glass epoxy, silicon wafer, glass, or ceramic, or the uncured sheet A is laminated to form an uncured film on the substrate. For laminating the uncured sheet A, a laminator may be used, or it may be manually laminated using a rubber roller on a hot plate. A vacuum laminator is preferably used in order to realize a laminate that does not bite voids at a higher speed. Subsequently, pattern processing is performed by photolithography, and heat treatment is performed after pattern processing as necessary to form an insulating layer.

  The electronic component of the present invention can be manufactured by laminating a conductive material such as an insulating layer and wiring on a substrate, but the final product may be obtained by removing the substrate by peeling or melting. In this case, a substrate in which a release layer, a soluble sacrificial layer, or the like is formed on the substrate in advance, a substrate having such a function on the outermost surface, or a substrate in which the substrate itself is soluble can be used. . Examples of such a peelable material include an adhesive whose adhesive strength is greatly reduced by UV curing or thermal curing, and a slightly tacky adhesive made of a silicone resin, and a soluble material such as copper. Metal, glass, metal oxide, etc. are raised.

  The method of forming the insulating layer using the paste A is not particularly limited, but is a screen printing method, a spray coating method, a blade coater, a die coater, a spin coater, an inkjet device, a coating method using a device such as a dispenser, and drying. And the curing process.

  The method for forming the uncured sheet A is not particularly limited, and examples thereof include a method in which a paste composition is applied onto a film and dried using an apparatus such as screen printing, a blade coater, or a die coater.

Examples of the present invention will be described below, but the present invention is not limited to these examples. Of the compounds used in the examples, those using abbreviations are shown below.
DMAc: N, N-dimethylacetamide THFA: tetrahydrofurfuryl alcohol The measurement method of each characteristic of the hardened | cured material obtained from the dispersion liquid of the barium sulfate particle | grains, the paste A, and the unhardened sheet | seat A is as follows.

<Measuring method of average particle diameter of aggregated raw barium sulfate particles before production of dispersion>
It measured using the optical microscope as follows. The particles were placed on a transparent plate such as glass, and the transparent plate on which the particles were placed was placed on the observation stage of an optical microscope. Light is applied from the lower side of the transparent plate, and the transmitted light image is taken into a computer as a digital image via a CCD camera ADP-240M (manufactured by Frobel Co., Ltd.) attached instead of the eyepiece of the optical microscope, and image processing With a soft FlvFs (manufactured by Flobel Co., Ltd.), the particle diameter when spherical approximation was obtained for any 100 particles observed was determined, and the number average particle diameter was calculated.

<Measurement method of average particle diameter of barium sulfate particles in dispersion>
On the collodion film deposited with carbon, the dispersion was dropped, and the organic solvent was dried and removed, and then the barium sulfate particles were observed with a transmission electron microscope H-7100FA (manufactured by Hitachi, Ltd.). The acceleration voltage was 100 kV. The observed image is captured in a computer as a digital image, and the number average particle diameter is obtained by obtaining the particle diameter when the spherical approximation is obtained for any 100 particles observed by the image processing software FlvFs (manufactured by Flowbell). Was calculated. In addition, when the primary particles were aggregated, the particle diameter as the aggregate was measured.

<Measuring method of average particle diameter of particles in uncured sheet A>
A cured film was produced by heat-treating or irradiating the uncured sheet. A sample thin film (about 100 nm) of this cured film was prepared by an ultrathin section method. The particles were observed with a transmission electron microscope H-7100FA (manufactured by Hitachi, Ltd.). The acceleration voltage was 100 kV. The observed image is captured in a computer as a digital image, and the number average particle diameter is obtained by obtaining the particle diameter when the spherical approximation is obtained for any 100 particles observed by the image processing software FlvFs (manufactured by Flowbell). Was calculated. In addition, when the primary particles were aggregated, the particle diameter as the aggregate was measured.

