JP2010229290A - Material for forming insulating layer and method for manufacturing electronic parts using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a material for forming an insulating layer that enables patterning with a high aspect ratio by an alkali-developing type photolithography method and is excellent in electrical and thermal-mechanical reliability. <P>SOLUTION: The material for forming an insulating layer includes (A) a carboxyl group-containing epoxy acrylate resin which is produced by reacting a bisphenol A type epoxy resin with acrylic acid and/or methacrylic acid to produce an epoxy acrylate resin and reacting the epoxy acrylate resin with a dibasic acid anhydride and contains a carboxyl group per molecule, (B) a polymerization accelerator and (C) an inorganic particle having a number average particle size of not less than 1 nm to not more than 50 nm. <P>COPYRIGHT: (C)2011,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.

  Along with miniaturization and high performance of electronic components, as an insulating material for electronic components, high-aspect ratio pattern processing is possible, and the material has the effect of improving the electrical and thermomechanical reliability of electronic components. Is required.

  As a material for realizing pattern processing at a high aspect ratio by an alkali development type photolithography method, a resin having a structure in which a carboxyl group is added to a photosensitive epoxy acrylate resin is known (for example, see Patent Document 1). However, when an electronic component is manufactured using this material as an insulating material, due to the difference in coefficient of linear expansion from the copper wiring that is a conductor, in a temperature cycle test such as PCT (pressure cooker test), copper wiring or insulating material is used. There was a problem that peeling or cracking occurred and thermomechanical reliability could not be obtained.

  On the other hand, 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, patents). References 2 and 3). However, in pattern processing by photolithography, irradiation light is scattered by inorganic particles dispersed in the resin, resulting in pattern thickening and cracks on the side of the pattern, forming a clear and fine pattern It was sometimes difficult. For this reason, when pattern processing with a narrow pitch and a high aspect ratio is performed as the insulating layer, adjacent convex portions are close to each other, and the concave portions between them are narrowed, or an uncured material residue may be generated.

  On the other hand, a technique is known in which barium sulfate particles having a number average particle diameter of 50 nm or less are dispersed to prepare a photosensitive resin composition, and pattern processing is performed to obtain an optical wiring that exhibits athermal properties (for example, (See Patent Document 4). However, in pattern processing by a photolithography method, when fine processing with a high aspect ratio is performed, pattern peeling or cracks may occur.

JP-A-10-90887 JP 2007-156404 A JP 2008-39863 A International Publication WO08 / 056639 Pamphlet

  As described above, when high-aspect ratio pattern processing is performed using a conventional insulating layer forming material, the conductor wiring and the insulating material are peeled or cracked due to the difference in the coefficient of linear expansion between the conductor wiring and the insulating material. There was a problem. In addition, in order to reduce the difference in coefficient of linear expansion from the conductor wiring, the insulating layer forming material containing inorganic particles causes pattern peeling and cracks in pattern processing at a high aspect ratio, and it is difficult to form a clear pattern. There was a case.

  The present invention is an insulating layer forming material which can be patterned with a high aspect ratio by an alkali development type photolithography method and is excellent in electrical and thermomechanical reliability. Moreover, it is a manufacturing method of the electronic component using this.

  The present invention is a carboxyl group-containing epoxy acrylate resin obtained by reacting a dibasic acid anhydride with an epoxy acrylate resin obtained by reacting (A) bisphenol A type epoxy resin with acrylic acid and / or methacrylic acid. The insulating layer forming material contains a resin having one carboxyl group in the molecule, (B) a polymerization accelerator, and (C) inorganic particles having a number average particle diameter of 1 nm to 50 nm.

  Further, the present invention provides an electronic device in which the insulating layer forming material is formed on a substrate to form an insulating layer, and then exposed and developed to form a recess in the insulating layer, and a conductor wiring is formed in the recess. It is a manufacturing method of components.

  The material for forming an insulating layer of the present invention does not cause pattern peeling or cracks and can be finely processed at a high aspect ratio. Furthermore, an insulating layer having a linear expansion coefficient close to that of a metal and excellent in electrical and thermomechanical reliability can be obtained by the curing process. This feature makes it possible to manufacture highly reliable electronic components such as inductors.

Top view of copper comb electrode Top view of spiral inductor of the present invention Sectional drawing which showed the manufacturing method of the spiral inductor of this invention Cross-sectional view of an electronic component consisting of a build-up multilayer wiring board Top view of the insulating layer (top layer) of the build-up multilayer wiring board Top view of insulating layer (center layer) of build-up multilayer wiring board Top view of insulating layer (lowermost layer) of build-up multilayer wiring board

  The insulating layer forming material of the present invention comprises (A) a carboxyl group-containing product obtained by reacting a dibasic acid anhydride with an epoxy acrylate resin obtained by reacting bisphenol A type epoxy resin with acrylic acid and / or methacrylic acid. An epoxy acrylate resin, which is a material containing a resin having one carboxyl group in one molecule, (B) a polymerization accelerator and (C) inorganic particles having a number average particle diameter of 1 nm to 50 nm.

  The insulating layer forming material of the present invention is not limited in its shape as long as the components (A) to (C) are contained, and may be, for example, a paste or an uncured sheet.

  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 fine processing at a high aspect ratio in the present invention means that the processed pattern has a shape whose height is higher than the width (the aspect ratio is larger than 1).

  If an insulating layer with a narrow pitch and a high aspect ratio can be formed, a conductor wiring with a high aspect ratio can be formed in the recess of the insulating layer. In order to reduce the mounting area of the circuit board and increase the density, it is necessary to reduce the cross-sectional area of the conductor wiring having a square cross section. However, if the cross-sectional area of the conductor wiring is reduced, the wiring resistance increases. Thus, problems such as delay of electric signals and crosstalk, or loss of power and generation of Joule heat occur. On the other hand, if a conductor wiring with a high aspect ratio can be formed, the bottom area can be reduced without reducing the cross-sectional area, and thus there is an advantage that the mounting area of the electronic component can be reduced without causing the above problem. . In addition, when the mounting area is reduced, the distance from the center to the end of the electronic component is shortened, so that the absolute value of expansion due to thermal fluctuation at the end of the electronic component is reduced, thereby reducing the generated stress and reliability as an electronic component. There is a merit that the property becomes high.

  For example, when an inductor is taken 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 conductor material such as a metal such as copper. When manufacturing such an inductor, a thin conductor layer (seed layer) is formed on a substrate in advance, an insulating layer is formed on the substrate using the material of the present invention, and insulation is performed by pattern processing. When the concave portion is formed in the layer, a spiral circuit made of a conductive material can be easily formed in the concave portion from which the insulating layer has been removed by electrolytic plating. Since the aspect ratio of the pattern processing of the insulating layer can be increased by using the material of the present invention, by forming the conductor material forming 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.

