JP3680854B2 - Paste composition and dielectric composition using the same - Google Patents

Description

  The present invention relates to a dielectric composition exhibiting characteristics suitable as a capacitor or an interlayer insulating material for a circuit material having a function as a capacitor or an optical wiring material.

  In recent years, with the demand for downsizing electronic devices, increasing the speed of signals, and increasing the capacity, the density of mounted circuit components has been increasing. However, electrical noise increases and data errors are becoming a problem. In order to suppress the generation of this electrical noise and to operate the semiconductor device stably, it is important to supply a necessary amount of current from a position close to the semiconductor device. For this purpose, it is effective to dispose a capacitor having a large capacity directly under the semiconductor device as a decoupling capacitor.

  Therefore, as a method of arranging a capacitor on the printed wiring board, there is a method of arranging an external capacitor such as a chip capacitor on the printed wiring board. However, from the viewpoint of miniaturization, it is advantageous to add an inorganic filler to the inner layer of the printed wiring board to give the printed wiring board itself a capacitor function, and a composite of inorganic filler and resin is used as an interlayer insulating material. A method (see Patent Documents 1 and 2) is known. However, the dielectric constant of the composite by the above method was as low as about 10-20.

The composite dielectric containing an inorganic filler can increase the relative dielectric constant by increasing the amount of the inorganic filler added, but if the content of the inorganic filler exceeds 50% by volume, the content of the inorganic filler may be increased. There was a problem that the dielectric constant did not increase. Moreover, since a high viscosity is obtained when a high dielectric constant inorganic filler is mixed with a resin in a large amount, a large amount of solvent is usually required.

  Conventional high dielectric compositions have been prepared by removing and solidifying a paste composition containing an inorganic filler, a resin and a solvent (see Patent Document 3). However, when the amount of the solvent used is large, there are disadvantages such as a decrease in heat resistance due to the residual solvent and a void in the surface layer.

  As a method for obtaining a high relative dielectric constant, a method of increasing the relative dielectric constant by adding a filler having two or more particle sizes and increasing the filling rate of the filler (see Patent Documents 4 and 5) is known. . However, the filler used in these has a large average particle diameter of the filler having the maximum average particle diameter as large as 5 μm or more, and the film thickness of the composite obtained by mixing this filler and resin is as thick as about 300 μm. I had to be.

In addition, as a method for increasing the dielectric constant, there is a method using an inorganic filler having a large particle size. The dielectric constant of the filler depends on the crystal structure of the filler. In general, in an inorganic crystal, as seen in barium titanate and the like, the displacement of the center of gravity of an anion and cation brings about a large dielectric constant. When used as a filler, when the particle size is reduced, the crystal particle size is generally reduced, the surface energy of the particles is increased, and the symmetry of the crystal structure becomes higher in order to reduce the energy of the entire system. When the symmetry of the crystal structure is increased, the displacement of the center of gravity of the anion and the cation is reduced, so that the dielectric constant is reduced. Therefore, the dielectric constant can be increased by using a filler having a large particle size. This effect is particularly remarkable in barium titanate. For example, there is an example (see Patent Document 6) in which barium titanate having an average particle size of 15 μm is used as a filler and ethyl carbitol (boiling point is 202 ° C.). However, since the particle size of the filler is large and the specific surface area of the filler is small, even when a solvent having a high boiling point is used, solvent removal during heating proceeds at a relatively low temperature in a short time. Then, since solvent removal occurs at a faster rate than the movement of the resin and filler accompanying the shrinkage of the entire system, a lot of voids are generated. The generation of voids causes a decrease in dielectric constant. If a filler having a large average particle diameter is used, the dielectric constant of the filler itself is increased, but even when a high boiling point solvent is used, the generation of voids cannot be suppressed as described above. As a result, the dielectric constant is 52, which is large. The value could not be obtained. Further, since a filler having a large average particle diameter of 15 μm is used (see Patent Document 6), the film thickness must be as large as 25 μm, and therefore the capacitance density is as small as 1.8 nF / cm ² .

  On the other hand, in order to reduce the size and thickness of the system mounted inside, development of high-density SiP (system in package) not only with memory but also with LSI with a large number of terminals is being carried out at a rapid pace. However, a capacitor built in this SiP is strongly required to be thin, and the film thickness of this capacitor interlayer insulating material is required to be 10 μm or less. Therefore, the conventional technology cannot satisfy the demand for thinning of 10 μm or less, and cannot meet the demand for thinning that has been rapidly increased in the performance enhancement of mobile devices such as mobile phones.

  Furthermore, since the capacitance of the capacitor is inversely proportional to the thickness of the interlayer insulating material, it is preferable to reduce the thickness of the interlayer insulating material from the viewpoint of increasing the capacitance of the capacitor.

An important basic characteristic required for interlayer insulating materials is a low linear expansion coefficient. The linear expansion coefficient of the resin itself is 50 ppm / ° C. or higher, which is very large as compared with the linear expansion coefficient (17 ppm / ° C.) of a metal serving as a wiring layer, for example, copper. Therefore, when an interlayer insulating material made only of resin is used, problems such as delamination and wiring rupture due to stress occur due to the difference in coefficient of linear expansion from the wiring layer. On the other hand, when an inorganic filler is combined with a resin, the linear expansion coefficient can be lowered. Therefore, when a composite in which an inorganic filler and a resin are mixed is used as an interlayer insulating material, the linear expansion of the wiring layer It becomes possible to approximate the value of the coefficient. However, in the conventional method, the inorganic filler could not be sufficiently filled, and the value could not be lowered to a value almost close to the linear expansion coefficient of the wiring layer.
JP-A-5-57852 (Claims) JP-A-6-85413 (Claims) JP-A-10-158472 (Claims) JP-A-53-88198 (Claims) JP 2001-233669 A (Claims) JP-A-8-293429 (paragraphs 13 to 20)

  In view of such a situation, the present invention aims to obtain a high dielectric composition having a low coefficient of linear expansion, and is further thinned sufficiently as an interlayer insulating material for large capacitance capacitors incorporated in high-density SiP. A dielectric composition and an optical wiring material are provided.