<Method for measuring linear expansion coefficient of cured product>
Using a TMA measuring device TMA / SS6100 manufactured by SII Nanotechnology, Inc., a strip-shaped cure obtained from an uncured sheet when the temperature is raised from room temperature to 120 ° C in a nitrogen atmosphere and then lowered to room temperature. The displacement of the dimensions of the object was measured with a tensile load of 10 mN, and the average linear expansion coefficient of the temperature rise and fall from 50 ° C to 70 ° C was calculated. In order to remove the temperature history of the linear expansion coefficient, the temperature increase and decrease were repeated twice, and the second measurement result was used as the displacement value.

<Method of insulation reliability test>
After forming and curing the insulating layer forming material of the present invention on a copper comb electrode (FIG. 1) having a line and space of 10 μm / 10 μm, a voltage of 20 V is applied in an atmosphere of a temperature of 85 ° C. and a relative humidity of 85%. The insulation reliability test was continued for 1000 hours. When the resistance value of 10 ⁸ Ω or higher was kept until 1000 hours, the evaluation result was evaluated as ◯. The copper comb electrode has a 0.08 μm thick Cr base electrode on a silicon wafer on which a 0.4 μm thick thermal oxide film and a 0.8 μm silicon nitride film are formed, and a thickness on the Cr base electrode. A 10 μm copper electrode patterned was used.

<Method of thermal cycle test>
For the spiral inductors created in each of the examples and comparative examples, a thermal cycle gas phase method in which a reciprocating operation at a low temperature of −45 ° C. and a high temperature of 100 ° C. is held in one temperature environment for 30 minutes and then moved to the other temperature. A thermal cycle test was conducted to check whether the insulating layer was peeled off or cracked. A sample in which no abnormality such as peeling or cracking was found in the insulating layer was marked as “◯”, and a sample in which abnormality such as peeling or cracking was seen was marked as “X”.

<Manufacture of dispersion>
Dispersions A to M were produced as follows. Barium sulfate secondary particles BF-40 (manufactured by Sakai Chemical Industry Co., Ltd., average secondary particle size of 15 μm, average primary particle size of 10 nm), a dispersant, and an organic solvent were mixed in respective mixing amounts shown in Table 1, Using a homogenizer “Excel Auto” (trade name, manufactured by Nippon Seiki Seisakusho Co., Ltd.), treatment was performed at a peripheral speed of 5 m / s at the tip of the rotary blade for 1 hour to disperse the barium sulfate particles.

  Subsequently, the above dispersion treated with a homogenizer was subjected to dispersion treatment using “Ultra Apex Mill UAM-015” (trade name) (manufactured by Kotobuki Industries Co., Ltd.), which is a bead mill. The beads were made of zirconia, the average particle diameter was 0.05 mm (manufactured by Nikkato Co., Ltd., YTZ balls), and the input amount was 400 g. The peripheral speed of the rotor of the bead mill was 9.5 m / s, and the liquid feeding pressure was 0.1 MPa. The dispersion treatment time was 10 hours for dispersions A to M, and the liquid was recovered after the dispersion treatment to obtain a dispersion of barium sulfate particles. Table 1 shows the average particle diameter of the barium sulfate particles in the dispersion at the end of dispersion.

  In Table 1, “HOA-MPL” (trade name) and “HOA-HH” (trade name) used as dispersants are compounds having a polymerizable group and a carboxyl group, manufactured by Kyoeisha Chemical Co., Ltd. “Light Ester P-1M” (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and “RDX63182” (trade name, manufactured by Daicel Cytec Co., Ltd.) are phosphate ester compounds having a polymerizable group. Further, “Disperbyk-111” (trade name, manufactured by Big Chemie Japan Co., Ltd.) is a phosphate ester compound that does not have a polymerizable group.

Example 1
9.8 g of the dispersion A and 5 g of the resin represented by the formula (11), 0.1 g of an oxime-based UV active polymerization accelerator OXE02 (manufactured by Ciba Specialty Chemicals), a silane coupling agent “ 0.2 g of KBM403 "(trade name, manufactured by Shin-Etsu Chemical Co., Ltd., chemical name: 3-glycidoxypropyltrimethoxysilane) was mixed using a ball mill to produce a paste composition. In this paste composition, the content of barium sulfate particles in the solid component excluding the organic solvent was 40% by weight.