  In the insulating layer forming material of the present invention, the resin (A) is a matrix resin component and has a photopolymerizable functional group and a carboxyl group, so that it can be subjected to alkali development type pattern processing by photolithography. When a carboxyl group is present in the matrix resin, the unexposed area is dissolved in an alkaline developer, and development is possible. However, when there are too many carboxyl groups in the matrix resin, on the contrary, the developer tends to infiltrate the exposed area, causing problems such as pattern peeling, poor adhesion, and cracks. In particular, when the matrix resin contains inorganic particles, such a problem is more likely to occur. Therefore, in order to realize good developability, it is necessary to optimize the amount of carboxyl groups in the matrix resin. In the resin (A) of the present invention, a carboxyl group is added to one of two hydroxyl groups in one molecule of a bisphenol A type epoxy acrylate resin, and the other hydroxyl group remains, so that development with an alkaline developer is possible. It is possible, and pattern peeling, poor adhesion, and cracks can be prevented. Therefore, good pattern processing with a high aspect ratio is possible.

  Dibasic acid anhydrides used for the reaction with the epoxy acrylate resin include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methylphthalic anhydride, 4-methylphthalic anhydride, 3-methyltetrahydroanhydride Examples thereof include phthalic acid, 4-methyltetrahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like.

  Among the resins of (A), a compound represented by the following general formula (1) is particularly preferable.

In the general formula (1), R ¹ and R ² represent a hydrogen atom or a methyl group, and may be the same or different. R ³ represents a monovalent group represented by any one of the following general formulas (2) to (6).

In said general formula (2)-(4), R < ⁴ > -R < ⁶ > shows a methyl group and ac is an integer of 0-2, respectively.

In the general formula (1), the photopolymerizable functional group is an acrylate group when R ¹ and R ² are hydrogen atoms, and a methacrylate group when R ¹ and R ² are methyl groups. 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 pattern can be formed by applying a photolithography method in which light is irradiated through a photomask. An acrylate group in which R ¹ and R ² are hydrogen atoms is preferable because the polymerizability becomes better.

  In the method for producing the resin (A), for example, 1 mol of acrylic acid or methacrylic acid is esterified with respect to 1 mol of the epoxy group of the bisphenol A type epoxy resin to obtain a bisphenol A type epoxy acrylate resin. Next, the resin (A) of the present invention can be produced by reacting a bisphenol A type epoxy acrylate resin with a dibasic acid anhydride. The content of the resin (A) in the reaction product obtained by reacting the bisphenol A type epoxy acrylate resin with the dibasic acid anhydride can be changed depending on the ratio of the epoxy acrylate resin to the dibasic acid anhydride. . For example, when 0.5 mol of a dibasic acid anhydride is reacted with 1 mol of a hydroxyl group of an epoxy acrylate resin, the reaction between the hydroxyl group of the epoxy acrylate resin and the dibasic acid anhydride occurs with a certain probability. The proportion of the resin (A) in the reaction product at the time when the dibasic acid anhydride was reacted was 50% by weight. The remaining products in the reaction product are an epoxy acrylate resin having two carboxyl groups in one molecule and an epoxy acrylate resin having no carboxyl group. The obtained reaction product may be used as it is as a matrix resin, or the resin (A) may be isolated and used using molecular exclusion chromatography or the like.

In particular, when R ¹ and R ² in the general formula (1) are hydrogen atoms and a resin in which R ³ is represented by the general formula (3) is used, a residue is generated during pattern processing by a photolithography method. This is preferable because a good pattern shape can be realized.

  The material for forming an insulating layer of the present invention contains the resin (A) that forms a matrix in a cured product, but may further contain a resin that forms a matrix. The resin used at this time has a polymerizable group such as polyamic acid, vinyl resin, norbornene resin, epoxy resin, acrylate resin, epoxy acrylate resin, cyanate resin, bismaleimide-triazine resin, benzocyclobutene resin, siloxane resin, etc. A thermosetting resin or a UV curable resin may be used. Moreover, thermoplastic resins, such as an aramid resin, a polystyrene, polyetherimide, polyphenylene ether, thermoplastic polyimide, are mentioned.

  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 insulating layer forming material for the use as which a light transmittance is requested | required, an epoxy resin, an acrylate resin, an epoxy acrylate resin, a siloxane resin etc. are used suitably.

  The content of the resin (A) in the insulating layer forming material is preferably 20% by weight or more, more preferably 40% by weight or more of the matrix resin component. When the resin of (A) is 20% by weight or more of the matrix resin component, the solubility of the unexposed area during development is improved in pattern processing by an alkali development type photolithography method, and the pattern of the exposed area is peeled off. Since the generation of cracks is reduced, good pattern processing at a high aspect ratio is possible. When the resin (A) is 40% by weight or more of the matrix resin component, these effects are further increased.

  When the resin (A) is produced by the above method and the obtained reaction product is used as a matrix resin as it is, 0.1 mol or more of dibasic acid anhydride is used per 1 mol of the hydroxyl group of the epoxy acrylate resin. When the reaction is carried out at a ratio of less than 0.9 mol, a reaction product containing 20% by weight or more of the resin (A) can be obtained, which is preferable for the above reason. Furthermore, when the dibasic acid anhydride is reacted at a ratio of 0.3 mol or more and less than 0.7 mol with respect to 1 mol of the hydroxyl group of the epoxy acrylate resin, a reaction product containing 40 wt% or more of the resin (A). Since the product can be obtained, this effect becomes larger and preferable.

  In the insulating layer forming material of the present invention, the (B) polymerization accelerator has a function of generating radicals by light irradiation and promoting polymerization of a resin or a dispersant in the material, and enables pattern processing by a photolithography method. ing. In particular, it is preferable to perform pattern processing by a photolithography method using the polymerization accelerator A represented by the following general formula (7) because pattern thickening is suppressed. By suppressing the pattern thickening, the surface of the pattern becomes flat and the generation of cracks is suppressed, and the development residue between patterns is reduced. Further, pattern processing with a narrow pitch and a high aspect ratio is possible, and a conductor wiring with a low resistance and a high aspect ratio can be realized.

In the general formula (7), R ⁷ and R ⁸ represent groups represented by any one of the following general formulas (8) to (11), and may be the same or different. R ^{9 to} R ¹¹ represent a hydrogen atom or a methyl group, and may be the same or different from each other.

  Although the reason why the pattern thickness is reduced when the polymerization accelerator represented by the general formula (7) is used is not clear, the light transmitted through the insulating layer forming material is Rayleigh scattered by the inorganic particles, and is transferred to the unexposed area. It is conceivable that the radical polymerization region protrudes from the exposed portion due to leakage of scattered light. According to the Rayleigh scattering theory, the magnitude of scattering decreases as the wavelength increases. The polymerization accelerator represented by the general formula (7) is considered to be less affected by Rayleigh scattering because the wavelength of light for generating radicals is relatively long at 400 nm, and thus pattern thickness is reduced.