That is, the present invention is an inorganic filler, an epoxy resin, and a solvent a paste composition comprising a boiling point 160 ° C. or more solvents, the solvent has a boiling point 160 ° C. or more solvents one or more, the inorganic filler The paste composition has an inorganic filler having an average particle size of 5 μm or less, and the total amount of solvent is 25% by weight or less of the total amount of the paste composition.

  Another embodiment of the present invention is a dielectric composition having an inorganic filler and a resin, wherein the inorganic filler has at least two types of average particle diameters, and the maximum average particle diameter of the average particle diameters The dielectric composition is characterized in that the maximum average particle size is 3 times or more with respect to the minimum average particle size.

  According to the present invention, a dielectric composition having a dielectric constant as high as 50 or more can be easily obtained. Furthermore, since the composition of the present invention has a low linear expansion coefficient almost similar to the linear expansion coefficient of the wiring metal, when used as an interlayer insulating material, problems such as peeling between the wiring layers and wiring tearing Therefore, a capacitor having high reliability can be obtained. Furthermore, a thin film having a uniform film thickness and uniform physical properties can be easily obtained. Since this is suitable for a large capacitance, it is useful for a capacitor incorporated in a high-density SiP and an interlayer insulating material for circuit board materials having a function as a capacitor.

The paste composition of the present invention comprises an inorganic filler, an epoxy resin, and a solvent, the inorganic filler has an inorganic filler having an average particle size of 5 μm or less, and the solvent contains a solvent having a boiling point of 160 ° C. or higher. And the total amount of solvent is 25 weight% or less of the total amount of paste composition, It is a paste composition characterized by the above-mentioned.

  The present invention also relates to a dielectric composition having an inorganic filler and a resin, including an inorganic filler having at least two types of average particle diameters, and the average particle diameter of the inorganic filler having the largest average particle diameter is 0. The dielectric composition is characterized in that the maximum average particle size is 3 times or more with respect to the minimum average particle size.

  The total amount of solvent in the paste composition of the present invention needs to be 25% by weight or less of the total amount of the paste composition. Preferably it is 20 weight% or less, More preferably, it is 10 weight% or less. Moreover, 1 weight% or more is preferable. When the amount of solvent is 25% by weight or less, generation of voids due to solvent volatilization during drying is suppressed, and the dielectric constant of the dielectric composition can be increased. In addition, since the amount of voids that can cause moisture absorption is small, changes in physical properties due to the influence of humidity and moisture can be reduced. Furthermore, the storage durability is excellent. When the amount of the solvent is more than 25% by weight, voids increase in the drying step and the thermosetting step for removing the solvent, and the relative dielectric constant of the dielectric composition often decreases. If the amount of the solvent is less than 1% by weight, the solvent is small and the viscosity and uniformity of the paste composition are impaired.

  As the filling rate of the inorganic filler increases, the influence of the amount of the solvent increases, and the effect of the present invention is particularly great when the inorganic filler is 85% by weight or more of the solid content contained in the paste composition.

  At least one of the solvents used in the present invention must have a boiling point of 160 ° C. or higher. Preferably it is 180 degreeC or more, More preferably, it is 200 degreeC or more. When the boiling point of the solvent is 160 ° C. or higher, the generation of voids is suppressed and the dielectric constant of the dielectric composition can be increased. When the boiling point is lower than 160 ° C., the volatilization rate of the solvent is fast, so that densification due to mass transfer during heat treatment cannot catch up, voids increase, and the dielectric constant of the dielectric composition often decreases. In addition, the solvent used in the present invention preferably has a boiling point of 300 ° C. or lower, more preferably 280 ° C. or lower. When the boiling point is higher than 280 ° C., the treatment for removing the solvent becomes high temperature, the resin is decomposed by the high temperature, and the dielectric property is deteriorated. On the other hand, when the temperature exceeds 300 ° C., the decomposition of the resin becomes more severe and the mechanical strength is lowered. The solvent used in the paste composition of the present invention may be only one solvent having a boiling point of 160 ° C. or higher, but may contain other solvents as long as it contains a solvent having a boiling point of 160 ° C. or higher.

  Solvents having a boiling point of 160 ° C or higher are mesitylene, acetonylacetone, methylcyclohexanone, diisobutylketone, methylphenylketone, dimethylsulfoxide, γ-butyrolactone, isophorone, diethylformamide, dimethylacetamide, N-methylpyrrolidone, γ-butyrolactam, ethylene glycol Examples thereof include acetate, 3-methoxy-3-methylbutanol and its acetate, 3-methoxybutyl acetate, 2-ethylhexyl acetate, oxalate ester, diethyl malonate, maleate ester, propylene carbonate, butyl cellosolve, ethyl carbitol and the like.

In the present invention, a solvent containing an ester structure is preferably used, more preferably a solvent containing a lactone structure. The most preferred solvent is γ-butyrolactone. The boiling point as used in the field of this invention is a boiling point under the pressure of 1 atmosphere, ie, 1.013 * 10 < ⁵ > N / m < ² >. The boiling point can be measured using a known technique and is not particularly limited. For example, the boiling point can be measured using a Swietoslawski boiling point meter.