  The paste composition was applied onto a PET film “SR-1” (trade name, Oiso Kogyo Co., Ltd.) (thickness: 38 μm) using a bar coater, and dried at 90 ° C. for 15 minutes using an oven in the atmosphere. And the uncured sheet | seat whose film thickness after drying is 45 micrometers and 10 micrometers was manufactured. All were transparent sheets.

Pattern workability evaluation by photolithography was performed on a sheet having a film thickness of 45 μm using a quartz glass mask having a line and space of 15 μm / 15 μm. Ultraviolet light exposure (curing) at 40 mJ / cm ² and development were performed using an ultrahigh pressure mercury lamp exposure apparatus (PEM-6M, manufactured by Union Optics Co., Ltd.). ELM-D (Mitsubishi Gas Chemical Co., Ltd.) was used as the developer. It was confirmed that pattern processing with a line and space of 15 μm / 15 μm was possible.

Further, this sheet was laminated on a copper comb electrode (FIG. 1) having a line and space of 10 μm / 10 μm, and an ultrahigh pressure mercury lamp exposure apparatus (PEM-6M, manufactured by Union Optics Co., Ltd.) was used to obtain 50 mJ / cm. ^When the insulation reliability test was conducted after being cured by exposure to ultraviolet rays of ^2, the resistance value of 10 ⁸ Ω or higher was kept until 1000 hours.

Next, a spiral inductor as shown in FIGS. An uncured sheet 6 having a thickness of 10 μm was laminated on the FR-4 glass epoxy substrate 5 on a hot plate at 80 ° C. using a rubber roller. As a curing treatment for the uncured sheet, an ultrahigh pressure mercury lamp exposure apparatus (PEM-6M, manufactured by Union Optics Co., Ltd.) was used to expose with an ultraviolet ray of 50 mJ / cm ² to obtain a cured film. A copper layer having a thickness of 0.2 μm was formed on the cured film by a sputtering method, and copper electroplating was further performed thereon so that the total thickness of copper was 10 μm, thereby forming a copper layer 7. .

An uncured sheet 8 having a thickness of 10 μm is laminated on the copper layer 7, and then an ultrahigh pressure mercury lamp exposure apparatus (manufactured by Union Optics Co., Ltd.) is used so as to open two 10 μm diameter vias using a quartz photomask. PEM-6M) ultraviolet exposure of 40 mJ / cm ² using (been cure) and development (Figure 3 (a)). ELM-D (Mitsubishi Gas Chemical Co., Ltd.) was used as the developer. A copper layer 7 having a thickness of 0.1 μm was formed on the entire surface by sputtering, and then a 6.5-turn spiral was formed by photolithography using a photoresist and copper etching using an aqueous copper chloride solution. (FIG. 3B). At this time, alignment adjustment was performed during exposure of the photoresist so that each of the inner end and the outer lead end of the spiral was on the lower via.

Subsequently, an uncured sheet 10 having a film thickness of 45 μm is laminated from above by a method similar to the above, and the lead portion of the feeding portion for the electrolytic copper plating in the subsequent step is directly above the 6.5-turn spiral. UV exposure (curing) and development at 40 mJ / cm ^{2 with} an ultrahigh pressure mercury lamp exposure apparatus (PEM-6M, manufactured by Union Optical Co., Ltd.) using a quartz photomask so that 4 becomes an unexposed portion and the pattern is removed. An insulating layer was formed (FIG. 3C). ELM-D (Mitsubishi Gas Chemical Co., Ltd.) was used as the developer. The width of the unexposed portion from which the spiral portion was removed was 15 μm, and the width of the portion remaining as the insulating layer was also 15 μm.