As a polymerization accelerator, R ⁷ in the general formula (7) is a group represented by the general formula (8), R ⁸ is a group represented by the general formula (11), and R ^{9 to} R ^11. Is preferably a methyl group because pattern weighting can be further suppressed. As a specific example of the polymerization accelerator represented by the general formula (7), “DAROCUR TPO” manufactured by Ciba Japan Co., Ltd. (R ⁷ and R ⁸ in the general formula (7) are represented by the general formula (8)). R ^{9 to} R ¹¹ are methyl groups), “IRGACURE 819” (R ⁷ in the general formula (7) is represented by the general formula (8), and R ⁸ is It is represented by the formula (11), and R ^{9 to} R ¹¹ are methyl groups).

  In order to accelerate the polymerization of the resin, a polymerization accelerator that generates radicals by heating may be contained in addition to the polymerization accelerator that generates radicals by light irradiation. When a polymerization accelerator that generates radicals by light irradiation and a polymerization accelerator such as peroxide that generates radicals by heating are used in combination, pattern processing by a photolithography method is possible, and curing can proceed further by subsequent heating. . Moreover, you may contain the polymerization accelerator which generate | occur | produces active species, such as a cation and an anion, and it can be used properly according to a use.

  The insulating layer forming material of the present invention contains (C) inorganic particles having a number average particle diameter of 1 nm to 50 nm. The inorganic particles in the insulating layer forming material include those in the state of primary particles in which aggregation is completely loosened and those in the state in which a plurality of primary particles are aggregated. Here, the particle diameter of the inorganic particles is the particle diameter of the primary particles that are not aggregated, and the particle diameter of the aggregates is the aggregate of the primary particles. As a method of measuring the number average particle diameter of the inorganic particles in the insulating layer forming material, the particles are directly observed by SEM (scanning electron microscope) or TEM (transmission electron microscope), and the number average of the particle diameter is calculated. The method of doing is mentioned.

The inorganic particles used in the present invention are not particularly limited, but Si, Al, Mg, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Ag, In, Sn, Sb, Te, Cs, Ba, Hf, Ta, W, Re, La, Ce, Pr, Nd, Pm, Sm, Eu, Examples thereof include oxides such as Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, single salts such as sulfates, carbonates, and fluorides, or double salts of MgAl ₂ O ₄ .

  If the refractive index difference between the matrix resin and the inorganic particles is reduced, it is suitable for patterning with a high aspect ratio. When light is incident on a material in which inorganic particles are dispersed in a matrix resin like the material of the present invention, Rayleigh scattering is caused by the dispersed inorganic particles. If the refractive index of the matrix resin and the inorganic particles are close, the Rayleigh scattering of the incident light will be small, so that the irradiated light will go deeper in the film thickness direction without being scattered, and high-aspect ratio pattern processing is easy It becomes. Since the refractive index of the resin (A) is generally in the range of 1.55 to 1.65, it is preferable to select inorganic particles having a refractive index in this range. For example, barium sulfate particles having a refractive index of 1.6 can be preferably used.

  On the other hand, since the Rayleigh scattering is proportional to the cube of the particle diameter of the dispersed inorganic particles, it is necessary to use small inorganic particles in order to suppress the scattering and perform good pattern processing at a high aspect ratio. There is. When the number average particle diameter of the inorganic particles in the insulating layer forming material is 50 nm or less, Rayleigh scattering of irradiation light is suppressed during exposure, so that processing with a high aspect ratio is facilitated, and processing under exposure conditions and development conditions is performed. The margin is widened. Moreover, in each form of the insulating layer forming material and the cured product, homogeneity is improved, and unevenness in electrical properties such as dielectric constant is reduced. Furthermore, when the number average particle diameter of the inorganic particles is 30 nm or less, the irradiation light at the time of exposure reaches almost a deeper position in the film thickness direction without being scattered and pattern processing with a larger aspect ratio becomes possible. On the other hand, when the number average particle diameter of the inorganic 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. When the number average particle diameter of the inorganic particles is 5 nm or more, this effect is further increased.

  In the present invention, the content of inorganic particles in the insulating layer forming material is preferably 30% by weight or more and 80% by weight or less with respect to the solid component. The linear expansion coefficient of the hardened | cured material obtained from the insulating layer forming material reduces that content of the inorganic particle with respect to the solid component of the insulating layer forming material is 30 weight% or more. The content of the inorganic particles with respect to the solid component of the insulating layer forming material is more preferably 50% by weight or more. When the content of the inorganic particles with respect to the solid component of the insulating layer forming material 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 during development is reduced. The content of inorganic particles with respect to the solid component in the insulating layer forming material is more preferably 70% by weight or less.

  The insulating layer forming material of the present invention may contain a dispersant in order to disperse the inorganic particles without aggregating them.

  The insulating layer forming material of the present invention preferably contains 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 and the inorganic component in the insulating layer forming material and the adhesion between the resin component in the composition and the inorganic substrate such as a silicon wafer are improved, and pattern processing by a photolithography method is performed. In this case, the effect of reducing the thinning and peeling of the pattern in the exposed portion 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 dispersant and the like are eluted, and the inorganic particles captured by the dispersant are also eluted. When the dispersant is detached from the inorganic particles during development, the inorganic particles whose surfaces are exposed are aggregated with each other, 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 bonding force between the inorganic particles, which are inorganic components, and the dispersant or resin, which is an organic component, so that the dispersibility of the inorganic particles during development is increased. The insulating layer in the unexposed part is quickly eluted and a residue is hardly generated.

  As silane coupling agents, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyl Trimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, etc. Is preferred. In addition, the content of the silane coupling agent in the insulating layer forming material is preferably 0.1% by weight or more and 10% by weight or less with respect to the solid component. When the content of the silane coupling agent relative to the solid component of the insulating layer forming material is 0.1% by weight or more, a sufficient effect by the silane coupling agent can be obtained. Further, general silane coupling agents such as those listed above have a refractive index of 1.45 or less, and there are many cases where the refractive index difference from inorganic particles is large. Therefore, it is preferable that the content of the silane coupling agent with respect to the solid component in the insulating layer forming material is 10% by weight or less because Rayleigh scattering is reduced and light transmittance is improved.

  The insulating layer forming material of the present invention may contain an organic solvent. As the organic solvent, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylimidazolidinone, dimethyl sulfoxide, γ-butyrolactone, ethyl lactate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol , Ethylene glycol mono-n-propyl ether, diacetone alcohol, tetrahydrofurfuryl alcohol and the like.

  Next, regarding the two forms of the insulating layer forming material paste and the uncured sheet of the present invention, the manufacturing method thereof will be described in detail. However, since a non-hardened sheet can be manufactured using a paste, first, the manufacturing method of a paste is demonstrated.

  As a method for producing the insulating layer forming material paste, for example, a method of dispersing inorganic particles in a dispersion apparatus in an organic solvent, and then mixing the obtained dispersion of inorganic particles with a resin, Examples include a method of mixing a commercially available product such as a slurry or sol in which inorganic particles are already dispersed in an organic solvent with a resin.