  As other solvents used in the present invention, those capable of dissolving the resin can be appropriately selected. Solvents include, for example, methyl cellosolve, N, N-dimethylformamide, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, isobutyl alcohol, isopropyl alcohol, tetrahydrofuran, toluene, chlorobenzene, trichloroethylene, benzyl alcohol, methoxymethylbutanol, ethyl lactate , Propylene glycol monomethyl ether and its acetate, and organic solvent mixtures containing one or more of these are preferably used.

  Examples of the shape of the inorganic filler include a spherical shape, a substantially spherical shape, an elliptical spherical shape, a needle shape, a plate shape, a scale shape, and a rod shape, and a spherical shape or a substantially spherical shape is particularly preferable. This is because spherical or substantially spherical fillers have the smallest specific surface area, and therefore are less likely to cause filler aggregation and resin fluidity reduction during filling. One of these can be used alone, or two or more can be mixed and used.

  In order to obtain a low linear expansion coefficient and a high relative dielectric constant, it is desirable to contain these inorganic fillers in the resin at a high filling rate.

  An organic resin generally used as an interlayer insulating material has a linear expansion coefficient of, for example, 30 to 50 ppm / ° C. for polyimide and 50 ppm / ° C. or more for epoxy resin. This is very large as compared with a linear expansion coefficient of 17 ppm / ° C. of a wiring metal, for example, copper, but the linear expansion coefficient can be lowered by mixing an inorganic filler.

  Further, in a dielectric composition composed of an inorganic filler and a resin, the relative dielectric constant of the dielectric composition is in accordance with a derivation formula for the relative dielectric constant of the composite, so-called logarithmic mixing rule (1) described below (ceramic material) Introduction to Science (Applied), Uchida Otsukuru Shinsha, WDKingery, translated by Komatsu Kazuzo et al., P912). The higher the content of the inorganic filler having a high dielectric constant, the higher the relative dielectric constant of the obtained dielectric composition.

ε: relative dielectric constant of the composite εi: relative dielectric constant of each component of the composite Vi: volume fraction of each component of the composite.

  In order to contain the inorganic filler in the resin at a high filling rate, it is preferable to use a mixture of two or more types having different average particle diameters. When a filler having a single particle size is filled, particularly when the filler is spherical or substantially spherical, a diamond-shaped void is formed between the filler and the filler when filled at a high density. The filler cannot enter. However, if the filler has a size smaller than the gap, the filler can further enter the gap, and the filling rate can be easily improved.

  In the inorganic filler included in the present invention, the difference ratio between the average particle diameter of the inorganic filler having the maximum average particle diameter and the average particle diameter of the inorganic filler having the minimum average particle diameter is preferably as large as possible. Is preferably at least 3 times, more preferably at least 5 times the minimum average particle size. When the difference ratio is small, it is difficult for small fillers to efficiently enter the gaps between large fillers. On the other hand, when the difference ratio is large, small fillers tend to aggregate and the dispersion stability decreases. Preferably it is 30 times or less, more preferably 10 times or less.

  When an inorganic filler having at least two types of average particle diameter is used, the total volume Va of the inorganic filler having the maximum average particle diameter and the total volume Vb of the inorganic filler having the minimum average particle diameter are 0.05 ≦ It is preferable to satisfy Vb / (Va + Vb) <0.5. That is, the amount of the small filler is preferably 5% or more and less than 50% of the total amount of the filler in terms of volume ratio. If it is less than 5%, the effect of increasing the filling amount by entering the void is hardly obtained, and if it is 50% or more, the volume occupied by the small filler is larger than the void formed by the large filler, and the interpenetration occurs. The effect of increasing the filling amount is reduced.

  In addition to these large fillers and small fillers, fillers of other particle sizes may be mixed, and the effect of improving the filling rate by mixing the fillers by appropriately selecting the particle size and blending ratio even if there are three or more types Is obtained.

  The inorganic filler used in the present invention includes at least two kinds of inorganic fillers having different average particle diameters, and the average particle diameter of the inorganic filler having the largest average particle diameter is preferably 5 μm or less. More preferably, it is 2 micrometers or less, More preferably, it is 1 micrometer or less. Moreover, it is 0.1 micrometer or more, More preferably, it is 0.2 micrometer or more, More preferably, it is 0.3 micrometer or more. Here, when a capacitor having a film thickness of 10 μm or less was made using an inorganic filler having a maximum average particle diameter of an average particle diameter larger than 5 μm, the filler was likely to protrude on the film surface, so that it was stable. It is difficult to obtain dielectric properties. Moreover, when the average particle diameter of the inorganic filler having the maximum average particle diameter is 2 μm or less, the filler in the filler dispersion liquid hardly settles. Furthermore, when the inorganic filler having the maximum average particle diameter has an average particle diameter of 1 μm or less, the filler is less likely to settle during long-term storage, and storage conditions may not be limited. On the other hand, when trying to obtain a material having a large relative dielectric constant, if the maximum average particle size is smaller than 0.1 μm, the symmetry of the crystal structure tends to be high because the specific surface area of those fillers is large. It is difficult to obtain a high dielectric constant phase, which causes a decrease in the dielectric constant of the dielectric composition. On the other hand, when the maximum average particle size is 0.2 μm or more, the filler surface area becomes small, the filler-dispersed paste hardly aggregates, the viscosity change is small, and kneading, dispersion, and coating processing are hardly affected. Furthermore, when the average particle size of the inorganic filler having the maximum average particle size is 0.3 μm or more, the average particle size of the inorganic filler having the maximum average particle size and the average particle size of the inorganic filler having the minimum average particle size Therefore, the filling ratio is not affected.