  Next, copper was deposited from the bottom of the pattern by electrolytic plating, and the circuit of the wiring 11 was formed so as to fill the spiral groove portion formed in the insulating layer with copper (FIG. 3D).

  Thereafter, an extraction electrode 3 having a thickness of 15 μm was provided. The extraction electrode was formed by using a photoresist to provide a layer having only the electrode formation portion opened, and then forming a copper layer having a thickness of 0.2 μm by sputtering. Subsequently, the copper other than the photoresist and the electrode forming portion was removed by lift-off. Thereafter, a layer having an opening only with the electrode forming portion was spread again using a photoresist, and a copper layer was formed by electrolytic plating so as to have a thickness of 15 μm.

  The inductance and Q value of the spiral inductor thus formed at a frequency of 2 GHz were evaluated using a high-frequency probe (manufactured by NP Corporation, MTF-100-SP) and a network analyzer (manufactured by Agilent Technologies, E8364A). The inductance was 7.5 nH and the Q value was 20. Further, when the thermal cycle test was conducted by the above method, no abnormality such as peeling or cracking was found in the insulating layer.

Examples 2-46
An uncured sheet A having the composition shown in Table 2 was produced in the same manner as in Example 1, and the number average particle diameter of barium sulfate particles in the uncured sheet A in paste A was measured and the developability was evaluated. . Moreover, the cured | curing material for physical-property value evaluation was manufactured by the method similar to Example 1 using this, and the linear expansion coefficient of cured | curing material was measured. Further, an insulation reliability test was conducted in the same manner as in Example 1. In addition, a thermal cycle test of a spiral inductor manufactured in the same manner as in Example 1 was performed. These results are shown in Tables 2-3. In Examples 31 to 36, when the paste composition was produced, Compound A used when the dispersion was produced without adding the resin was added. Here, the resin A is represented by the above formula (11), and the resin B is represented by the above formula (12). The silane coupling agent “KBM503” (trade name) is manufactured by Shin-Etsu Chemical Co., Ltd., and the chemical name is 3-methacryloxypropyltrimethoxysilane. In addition, about the Example in which the thin-film-like residue existed in the substrate surface of the unexposed part after image development, it described as "There is a residue in an unexposed part" in the developability column of Table 3. Residues can cause poor connection when electrical connection is made at the bottom of the via.

  Since the inductance of the manufactured spiral inductor largely depends on the structure and the wiring resistance, this point is the same, and therefore there is no significant difference between the examples.

Example 47
A paste composition was prepared in the same manner as in Example 1, an insulating layer was formed using this paste composition as a coating solution, and a spiral inductor similar to that in Example 1 was prepared. The coating film was dried with the coating liquid in each step for 15 minutes at 90 ° C. using an oven in the air. The manufactured spiral inductor had an inductance of 7.5 nH and a Q value of 20.

Comparative Example 1
An uncured sheet having a film thickness of 10 μm and 45 μm was prepared in the same manner as in Example 1 except that barium sulfate particles having an average particle diameter of 0.3 μm (trade name: B30, manufactured by Sakai Chemical Industry Co., Ltd.) were used. did. All sheets were cloudy and translucent. Using this uncured sheet having a film thickness of 45 μm, pattern processability by photolithography was evaluated in the same manner as in Example 1. Although searching for appropriate exposure and development conditions, pattern formation was not possible.

On the other hand, since it was confirmed that an uncured sheet with a film thickness of 10 μm can be patterned with a line and space of 15 μm / 15 μm, this sheet was laminated on a copper comb electrode (FIG. 1) with a line and space of 10 μm / 10 μm. When an insulation reliability test was performed in the same manner as in Example 1, the resistance value of 10 ⁸ Ω or higher was kept until 1000 hours. Further, a spiral inductor was produced in the same manner as in Example 1 by using an uncured sheet having a thickness of 10 μm instead of both the uncured sheet having a thickness of 10 μm and 45 μm in Example 1. The manufactured spiral inductor had an inductance of 5 nH and a Q value of 10. Further, when the thermal cycle test was conducted by the above method, peeling and cracking were observed in the insulating layer.