  First, a method for producing a dispersion in which inorganic particles are dispersed in an organic solvent will be described. Inorganic particles (including secondary particles and aggregated particles) having a number average primary particle size of 50 nm or less, a dispersant, an organic solvent, and, if necessary, the resin (A) and / or other resins and polymerization promotion An agent, an antifoaming agent, a pH adjuster, an antioxidant, a polymerization inhibitor, a plasticizer, a silane coupling agent and the like are mixed in a predetermined amount and stirred. However, it is preferable to add a polymerization accelerator or the like immediately before manufacturing the paste from the viewpoint of the storage stability of the dispersion. Immediately after mixing, since the air layer covers the surface of the inorganic particles, the inorganic 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 inorganic particles and the organic solvent are completely wetted.

  When mixing the inorganic particles, the total amount of the resin necessary for producing the target paste or a part thereof may be added. Compared with the case where the resin is added after the dispersion treatment, the resin and the inorganic particles can be uniformly mixed when 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. The necessary amount of the dispersant 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, a dispersant and other substances can be gradually added while measuring properties such as the viscosity of the dispersion during the dispersion treatment.

  After mixing and stirring inorganic particles (including secondary particles and those in an aggregated state), a dispersant, an organic solvent, and other necessary substances, the inorganic particles are dispersed in a dispersing device.

  Examples of the dispersing apparatus include bead mills such as “Ultra Apex Mill” manufactured by Kotobuki Industries Co., Ltd. and “Star Mill” 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 inorganic 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, a shear stress sufficient to disperse the aggregated inorganic particles can be obtained.

  As the material of the beads, ceramic, glass, metal or the like can be used. Specific examples 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, first, a dispersion process is performed using beads having an average particle diameter of 0.5 mm until the dispersed particle diameter of the inorganic particles reaches about 100 nm, and then a dispersion process is performed using finer beads. Also good.

  The time spent for the dispersion treatment is appropriately set depending on the types and composition ratios of the substances constituting the dispersion liquid such as inorganic particles, dispersant, and organic solvent. In addition, sampling the dispersion at regular intervals and measuring the average particle size of the inorganic particles in the dispersion makes it possible to grasp the change over time in the dispersion state and determine the end point of the dispersion process. preferable. As an apparatus for measuring the average particle size of the inorganic particles in the dispersion, “Zeta Sizer Nano ZS” manufactured by Sysmex Corporation, which is a dynamic light scattering method, can be mentioned.

  Next, a method for producing a paste by mixing the dispersion obtained by the above method with the resin (A) and / or other resin will be described. However, when all the substances necessary for producing the target paste are mixed during the production of the dispersion, the dispersion obtained by the above method becomes a paste.

  First, a predetermined amount of the inorganic particle dispersion and the resin (A) and / or other resin are mixed to produce a paste. When mixing, the dispersion may be injected into the resin until a predetermined amount is reached, or the resin may be injected into the dispersion until a predetermined amount is reached. It is also possible to adjust the composition by further adding a dispersant during the production of the paste.

  In order to make the paste obtained by mixing a predetermined amount of the dispersion liquid and resin, etc., more uniform, a treatment using a ball mill or a roll mill can be performed. Also, if air bubbles are mixed in the paste due to the mixing process, leave the solution under a reduced pressure, or remove the air bubbles by using a stirring defoamer, etc., into the cured product produced using the paste. Air bubbles can be avoided.

  In order to adjust the viscosity of the paste, 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 the dispersant or the resin may be appropriately advanced by heat treatment or light irradiation.

  Next, an example of a method for producing an uncured sheet of the insulating layer forming material will be described. The paste produced as described above is applied onto a substrate, the organic solvent is removed, and an uncured sheet is produced. Polyethylene terephthalate (PET) or the like can be used for the base material to which the paste is applied. When it is necessary to peel and remove the PET film as a base material when using an uncured sheet bonded to a substrate such as a silicon wafer, use a PET film whose surface is coated with a release agent such as a silicone resin. When used, the uncured sheet and the PET film can be easily peeled off, which is preferable.

  As a method for applying the paste onto the PET film, screen printing, spray coater, bar coater, blade coater, die coater, spin coater or the like can be used. 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 cured product obtained by the next curing treatment may be in an uncured state or may have poor thermomechanical properties.

  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. Further, in order to protect the surface of the uncured sheet from dust in the atmosphere, a cover film may be bonded to the surface. When the solid content concentration of the paste 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.

  When laminating the uncured sheet produced by the above method on another substrate, even if using a laminator such as a roll laminator or a vacuum laminator, manually using a rubber roller on the substrate heated on the hot plate You may stick together. After bonding to the substrate, the PET film is peeled off after sufficiently cooling.

  Next, a method of forming an insulating layer using the paste or uncured sheet manufactured as described above and patterning the insulating layer by photolithography will be described.

  First, an insulating layer is formed on a substrate by a method in which a paste is applied to the substrate and dried, or a method in which an uncured sheet is bonded onto the substrate. Next, light corresponding to the absorption wavelength band of the polymerization accelerator is irradiated through a mask designed to allow light to pass through only necessary portions corresponding to the pattern. 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 ultra-high pressure mercury lamp exposure apparatus “PEM-6M” (manufactured by Union Optical Co., Ltd.). When the curing mechanism of the insulating layer forming material of the present invention is radical polymerization, it is preferable to perform an exposure treatment in a nitrogen atmosphere in order to prevent 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 may become thick due to scattering of irradiation light inside the insulating layer during exposure. In this case, if the UV absorber is added to the insulating layer forming material, the UV absorber absorbs the weak light leaking from the exposed area and suppresses the scattering, so the pattern edge can be kept sharp. preferable. The scattering of light inside the insulating layer is largely due to Rayleigh scattering from inorganic particles, and the shorter the wavelength, 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 treatment, the substrate is immersed in a developer, the insulating layer in the portion not exposed 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.

  Developers used for developing the insulating layer of the present invention include tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine. An aqueous solution of a compound exhibiting alkalinity such as dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and the like is preferable.

  Among them, it is preferable to use an alkaline aqueous solution containing an anionic surfactant represented by the following general formula (12).

In the general formula ^{(12), R} 12 represents an alkyl group or alkoxyl group having 5 to 18 carbon atoms, d is an integer of 1-2. R ¹³ represents a group represented by the following general formula (13), and e is an integer of 0 to 2. R ¹⁴ represents an alkyl group having 5 to 18 carbon atoms or an alkoxyl group, and f is an integer of 0 to 2. R ¹⁵ represents a group represented by the following general formula (13), and g is an integer of 1 to 2.

In the general formula (13), M is Na, K or NH ₄ .

  When the anionic surfactant represented by the general formula (12) is included, the removal rate of the unexposed portion of the insulating layer of the present invention is increased, and the effect of suppressing the generation of residues is increased. This is considered to be because the surfactant has a function of improving the affinity between the material of the present invention and the alkaline aqueous solution and quickly transporting the aqueous solution into the material. By increasing the removal rate of the unexposed area, it is possible to prevent the developer from penetrating into the exposed area and swelling the pattern and deforming the shape. In the case where the conductor wiring is formed by plating or the like, there is an effect of improving the adhesion with the base layer.