Moreover, in this invention, it is preferable that the average particle diameter of the inorganic filler which has the minimum average particle diameter is 0.01-0.1 micrometer. Furthermore, it is more preferable to use a 0.04-0.06 micrometer thing. Since it is necessary to take a difference ratio between the maximum average particle size and the minimum average particle size, the inorganic filler having the minimum average particle size is appropriately selected from the above range depending on the maximum average particle size. The average particle size of the inorganic filler having the smallest average particle size can be increased by increasing the difference ratio from the average particle size of the inorganic filler having the largest average particle size. For this reason, the average particle diameter of the inorganic filler having the smallest average particle diameter is preferably 0.1 μm or less, more preferably, considering the preferred range of the average particle diameter of the inorganic filler having the largest average particle diameter. 0.06 μm or less. When the average particle size of the inorganic filler having the minimum average particle size is 0.04 μm or more, re-aggregation after dispersion hardly occurs and the dispersion stability of the paste is good. The average particle size of the inorganic filler having the minimum average particle size is 0 . When the thickness is 01 μm or more, the fillers are less likely to agglomerate, so that the aggregates are easily broken and dispersed.

  The average particle size contained in the paste composition and the dielectric composition of the present invention is measured using XMA on an ultrathin slice obtained by forming a dielectric composition thin film and cutting the film cross section in the film thickness direction of the thin film. It can be measured by measurement and observation with a transmission electron microscope (TEM). Since the transmittance with respect to the electron beam is different between the inorganic filler and the resin, the inorganic filler and the resin can be identified by the difference in contrast in the TEM observation image. When a plurality of types of inorganic fillers are used, each inorganic filler can be identified by elemental analysis based on XMA measurement and crystal structure analysis by electron diffraction image observation. The distribution of the area of the filler and resin thus obtained is obtained by image analysis, and the particle diameter can be calculated from the area by approximating the cross section of the inorganic filler to be circular. The particle size may be evaluated for TEM images with a magnification of 5000 times and 40000 times. The calculated particle size distribution is represented by a histogram in increments of 0.1 μm in a TEM image with a magnification of 5000 times and a histogram in 0.01 μm increments in a TEM image with a magnification of 40000 times. Is the average particle size. In the present invention, “having at least two kinds of average particle diameters” means that there are two or more maximum values, and two or more maximum values in the particle size distribution of the inorganic filler contained in the composition. It exists. As an evaluation method of the particle size distribution, a scanning electron microscope (SEM) may be used instead of TEM in the above method.

  Other methods include a dynamic light scattering method that measures the fluctuation of the scattered light due to the Brownian motion of the filler, and an electrophoretic light scattering method that measures the Doppler effect of the scattered light when the filler is electrophoresed. Can be measured. Examples of laser diffraction and scattering type particle size distribution measuring apparatuses include LA-920 manufactured by Horiba, SALD-1100 manufactured by Shimadzu, and MICROTRAC-UPA150 manufactured by Nikkiso.

  As the dielectric properties of the inorganic filler, those having a relative dielectric constant of 50 to 30,000 are preferably used. When an inorganic filler having a relative dielectric constant of less than 50 is used, a dielectric composition having a sufficiently large relative dielectric constant cannot be obtained. Moreover, when the relative dielectric constant exceeds 30000, the temperature characteristic of the relative dielectric constant tends to deteriorate, which is not preferable. The relative dielectric constant of the inorganic filler here refers to the relative dielectric constant of a sintered body obtained by heating and firing the inorganic filler as a raw material powder. The relative dielectric constant of the sintered body is measured, for example, by the following procedure. The inorganic filler is mixed with a binder resin such as polyvinyl alcohol, an organic solvent or water to prepare a paste-like composition, which is then filled into a pellet molding machine and dried to obtain a pellet-like solid. By baking the pellet-shaped solid material at, for example, about 900 to 1200 ° C., the binder resin can be decomposed and removed, the inorganic filler can be sintered, and a sintered body consisting only of the inorganic component can be obtained. At this time, the voids in the sintered body are sufficiently small, and the porosity calculated from the theoretical density and the measured density is required to be 1% or less. Upper and lower electrodes are formed on this sintered pellet, and the relative dielectric constant is calculated from the measurement results of capacitance and dimensions.

  Inorganic fillers are barium titanate, barium zirconate titanate, strontium titanate, calcium titanate, bismuth titanate, magnesium titanate, barium neodymium titanate, barium tin titanate, magnesium niobium Barium oxide, barium magnesium tantalate, lead titanate, lead zirconate, lead zirconate titanate, lead niobate, lead magnesium niobate, lead nickel niobate, lead tungstate, tungsten Examples thereof include calcium oxide, lead magnesium tungstate, and titanium dioxide. The barium titanate system includes solid solutions based on barium titanate, in which some elements in the barium titanate crystal are replaced with other elements or other elements are infiltrated into the crystal structure. It is a generic name. Other barium zirconate titanate, strontium titanate, calcium titanate, bismuth titanate, magnesium titanate, barium neodymium titanate, barium tin titanate, barium magnesium niobate, magnesium tantalate Barium, lead titanate, lead zirconate, lead zirconate titanate, lead niobate, lead magnesium niobate, lead nickel niobate, lead tungstate, calcium tungstate, magnesium tungstic acid Both lead-based and titanium dioxide-based are the same, and are generic names including solid solutions that use each as a base material.