Comparative Example 2
6 g of THFA, 5 g of the resin represented by the formula (11), 0.1 g of oxime-based UV active polymerization accelerator OXE02 (manufactured by Ciba Specialty Chemicals), silane coupling agent “KBM403” ( 0.2 g of trade name, manufactured by Shin-Etsu Chemical Co., Ltd., chemical name: 3-glycidoxypropyltrimethoxysilane) was mixed using a ball mill to prepare a resin solution. Using this resin solution, uncured sheets having a film thickness of 10 μm and 45 μm were prepared. When an uncured sheet having a film thickness of 45 μm was used to evaluate pattern processability by photolithography in the same manner as in Example 1, pattern processing with a line and space of 15 μm / 15 μm was achieved. Cracks occurred. This sheet was laminated on a copper comb electrode (FIG. 1) having a line and space of 10 μm / 10 μm, and an insulation reliability test was performed in the same manner as in Example 1. As a result, a resistance value of 10 ⁸ Ω or more was obtained up to 1000 hours. Could not hold.

  Next, a spiral inductor was produced in the same manner as in Example 1 by using an uncured sheet having a film thickness of 10 μm and 45 μm. The manufactured spiral inductor had an inductance of 5 nH and a Q value of 10. Further, when the thermal cycle test was conducted by the above method, peeling and cracking were observed in the insulating layer.

Top view of insulation reliability test board Top view of spiral inductor of the present invention Sectional drawing which showed the manufacturing method of the spiral inductor of this invention

Explanation of symbols

1 Copper electrode 2 Silicon substrate 3 Extraction electrode 4 Lead electrode for electrolytic plating
5 Insulating layer 7 formed from uncured sheet 7 Copper layer 8 Insulating layer 9 formed from uncured sheet Copper layer 10 Insulating layer 11 formed from uncured sheet

Claims (8)

(A) Barium sulfate particles having an average particle diameter of 1 nm or more and 40 nm or less, and (B) a compound having a polymerizable group and a carboxyl group, or a phosphoric acid ester compound having a polymerizable group. The insulating layer-forming material according to claim 1, wherein the compound having a polymerizable group and a carboxyl group contains a compound represented by the following general formula (1).

(In the general formula (1), R ¹ represents a hydrogen atom or a methyl group. R ² represents a divalent group represented by any one of the following general formulas (2) to (4).)

(In the above general formulas (2) to (4), n and m are each an integer of 1 to 3) The insulating layer forming material according to claim 2, wherein R ¹ in the general formula (1) is a hydrogen atom, R ² is a divalent group represented by the general formula (4), and n is 2. 4. The material for forming an insulating layer according to any one of claims 1 to 3, wherein the phosphate ester compound having a polymerizable group contains a compound represented by the following general formula (5).

(In said general formula (5), R < ³ > -R < ⁵ > shows the monovalent group or hydrogen atom represented by either of the following general formula (6)-(10), and R < ³ > -R < ⁵ > is the same. (However, all of R ^{3 to} R ⁵ may not be hydrogen atoms.)

(In the general formulas (6) to (10), R ^{6 to} R ⁹ represent a hydrogen atom or a methyl group. R ^{10 to} R ¹¹ are divalent groups having 1 to 10 carbon atoms, and R ¹² represents a hydroxyl group. A divalent group having 1 to 10 carbon atoms. The material for forming an insulating layer according to claim 4, wherein at least one of R ^{3 to} R ⁵ in the general formula (5) is a monovalent group represented by the general formula (8). Furthermore, the insulating layer forming material of any one of Claims 1-5 containing resin which has a polymeric group. The insulating layer forming material according to claim 6, wherein the resin having a polymerizable group includes a resin represented by the following formula (11) or (12).

The electronic component which formed the conductor wiring in the recessed part formed by exposing and developing the layer which consists of an insulating layer formation material in any one of Claims 1-7.

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