  Specific examples of the anionic surfactant represented by the general formula (12) include sodium alkyl diphenyl ether sulfonate, potassium alkyl diphenyl ether sulfonate, ammonium alkyl diphenyl ether sulfonate, sodium alkyl diphenyl ether disulfonate, potassium alkyl diphenyl ether disulfonate. And ammonium alkyldiphenyl ether disulfonate.

  Next, the example of the manufacturing method of the electronic component using the insulating layer forming material of this invention is demonstrated.

  A copper film is formed on a substrate such as a glass substrate, a silicon wafer, a glass epoxy substrate, a ceramic substrate, or a plastic film by a sputtering method, and by photolithography using a photoresist and etching of copper using an aqueous copper chloride solution, A desired pattern processing is performed on the copper film. Next, an insulating layer is formed on the substrate by a method of applying a paste and drying, or a method of bonding an uncured sheet, and patterning the insulating layer so that the underlying copper sputtered film pattern is exposed by a photolithography method. . If necessary, heat treatment is performed after pattern processing to cure the insulating layer. Next, a copper layer is formed by electrolytic plating using the copper sputtered film exposed in the recess of the insulating layer as an electrode. The insulating layer embedded with the copper layer thus obtained can be used as an electronic component such as a resistor, a capacitor, or an inductor. Moreover, on the obtained insulating layer, if necessary, by forming one or more insulating layers and copper layers, forming a semiconductor layer between the layers, or performing via processing or connection terminal formation, Electronic components such as LED elements and TFTs can also be manufactured. Furthermore, by combining these electronic components and performing IC mounting or sealing as necessary, more complex electronic components such as power modules, LED modules, and MEMS can be manufactured.

  The electronic component of the present invention can be manufactured by laminating an insulating layer and a conductor 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 previously formed on the substrate, or a substrate that is soluble can be used. Examples of such releasable materials include adhesives whose adhesive strength is greatly reduced by UV curing and thermal curing, and slightly adhesive adhesives made of silicone resin. A metal, glass, a metal oxide, etc. are mentioned.

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.
THFA: Tetrahydrofurfuryl alcohol TMAH: Tetramethylammonium hydroxide The measurement method of each characteristic of the hardened | cured material obtained from the dispersion liquid of barium sulfate particle | grains and the insulating layer forming material is as follows.

<Method for measuring number 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.

<Method for measuring number average particle diameter of inorganic particles in dispersion>
On the collodion film on which carbon was vapor-deposited, the dispersion was dropped, and the organic solvent was removed by drying. Then, 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 number average particle diameter of inorganic particles in cured product>
The uncured sheet-shaped insulating layer forming material was exposed on the entire surface and then heated at 200 ° C. for 1 hour (in a nitrogen atmosphere) to prepare a cured film. 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 taken into a computer as a digital image, and the particle diameter is obtained by calculating the particle diameter when approximating the spherical shape of any 100 particles observed with the image processing software “FlvFs” (manufactured by Flobel Co., Ltd.). The particle size 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>
A non-cured sheet-like insulating layer forming material having a film thickness of 50 μm is placed on a 50 μm-thick uncured sheet-like insulating layer forming material placed on a hot plate at 80 ° C. using a rubber roller. Combined. Next, using a super high pressure mercury lamp exposure apparatus “PEM-6M” (manufactured by Union Optical Co., Ltd.), the whole line exposure was performed at an exposure amount of 300 mJ / cm ² (wavelength 365 nm conversion), and then the PET film was peeled off in nitrogen. Heated at 200 ° C. for 1 hour to produce a cured product. The obtained cured product was cut into a square having a side of about 5 mm, and several layers were stacked using a TMA measuring device “TMA / SS6100” manufactured by SII NanoTechnology Co., Ltd. Measured. A displacement value was measured when the temperature was raised from room temperature to 120 ° C. in a nitrogen atmosphere with an indentation load of 50 mN, and the temperature was lowered again to room temperature, 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>
A paste-like insulating layer forming material was applied onto a copper comb electrode (FIG. 1) having a line and space of 10 μm / 10 μm using a tip of a tweezers and dried at 90 ° C. for 1 hour in the atmosphere. Next, using an ultra-high pressure mercury lamp exposure apparatus “PEM-6M” (manufactured by Union Optics), the entire line was exposed at an exposure dose of 300 mJ / cm ² (wavelength 365 nm conversion), and then heated in nitrogen at 200 ° C. for 1 hour. A sample for evaluation was prepared. Between the electrodes of the obtained sample for evaluation, a voltage of 20 V was continuously applied in an atmosphere at a temperature of 85 ° C. and a relative humidity of 85%, and an insulation reliability test was performed 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 includes a chromium under electrode having a thickness of 0.08 μm on a silicon wafer on which a thermal oxide film having a thickness of 0.4 μm and a silicon nitride film having a thickness of 0.8 μm are formed. Further, a copper electrode having a thickness of 10 μm patterned was used.

<Method of thermal cycle test>
An electronic component having an IC chip mounted on a spiral inductor or a build-up multilayer wiring board produced in each example and comparative example was held in one temperature environment for 30 minutes by reciprocation at a low temperature of −45 ° C. and a high temperature of 100 ° C. A thermal cycle test was performed 1000 cycles later by a thermal cycle gas phase method of moving to the other temperature, and the presence or absence of peeling or cracking of the insulating layer was confirmed. A sample in which no abnormality such as peeling or cracking was observed was marked with ◯, and a sample in which abnormality such as peeling or cracking was observed was marked with ×.

<Manufacture of dispersion>
Dispersions A to D were produced as follows. Barium sulfate secondary particles “BF-40” (manufactured by Sakai Chemical Industry Co., Ltd., average secondary particle size 15 μm, average primary particle size 10 nm) and dispersant “HOA-MPL” (manufactured by Kyoeisha Chemical Co., Ltd.) The organic solvent THFA was mixed in each mixing amount shown in Table 1 and charged into a 500 ml plastic container filled with 1 kg of zirconia beads having an average particle diameter of 5 mm (manufactured by Nikkato Co., Ltd., YTZ balls), and a ball mill frame The barium sulfate particles were dispersed by rotating at 200 rpm for 24 hours.

  Subsequently, the above dispersion treated with a ball mill mount was subjected to dispersion treatment using “Ultra Apex Mill UAM-015” (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 was performed for the time shown in Table 1, and after the dispersion treatment was completed, the liquid was recovered to obtain a dispersion of barium sulfate particles. Table 1 shows the number average particle diameter of the barium sulfate particles in the dispersion at the end of the dispersion.