  In particular, it is preferable to use a filler having a perovskite crystal structure or a composite perovskite crystal structure. Of these, one kind can be used alone, or two or more kinds can be used in combination, but at least two kinds of inorganic fillers having different average particle diameters have the same chemical composition in terms of dielectric properties. Therefore, it is preferable. In particular, when obtaining a dielectric composition having a high dielectric constant, it is preferable to use a compound mainly composed of barium titanate from the viewpoint of compatibility with commercial convenience. However, for the purpose of improving dielectric properties and temperature stability, a small amount of a shifter, a depressor, etc. may be added.

  Examples of the method for producing the inorganic filler include solid phase reaction methods, hydrothermal synthesis methods, supercritical hydrothermal synthesis methods, sol-gel methods, and oxalate methods. As a method for producing the inorganic filler having the maximum average particle size, it is preferable to use a solid phase reaction method or an oxalate method from the viewpoint of high relative dielectric constant and quality stability. In addition, it is preferable to use one of the hydrothermal synthesis method, the supercritical hydrothermal synthesis method, and the sol-gel method as the method for producing the inorganic filler having the minimum average particle size because it is easy to reduce the particle size. .

  As a ratio of the inorganic filler and the resin contained in the paste composition and the dielectric composition of the present invention, the ratio Vf of the inorganic filler to the total volume of the total volume of the inorganic filler and the total volume of the resin solids is 50% or more and 95. % Or less is preferable. More preferably, it is 70% or more and 90% or less. When the inorganic filler content Vf is 50% or more, a sufficiently large relative dielectric constant can be obtained, and a small thermal expansion coefficient can be obtained. Further, when the inorganic filler content Vf is 70% or more, the effect of using the inorganic filler having at least two kinds of average particle diameters becomes remarkable, and a large relative dielectric constant is obtained. On the other hand, when the inorganic filler content Vf is 95% or less, the generation of voids in the composition can be suppressed, a sufficiently large relative dielectric constant can be obtained, the moisture absorption due to the voids is small, and the physical properties are moisture and humidity. It is hard to be affected by. Moreover, when the inorganic filler content Vf is 90% or less, the adhesiveness after PCT (pressure cooker test), which is a durability promotion test, is unlikely to decrease.

  Next, as the resin used in the present invention, both thermoplastic and thermosetting resins can be selected.

  As the thermoplastic resin, for example, polyphenylene ether, polyphenylene sulfide, polyether sulfone, polyether imide, liquid crystal polymer, polystyrene, polyethylene, fluorine resin, or the like can be used.

  Thermosetting resins include, for example, epoxy resins, phenol resins, siloxane resins, polyimides, acrylic resins, cyanate resins, benzocyclobutene resins, and other resins that are generally used for insulating layers of printed wiring boards. Can be used. From the viewpoint of solder heat resistance, it is preferable to use a thermosetting resin, and in particular, an epoxy resin is preferably used from the viewpoint of thermosetting shrinkage and viscosity.

  Here, the epoxy resin is a resin having a prepolymer containing two or more epoxy groups (oxirane rings) in the molecular structure. The prepolymer preferably has a biphenyl skeleton or a dicyclopentadiene skeleton from the viewpoint of dielectric properties. Moreover, you may have a hardening | curing agent and hardening agents, such as a phenol novolak resin, a bisphenol A type novolak resin, an aminotriazine compound, a naphthol compound, can be used for a hardening | curing agent. Further, it is possible to add a curing accelerator such as a metal chelate compound such as triphenylphosphine, a benzimidazole compound, or tris (2,4-pentanedionato) cobalt.

The paste composition of the present invention is obtained by dispersing an inorganic filler in a resin. For example, making an inorganic filler in addition to the resin solution, mixing and method of dispersing, and the like in advance the inorganic filler to prepare a dispersion dispersed in a suitable solvent agents, letdown method of mixing the dispersion and the resin solution Is done. Further, a method of dispersing the inorganic filler into the resin or solvent dosage is not particularly limited, for example, ultrasonic dispersion, a ball mill, a roll mill, Clearmix, homogenizer, a method can be used such as media disperser, in particular, From the viewpoint of dispersibility, it is preferable to use a ball mill or a homogenizer.

  When dispersing the inorganic filler, in order to improve dispersibility, for example, surface treatment of the inorganic filler, addition of a dispersant, addition of a surfactant, addition of a solvent, and the like may be performed. Examples of the surface treatment of the inorganic filler include rosin treatment, acid treatment, basic treatment and the like, in addition to treatment with various coupling agents such as silane, titanium, and aluminum, fatty acids, and phosphate esters. Examples of the addition of the dispersant include dispersants having an acid group such as phosphoric acid, carboxylic acid, fatty acid, and esters thereof. In particular, compounds having a phosphate ester skeleton are preferably used. . In addition, addition of nonionic, cationic, anionic surfactants, wetting agents such as polyvalent carboxylic acids, amphoteric substances, and resins having highly sterically hindered substituents can be mentioned. Moreover, the polarity of the system at the time of dispersion or after dispersion can be controlled by addition of a solvent. Moreover, the paste composition may contain a stabilizer, a dispersant, an anti-settling agent, a plasticizer, an antioxidant, and the like, if necessary.

  The content of the inorganic filler in the solid content contained in the paste composition of the present invention is preferably 85% by weight or more and 99% by weight or less, more preferably 90% by weight or more, and further preferably 94% by weight or more. It is. When the content of the inorganic filler is 85% by weight or more, the relative dielectric constant of the composition can be easily increased. According to the present invention, a dielectric composition having a high relative dielectric constant can be obtained as the content of the inorganic filler is increased. When the content is 99% by weight or less, the moldability during film formation is facilitated, and Easy to control filler dispersion. In addition, solid content means what combined the inorganic filler, resin, and other additives.