<Synthesis of Resin (A)>
Synthesis example 1
A bisphenol A type epoxy acrylate resin was obtained using 372 parts by weight of bisphenol A type epoxy resin “jER828” (epoxy equivalent 186 g, manufactured by Japan Epoxy Resin Co., Ltd.) and 144 parts by weight of acrylic acid. Thereafter, 152 parts by weight of tetrahydrophthalic anhydride was added to obtain a reaction product containing the resin (A).

The obtained reaction product was separated by gel permeation chromatography (GPC) and subjected to composition analysis by ¹ H-NMR spectrum measurement. As a result, 40% of the epoxy acrylate resin having one carboxyl group in one molecule was obtained. The epoxy acrylate resin having 2 carboxyl groups in the molecule was 20%, the epoxy acrylate resin having no carboxyl group was 20%, and the polymer component having a dimer or higher was 20%.

  Further, a reaction product containing the resin (A) is separately synthesized by the above method, and the composition is separated by GPC, and the epoxy acrylate resin (resin A) having one carboxyl group in one molecule is carboxyl group in one molecule. Two epoxy acrylate resins (resin B) and an epoxy acrylate resin (resin C) having no carboxyl group were obtained. The developing solvent (THFA) was removed by concentrating the obtained resins A to C with an evaporator.

Synthesis example 2
A bisphenol A type epoxy acrylate resin was obtained using 372 parts by weight of bisphenol A type epoxy resin “jER828” (epoxy equivalent 186 g, manufactured by Japan Epoxy Resin Co., Ltd.) and 144 parts by weight of acrylic acid. Thereafter, 100 parts by weight of succinic anhydride was added to obtain a reaction product containing the resin (A).

The obtained reaction product was separated by gel permeation chromatography (GPC) and subjected to composition analysis by ¹ H-NMR spectrum measurement. As a result, 40% of the epoxy acrylate resin having one carboxyl group in one molecule was obtained. The epoxy acrylate resin having 2 carboxyl groups in the molecule was 20%, the epoxy acrylate resin having no carboxyl group was 20%, and the polymer component having a dimer or higher was 20%.

Example 1
In 10.0 g of the reaction product obtained in Synthesis Example 1, 45.3 g of dispersion A, polymerization accelerator “IRGACURE 819” (manufactured by Ciba Japan Co., Ltd., R ⁷ in general formula (7) is represented by general formula (8) A polymerization accelerator in which R ⁸ is a monovalent group represented by the general formula (11) and R ^{9 to} R ¹¹ are methyl groups) 0.5 g, silane cup Ring material "KBM-503" (manufactured by Shin-Etsu Chemical Co., Ltd., chemical name: 3-methacryloxypropyltrimethoxysilane) 0.15 g was mixed using a ball mill to produce a paste-like insulating layer forming material. . In this insulating layer forming material, the content of barium sulfate particles in the solid component excluding the organic solvent was 60% by weight.

  The paste-like insulating layer forming material was applied onto a PET film “SR-1” (thickness: 38 μm, manufactured by Otsuki Kogyo Co., Ltd.) using a bar coater, dried in air at 90 ° C. for 15 minutes, and dried. Subsequent film thicknesses of 50 μm and 10 μm were produced as uncured sheet-like insulating layer forming materials. The number average particle diameter of the barium sulfate particles in the cured product obtained by curing the uncured sheet-like insulating layer forming material was 13 nm, and the linear expansion coefficient of the cured product was 25 ppm / ° C.

Next, an uncured sheet-like insulating layer forming material having a film thickness of 50 μm was bonded to a silicon wafer on a silicon wafer on an 80 ° C. hot plate to form an insulating layer. A quartz photomask with a line-and-space (L / S) pattern is set on an ultra-high pressure mercury lamp exposure device “PEM-6M” (manufactured by Union Optics Co., Ltd.), and the insulating layer and the photomask are brought into close contact with each other. Full line exposure was performed at an exposure amount of 100 mJ / cm ² (wavelength 365 nm conversion). After the exposure, development was performed using a spray type developing device “AD-3000” (manufactured by Takizawa Sangyo Co., Ltd.). Developer A, which is a 3 wt% TMAH aqueous solution, was used as the developer. However, Developer A contains 2% by weight of sodium dodecyl diphenyl ether disulfonate as a surfactant.

  When the L / S pattern of the insulating layer after development was confirmed using an optical microscope, the pattern had a clear outline and no cracks occurred up to a narrow pitch of 10 μm / 10 μm. It was confirmed that there was no peeling of the pattern and the pattern was processed well.

Moreover, when the insulation reliability test of the hardened | cured material obtained from the uncured sheet-like insulating layer forming material was conducted, the resistance value of 10 ⁸ Ω or higher was kept until 1000 hours.

Next, a spiral inductor as shown in FIGS. 2 to 3 was produced using this uncured sheet-like insulating layer forming material. An uncured sheet-like insulating layer forming material 6 having a film thickness of 10 μm was bonded onto the FR-4 glass epoxy substrate 5 on a hot plate at 80 ° C. using a rubber roller. Next, using an ultra-high pressure mercury lamp exposure apparatus “PEM-6M” (manufactured by Union Optical Co., Ltd.), full line exposure was performed at an exposure amount of 100 mJ / cm ² (wavelength 365 nm conversion) to obtain an insulating layer. A copper layer having a thickness of 0.2 μm was formed on this insulating layer by sputtering, and copper was further plated on the copper so that the total thickness of copper was 10 μm, thereby forming a copper layer 7.

An uncured sheet-like insulating layer forming material 8 having a film thickness of 10 μm is bonded onto the copper layer 7, and then an ultra high pressure mercury lamp exposure apparatus “PEM” is formed through a quartz photomask so as to open two vias having a diameter of 10 μm. Using −6M ″ (manufactured by Union Optics Co., Ltd.), full line exposure was performed at an exposure amount of 100 mJ / cm ² (converted to a wavelength of 365 nm), followed by development (FIG. 3A). Developer A was used as the developer. A copper layer 9 having a thickness of 0.1 μm is formed on the entire surface by a sputtering method, and then L / S is 15 μm in 6.5 turns by photolithography using a photoresist and copper etching using an aqueous copper chloride solution. / 15 μm spiral was produced. (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-like insulating layer forming material 10 having a film thickness of 50 μm is laminated from above by the same method as described above, for the above-mentioned 6.5-turn spiral and for electrolytic copper plating in a later step. Using an ultra high pressure mercury lamp exposure apparatus “PEM-6M” (manufactured by Union Optical Co., Ltd.) through a quartz photomask so that the lead-out part 4 of the power supply part becomes an unexposed part and the pattern is removed, an exposure amount of 100 mJ / After full line exposure at cm ² (wavelength 365 nm conversion), development was performed to form an insulating layer (FIG. 3C). Developer A was used as the developer.

  Next, copper was deposited from the bottom of the pattern by electrolytic copper plating, and the circuit of the wiring 11 was formed so as to fill the concave portion formed in a spiral shape 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. After that, a layer in which only the electrode formation part was opened was provided again using a photoresist, a copper layer was formed by electrolytic plating so as to have a thickness of 15 μm, and heated at 200 ° C. in nitrogen for 1 hour.