  The dielectric composition of the present invention is a dielectric composition comprising an inorganic filler and a resin, and the amount of the inorganic filler is 85 to 99% by weight of the total solid content contained in the dielectric composition. And the porosity is 30 volume% or less.

  As a method for obtaining the dielectric composition of the present invention, for example, first, a paste composition in which an inorganic filler is mixed with a resin is prepared, the paste composition is applied to an adherend (for example, a substrate), and a solvent is removed. There is a method of obtaining a dielectric composition by solidifying. At this time, solidification by heat, light, etc. is mentioned as a solidification method. However, since the dielectric composition of the present invention is not a sintered body, it is not necessary to completely decompose and remove the resin, and it is preferable to heat at a temperature within the heat resistant temperature range of the electronic component, for example, 500 ° C. or less. .

  The porosity of the dielectric composition needs to be 30% by volume or less, preferably 20% by volume or less, and more preferably 10% by volume or less. When the porosity is larger than 30% by volume, the proportion of the inorganic filler in the film volume is low, and it is difficult to obtain a dielectric composition having a relative dielectric constant of 50 or more. Further, it is not preferable because a decrease in insulation resistance, an increase in leakage current, and a decrease in bending strength occur.

  Here, as a method of setting the porosity to 30% by volume or less, for example, it can be achieved by appropriately selecting the inorganic filler, resin, and solvent from the above, but the paste composition has a boiling point of 160 ° C. or higher. This can be easily achieved by including at least one solvent and having a total volume of 25% or less of the total amount of the paste composition.

  For example, in order to make the porosity 20 volume% or less, the porosity can be made 20 volume% or less when the paste composition contains at least one solvent having a lactone structure. Of the solvents having a lactone structure, γ-butyrolactone is most preferred.

Method of measuring the porosity of the dielectric composition, gas adsorption method, mercury porosimetry, positron annihilation method, such as small angle X-ray scattering method, can be appropriately selected according to the use, in the present invention, dielectrics From the density of the composition, the porosity is determined by the following procedures (1) to (3).

(1) Weigh the dielectric composition obtained by applying the paste composition onto the weighed shaped substrate, removing the solvent, and solidifying it.
(2) When the weight of the substrate is W1, the weight of the substrate and the dielectric composition is W2, the density of the dielectric composition is D, and the volume is V, the density of the dielectric composition D = (W2-W1) / V.
(3) Using a thermogravimetry apparatus (TGA), the dielectric composition is heated to 900 ° C. at a temperature rising rate of 10 ° C./min in the air atmosphere and held at 900 ° C. for 30 minutes to remove the binder. And the ratio of the inorganic filler and the resin contained in the dielectric composition was measured. When the volume of the inorganic filler is Wc, the specific gravity is ρc, the volume of the resin is Wp, the specific gravity is ρp, and the porosity is P, the porosity P can be obtained by the following equation. Porosity P (volume%) = {(V−Wc / ρc−Wp / ρp) / V} × 100.

  The paste composition of the present invention is preferably applied onto an adherend (for example, a substrate), and the solvent is removed and solidified to form a dielectric composition. The method for applying the paste composition onto the adherend is not particularly limited, and examples thereof include a spinner, screen printing, blade coater, and die coater. Thus, the dielectric composition can be easily obtained by removing the solvent and thermosetting the applied film using a heating device such as a hot plate or an oven.

  The adherend to which the paste composition is applied can be selected from, for example, an organic substrate, an inorganic substrate, and those in which circuit constituent materials are arranged on these substrates. Examples of organic substrates include glass-based copper-clad laminates such as glass cloth / epoxy copper-clad laminates, composite copper-clad laminates such as glass nonwoven fabrics / epoxy copper-clad laminates, polyetherimide resin substrates, polyethers Examples include heat-resistant / thermoplastic substrates such as ketone resin substrates and polysulfone resin substrates, polyester copper-clad film substrates, and polyimide copper-clad film substrates.

  Examples of inorganic substrates include ceramic substrates such as alumina substrates, aluminum nitride substrates, and silicon carbide substrates, and metal substrates such as aluminum base substrates and iron base substrates. Examples of circuit components include conductors containing metals such as silver, gold and copper, resistors containing inorganic oxides, low dielectrics containing glassy materials and / or resins, resins and inorganics Examples thereof include a high dielectric material containing a filler and the like, and an insulator containing a glass-based material.

  The form of the dielectric composition of the present invention is not particularly limited, and can be selected according to applications such as a film shape, a rod shape, a spherical shape, etc., but a film shape is particularly preferable. The membrane here includes a film, a sheet, a plate, a pellet and the like. Of course, it is also possible to perform pattern formation according to applications such as via hole formation for conduction, adjustment of impedance, capacitance or internal stress, or provision of a heat dissipation function.

  When the dielectric composition is used as a film, the film thickness can be arbitrarily set within a range where the capacitance satisfies a desired value, but is preferably 0.5 μm or more and 20 μm or less. More preferably, it is not less than 2 μm and not more than 20 μm. In order to secure a large capacitance as a capacitor, it is preferable that the film thickness is thin. However, if the thickness is less than 0.5 μm, pinholes are easily generated, and electrical insulation is difficult to obtain. When the thickness is 2 μm or more, the dielectric loss tangent hardly increases after PCT (pressure cooker test) which is a durability promotion test. On the other hand, if the film thickness exceeds 20 μm, a large relative dielectric constant is required to obtain sufficient capacitor performance, and it may be difficult to improve the mounting density.

  The use of the paste composition and the dielectric composition of the present invention is not particularly limited. For example, the paste composition and the dielectric composition are used as an interlayer insulating material for a built-in capacitor of a printed wiring board as a high dielectric constant layer. It can be applied to various electronic parts and devices such as radio antennas, electromagnetic shields, and optical wiring materials.

  The dielectric composition of the present invention is preferably used as an interlayer insulating material for capacitors. The method for forming the interlayer insulating material for capacitors using the dielectric composition is not particularly limited. For example, as described above, after a high dielectric is formed on a substrate, it can be obtained by appropriately forming an electrode.

The capacitance per area of the capacitor interlayer insulating material produced using the dielectric composition of the present invention is preferably in the range of 5 nF / cm ² or more. More preferably, it is in the range of 10 nF / cm ² or more. When the capacitance is smaller than 5 nF / cm ² , when used as a decoupling capacitor, the entire system cannot be sufficiently separated from the power supply system and cannot function sufficiently as a decoupling capacitor.

  The smaller the capacitance change in temperature and the in-plane variation, the better in terms of circuit design. The temperature change is preferably as small as possible. For example, it is preferable to satisfy the X7R characteristic (capacitance temperature change rate within −15% at −55 to 125 ° C.). The in-plane variation in capacitance is preferably 5% or less (average capacitance value−5% ≦ capacitance ≦ average capacitance value + 5%) with respect to the average value.

  In order to reduce the power loss of the power source, the dielectric loss tangent of the capacitor is preferably in the range of 0.01 to 5%, and more preferably in the range of 0.01 to 1%. Here, electrical characteristics such as capacitance and dielectric loss tangent are measured values at a frequency of 20 k to 1 GHz.

  The dielectric composition of the present invention can be preferably used as an optical wiring material. Optical wiring refers to wiring in a system in which signal transmission between LSIs, modules, boards, and the like is performed not by normal electrical signals but by optical signals. When an optical wiring is formed on or in the mounting substrate, a structure in which a layer having a high refractive index is sandwiched between layers having a low refractive index is employed. It is also possible to substitute a layer having a low refractive index with a space. When used as an optical wiring material, it is important to use an inorganic filler that is sufficiently smaller than the wavelength of the light in order to reduce the scattering of light for signal transmission guided in the optical wiring. The particle size is preferably ¼ or less. Further, the refractive index, the temperature dependency of the refractive index, and the thermal expansion coefficient can be controlled from the selection of the inorganic filler material, the content, and the selection of the resin material. This broadens the range of choice of substrate material for forming the optical wiring layer, making it possible to use not only conventional materials made of inorganic materials such as silicon and ceramics, but also substrates made of organic materials. Become.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

Example 1
323 parts by weight of barium titanate filler (manufactured by Sakai Chemical Co., Ltd., BT-05, average particle size: 0.5 μm) and 18 parts by weight of γ-butyrolactone were mixed and dispersed for 1 hour under ice cooling using a homogenizer. A liquid A-1 was obtained. 10 parts by weight of epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EPPN502H), 10 parts by weight of phenol novolac resin (manufactured by Dainippon Ink Industries, Ltd., TD-2131), curing accelerator (manufactured by Hokuko Chemical Co., Ltd.) 0.6 parts by weight of phenylphosphine) and 20 parts by weight of γ-butyrolactone were mixed to obtain an epoxy resin solution B-1. Dispersion A-1 and epoxy resin solution B-1 were mixed using a ball mill to prepare paste composition C-1. The boiling point of γ-butyrolactone is 204 ° C. The paste composition C-1 was applied onto a 300 μm thick aluminum substrate using a die coater, dried in an oven at 80 ° C. for 15 minutes, and then cured at 175 ° C. for 1 hour to form a film. A high dielectric composition having a thickness of 10 μm was obtained.

Next, an aluminum electrode having a diameter of 11 mm is formed on this high dielectric composition by vapor deposition, and the dielectric characteristics at 1 MHz are determined in accordance with JIS K 6911 using impedance analyzer HP4284A and sample holder HP16451B (both manufactured by Hewlett Packard). Table 1 shows the measurement results. The dielectric constant of the high dielectric composition was 82, the dielectric loss tangent was 2.8%, and the capacitance per area was 7.3 nF / cm ² . The porosity was 9% by volume.

Example 2
A paste composition C-1 was produced in the same manner as in Example 1. Next, 22.6 parts by weight of γ-butyrolactone was further added to prepare paste composition C-2 so that the amount of solvent in the paste composition was 15% by weight. Table 1 shows the results of preparing a high dielectric composition and evaluating the dielectric properties based on the method of Example 1. The high dielectric composition had a relative dielectric constant of 73, a dielectric loss tangent of 3.4%, and a capacitance per area of 4.3 nF / cm ² . The porosity was 12% by volume.

Examples 3-4
Γ-Butyrolactone was further added to paste composition C-1, and paste compositions C-3 to C-4 having different solvent amounts were prepared so that the solvent amount in the paste composition was 20 and 25% by weight. Table 1 shows the results of preparing a high dielectric composition and evaluating the dielectric properties based on the method of Example 1. A high dielectric composition having a porosity of 20% by volume or less and a relative dielectric constant of 50 or more was obtained.

Comparative Example 1
Γ-Butyrolactone was added to paste composition C-1, and paste composition D-1 in which the amount of solvent in the paste composition was 40% by weight was produced. Table 4 shows the results of preparing a high dielectric composition and evaluating the dielectric properties based on the method of Example 1. When the amount of solvent contained in the paste composition was 40% by weight of the total amount, the porosity was 31% by volume and the relative dielectric constant was 41.