  The inductance and Q value of the spiral inductor thus formed at a frequency of 2 GHz were evaluated using a high-frequency probe “MTF-100-SP” (manufactured by NP Corporation) and a network analyzer “E8364A” (manufactured by Agilent Technologies). . The inductance was 8 nH and the Q value was 22. 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 2-6
Using the resin A, resin B, resin C and raw materials other than the resin obtained by separating the reaction product obtained in Synthesis Example 1 in the composition shown in Table 2, paste-like treatment is performed in the same manner as in Example 1. And an uncured sheet-like material for forming an insulating layer was produced, and various evaluations were performed. The evaluation results are shown in Table 3. In Example 5, a search for appropriate exposure and development conditions was performed, but a pattern of L / S = 15 μm / 15 μm could not be formed. Therefore, L / S = 15 μm using an uncured sheet having a thickness of 10 μm. It was confirmed that a pattern processing of / 15 μm can be performed, and a material having a film thickness of 10 μm was used as the uncured sheet-like insulating layer forming material 10 when the spiral inductor was manufactured.

Examples 7-14
Using the reaction product obtained in Synthesis Example 1 and other raw materials in the composition shown in Table 2, paste-like and uncured sheet-like insulating layer forming materials were produced in the same manner as in Example 1, Evaluation was performed. The evaluation results are shown in Table 3.

In Example 9, “DAROCUR TPO” (manufactured by Ciba Japan Co., Ltd., R ⁷ and R ⁸ in the general formula (7) are represented by the general formula (8) as a polymerization accelerator, and R ⁹ to R ¹¹ is using a a) methyl group, was used as the polymerization accelerator in examples 10, 14 "IRGACURE OXE02" (manufactured by Ciba Japan Co., Ltd., an oxime ester compound). The developer B used in Examples 11 to 14 was a 3 wt% TMAH aqueous solution containing 2 wt% potassium dodecyl diphenyl ether disulfonate as a surfactant, and the developer C was 2 ammonium dodecyl diphenyl ether disulfonate as a surfactant. The 3% by weight TMAH aqueous solution and developer D containing 3% by weight are 3% by weight TMAH aqueous solution containing no surfactant. Further, in Examples 10 and 13 and 14, suitable exposure and development conditions were searched, but a pattern of L / S = 15 μm / 15 μm could not be formed. Therefore, an uncured sheet having a film thickness of 10 μm was used. It was confirmed that / S = 15 μm / 15 μm patterning was possible, and a material having a film thickness of 10 μm was used as the uncured sheet-like insulating layer forming material 10 when the spiral inductor was manufactured.

Example 15
Except that the resin was changed to the reaction product obtained in Synthesis Example 2, paste-like and uncured sheet-form insulating layer forming materials were produced in the same manner as in Example 1, and various evaluations were performed. The evaluation results are shown in Table 3.

Example 16
Barium sulfate particle dispersion A was changed to alumina particle dispersion “NANOBYK-3610” (manufactured by Big Chemie Japan Co., Ltd., dispersion particle diameter 20 nm), and the inclusion of alumina particles in the solid component of the paste-like insulating layer forming material A paste-like and uncured sheet-like material for forming an insulating layer was produced in the same manner as in Example 1 except that the amount was 40% by weight, and various evaluations were performed. The evaluation results are shown in Table 3. Although searching for appropriate exposure and development conditions was performed, a pattern with L / S = 15 μm / 15 μm could not be formed. Therefore, a pattern with L / S = 15 μm / 15 μm was used using an uncured sheet with a thickness of 10 μm. It was confirmed that processing was possible, and when the spiral inductor was manufactured, the material 10 for forming the uncured sheet-like insulating layer 10 having a film thickness of 10 μm was used.

Example 17
Barium sulfate particle dispersion A was changed to silica particle dispersion “MIBK-ST” (manufactured by Nissan Chemical Co., Ltd., dispersion particle diameter 12 nm), and the content of alumina particles in the solid component of the paste-like insulating layer forming material A paste-like and uncured sheet-like material for forming an insulating layer was produced in the same manner as in Example 1 except that the content was changed to 40% by weight, and various evaluations were performed. The evaluation results are shown in Table 3. Although searching for appropriate exposure and development conditions was performed, a pattern with L / S = 15 μm / 15 μm could not be formed. Therefore, a pattern with L / S = 15 μm / 15 μm was used using an uncured sheet with a thickness of 10 μm. It was confirmed that processing was possible, and when the spiral inductor was manufactured, the material 10 for forming the uncured sheet-like insulating layer 10 having a film thickness of 10 μm was used.

Example 18
An uncured sheet-like material for forming an insulating layer is manufactured in the same manner as in Example 1, and an IC chip is formed on a build-up multilayer wiring board having three wiring layers as shown in FIGS. The mounted electronic component was manufactured. FIG. 4 is a cross-sectional view of the electronic component, and three wiring layers are shown in FIGS. 5 to 7 in order from the top. In addition, the dashed-dotted line of FIGS. 5-7 has shown the position of the pattern of the uppermost layer so that arrangement | positioning of the pattern of each layer may be understood. FIG. 4 is a cross section taken along the broken line AA ′ in FIG.

First, an uncured sheet-like insulating layer forming material 21 having a film thickness of 50 μm was bonded onto the FR-4 glass epoxy substrate 20 on an 80 ° C. hot plate using a rubber roller. Next, using a super high pressure mercury lamp exposure apparatus “PEM-6M” (manufactured by Union Optical Co., Ltd.) through a quartz photomask so as to open four recesses having a width of 15 μm as shown in FIG. After full line exposure at / cm ² (wavelength 365 nm conversion), development was performed. Developer A was used as the developer. Subsequently, copper was deposited from the bottom of the pattern to the same height as the insulating layer by electroless copper plating in the formed recess, thereby forming a first (lowermost) wiring layer.

  Next, second and third wiring layers were formed in the same manner as the first layer, and heated in nitrogen at 200 ° C. for 1 hour to cure the insulating layer. The second copper layer is composed of eight vias, and the diameter of each via is 30 μm (FIG. 6). The third (top) copper layer is connected to 12 of the 16 external electrodes on the outer periphery and 12 of the 16 internal IC bonding pads by a wiring with a width of 15 μm. (FIG. 5). Subsequently, a solder resist layer 27 was formed on portions other than the uppermost external electrode and the IC bonding pad to manufacture a build-up multilayer wiring board.

  Next, using a flip chip bonder, the IC chip 29 on which the solder bump electrodes 28 were formed was flip-chip mounted on the build-up multilayer wiring board to obtain an electronic component. The IC chip used is a TEG chip in which 16 solder bump electrodes are conducted inside the IC chip.

  When the manufactured electronic component was subjected to a thermal cycle test, no abnormality such as peeling or cracking was found in the insulating layer. In addition, when the resistance value between any two external bonding pad portions was confirmed after the test, it was confirmed that conduction was made between any pads, delamination inside the multilayer wiring board, and the bonding portion with the IC chip. It was confirmed that there was no peeling.

Comparative Example 1
Paste and uncured sheets were prepared in the same manner as in Example 1 except that the resin B5.0 g and the resin C5.0 g obtained by separating the reaction product obtained in Synthesis Example 1 were used as the resin. A material for forming an insulating layer was manufactured and various evaluations were performed. The evaluation results are shown in Table 3. In addition, there were many residues between patterns at the time of development, and a clear pattern could not be formed, and a spiral inductor could not be produced.

Comparative Example 2
Forming an insulating layer in the form of a paste and an uncured sheet in the same manner as in Example 1 except that 10.0 g of the resin B obtained by separating the reaction product obtained in Synthesis Example 1 was used as the resin. Materials were manufactured and various evaluations were performed. The evaluation results are shown in Table 3. Note that pattern peeling and cracks occurred during development, and a clear pattern could not be formed, and a spiral inductor could not be produced.

Comparative Example 3
In the same manner as in Example 1 except that the resin C10.0 g obtained by separating the reaction product obtained in Synthesis Example 1 was used as the resin, forming a paste-like and uncured sheet-like insulating layer Materials were manufactured and various evaluations were performed. The evaluation results are shown in Table 3. It should be noted that the unexposed portion did not dissolve in the developer during development, and pattern processing could not be performed, and a spiral inductor could not be produced.

Comparative Example 4
Using 10.0 g of the reaction product obtained in Synthesis Example 1 and Dispersion D as the resin in the composition shown in Table 2, using the same method as in Example 1 for forming a paste-like and uncured sheet-like insulating layer Materials were manufactured and evaluated in various ways. The evaluation results are shown in Table 3. Although searching for appropriate exposure and development conditions was performed, a pattern with L / S = 15 μm / 15 μm could not be formed. Therefore, a pattern with L / S = 15 μm / 15 μm was used using an uncured sheet with a thickness of 10 μm. It was confirmed that processing was possible, and when the spiral inductor was manufactured, the material 10 for forming the uncured sheet-like insulating layer 10 having a film thickness of 10 μm was used.

Comparative Example 5
Paste and uncured sheets were obtained in the same manner as in Example 16 except that the resin B5.0 g and the resin C5.0 g obtained by separating the reaction product obtained in Synthesis Example 1 were used as the resin. A material for forming an insulating layer was manufactured and various evaluations were performed. The evaluation results are shown in Table 3. In addition, there were many residues between patterns at the time of development, and a clear pattern could not be formed, and a spiral inductor could not be produced.

Comparative Example 6
Paste and uncured sheets were obtained in the same manner as in Example 17 except that the resin B5.0 g and the resin C5.0 g obtained by separating the reaction product obtained in Synthesis Example 1 were used as the resin. A material for forming an insulating layer was manufactured and various evaluations were performed. The evaluation results are shown in Table 3. In addition, there were many residues between patterns at the time of development, and a clear pattern could not be formed, and a spiral inductor could not be produced.

1 Copper electrode 2 Silicon wafer 3 Extraction electrode 4 Lead electrode for electrolytic plating
5 FR-4 glass epoxy substrate 6 Insulating layer 7 formed from uncured sheet-like insulating layer forming material 7 Copper layer 8 Insulating layer 9 formed from uncured sheet-like insulating layer forming material Copper layer 10 Uncured sheet-like insulating layer Insulating layer 11 formed from forming material Copper wiring 20 FR-4 glass epoxy substrate 21 Insulating layer 22 formed from uncured sheet-like insulating layer forming material Copper layer 23 Insulating formed from uncured sheet-like insulating layer forming material Layer 24 Copper layer 25 Insulating layer 26 formed from uncured sheet-like insulating layer forming material Copper layer 27 Solder resist layer 28 Solder bump electrode 29 IC chip

Claims (10)

(A) A carboxyl group-containing epoxy acrylate resin obtained by reacting a dibasic acid anhydride with an epoxy acrylate resin obtained by reacting bisphenol A type epoxy resin with acrylic acid and / or methacrylic acid. A material for forming an insulating layer comprising a resin having one group, (B) a polymerization accelerator, and (C) inorganic particles having a number average particle diameter of 1 nm to 50 nm. The insulating layer-forming material according to claim 1, wherein the resin (A) is a compound represented by the following general formula (1).

(In the general formula (1), R ¹ and R ² represent a hydrogen atom or a methyl group, and may be the same or different. R ³ is represented by any one of the following general formulas (2) to (6). Group to be used.)

(In said general formula (2)-(4), R < ⁴ > -R < ⁶ > shows a methyl group and ac is 0-2, respectively.) The insulating layer-forming material according to claim ² , wherein R ¹ and R ² in the general formula (1) are hydrogen atoms, and R ³ is a group represented by the general formula (3). (B) The material for forming an insulating layer according to any one of claims 1 to 3, wherein the polymerization accelerator is a compound represented by the following general formula (7).

(In the general formula (7), ^{R 7} and ^{R 8} represents a group represented by any one of the following general formula (8) to (11), optionally the same or different ^.R 9 ^{to R 11} Represents a hydrogen atom or a methyl group, which may be the same or different.

R ⁷ in the general formula (7) is a group represented by the general formula (8), R ⁸ is a group represented by the general formula (11), and R ^{9 to} R ¹¹ are methyl groups. 4. The insulating layer forming material according to 4. The material for forming an insulating layer according to any one of claims 1 to 5, wherein the inorganic particles are barium sulfate particles. An electronic component having an insulating layer made of the insulating layer forming material according to claim 1, wherein a concave portion is formed in the insulating layer, and a conductor wiring is formed in the concave portion. After forming the insulating layer forming material according to claim 1 on a substrate to form an insulating layer, a recess is formed in the insulating layer by exposure and development, and a conductor wiring is formed in the recess. Manufacturing method for electronic parts. After forming the insulating layer forming material according to claim 1 on a substrate to form an insulating layer, a recess is formed in the insulating layer by exposure and development, and a conductor wiring is formed in the recess. A method of manufacturing an electronic component, wherein an insulating layer having a conductor wiring formed in a recess is further formed on the layer. The method for producing an electronic component according to claim 8 or 9, wherein an alkaline aqueous solution containing an anionic surfactant represented by the following general formula (12) is used as the developer.

(In the general formula (12), R ¹² represents an alkyl group or alkoxyl group having 5 to 18 carbon atoms, d is 1 to 2. R ¹³ represents a group represented by the following general formula (13), e is 0 to 2. R ¹⁴ represents an alkyl group or alkoxyl group having 5 to 18 carbon atoms, f is 0 to 2. R ¹⁵ represents a group represented by the following general formula (13), and g Is 1-2.)

(In the general formula (13), M is Na, K, or NH _4. )

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