Example 5
323 parts by weight of barium titanate (manufactured by Sakai Chemical Co., Ltd., BT-05, average particle size: 0.5 μm), 0.2 part by weight of dispersant (BYK-W903, manufactured by BYK Chemie), γ-butyrolactone 18 A part by weight was kneaded using a homogenizer to obtain dispersion A-2. Dispersion A-2 and epoxy resin solution B-1 were mixed using a ball mill to prepare paste composition C-5. Table 1 shows the results of preparing a high dielectric composition and evaluating the dielectric properties based on the method of Example 1. The relative dielectric constant was 102, the dielectric loss tangent was 3.6%, the capacitance per area was 11.3 nF / cm ² , and the porosity was 6% by volume.

Example 6
Γ-butyrolactone was added to paste composition C-5 to prepare paste composition C-6 in which the amount of solvent in the paste composition was 15% by weight. Table 1 shows the results of preparing a high dielectric composition and evaluating the dielectric properties based on the method of Example 1. The relative dielectric constant was 95, the dielectric loss tangent was 3.1%, the capacitance per area was 8.4 nF / cm ² , and the porosity was 7% by volume.

Example 7
A paste composition was prepared in the same manner as the paste composition C-2 except that the solvent was N-methyl 2-pyrrolidone, thereby preparing a paste composition C-7. The boiling point of N-methyl 2-pyrrolidone is 202 ° C. Table 1 shows the results of producing a high dielectric composition based on the method of Example 1 and evaluating the dielectric properties. The relative dielectric constant was 58, the dielectric loss tangent was 4.6%, the capacitance per area was 5.3 nF / cm ² , and the porosity was 26% by volume.

Example 8
A paste composition was prepared in the same manner as the paste composition C-2 except that the solvent was ethylene glycol diacetate, thereby preparing a paste composition C-8. The boiling point of ethylene glycol diacetate is 190 ° C. Table 1 shows the results of producing a high dielectric composition based on the method of Example 1 and evaluating the dielectric properties. The relative dielectric constant was 64, the dielectric loss tangent was 4.8%, the capacitance per area was 5.7 nF / cm ² , and the porosity was 21% by volume.

Example 9
A paste composition was prepared in the same manner as the paste composition C-2 except that the solvent was ethyl carbitol to prepare a paste composition C-9. The boiling point of ethyl carbitol is 202 ° C. Table 2 shows the results of producing a high dielectric composition based on the method of Example 1 and evaluating the dielectric properties. The relative dielectric constant was 50, the dielectric loss tangent was 2.2%, the capacitance per area was 4.4 nF / cm ² , and the porosity was 30% by volume.

Comparative Example 2
A paste composition was prepared in the same manner as the paste composition C-2 except that the solvent was morpholine, and a paste composition D-2 was prepared. The boiling point of morpholine is 128 ° C. Table 4 shows the results of producing a high dielectric composition based on the method of Example 1 and evaluating the dielectric properties. The relative dielectric constant was 35, the dielectric loss tangent was 5.8%, the capacitance per area was 2.6 nF / cm ² , and the electrical characteristics were inferior. The porosity was 32% by volume.

Comparative Example 3
A paste composition was prepared in the same manner as the paste composition C-2 except that the solvent was propylene glycol monomethyl acetate to prepare a paste composition D-3. The boiling point of propylene glycol monomethyl acetate is 146 ° C. Table 4 shows the results of producing a high dielectric composition based on the method of Example 1 and evaluating the dielectric properties. The relative dielectric constant was 46, the dielectric loss tangent was 4.7%, and the capacitance per area was 2.7 nF / cm ² , indicating poor electrical characteristics. The porosity was 35% by volume.

Example 10
494 parts by weight of barium titanate (manufactured by Sakai Chemical Co., Ltd., BT-05, average particle size: 0.5 μm) and 71 parts by weight of γ-butyrolactone were kneaded using a homogenizer to obtain dispersion A-3. Dispersion A-3 and epoxy resin solution B-1 were mixed using a ball mill to prepare paste composition C-10. Table 2 shows the results of producing a high dielectric composition based on the method of Example 1 and evaluating the dielectric properties. The relative dielectric constant was 79, the dielectric loss tangent was 3.4%, the capacitance per area was 5.8 nF / cm ² , and the porosity was 13% by volume.

Example 11
185 parts by weight of barium titanate (manufactured by Sakai Chemical Co., Ltd., BT-05, average particle size: 0.5 μm) and 16 parts by weight of γ-butyrolactone were kneaded using a homogenizer to obtain dispersion A-4. Dispersion A-4 and epoxy resin solution B-1 were mixed using a ball mill to prepare paste composition C-11. Table 2 shows the results of producing a high dielectric composition based on the method of Example 1 and evaluating the dielectric properties. The relative dielectric constant was 76, the dielectric loss tangent was 3.2%, the capacitance per area was 8.4 nF / cm ² , and the porosity was 5% by volume.

Example 12
A paste composition C-12 was produced in the same manner as in Example 2, except that barium titanate (manufactured by Toho Titanium Co., Ltd., SB05, average particle size: 0.5 μm) was used as the high dielectric constant inorganic filler. did. Table 2 shows the results of producing a high dielectric composition based on the method of Example 1 and evaluating the dielectric properties. The relative dielectric constant was 70, the dielectric loss tangent was 2.9%, the capacitance per area was 6.2 nF / cm ² , and the porosity was 14% by volume.

Example 13
A paste composition C-13 was prepared in the same manner as in Example 2 except that strontium titanate (manufactured by Sakai Chemical Co., Ltd., ST-03, average particle size: 0.3 μm) was used as the high dielectric constant inorganic filler. Produced. Table 2 shows the results of producing a high dielectric composition based on the method of Example 1 and evaluating the dielectric properties. The relative dielectric constant was 65, the dielectric loss tangent was 1.2%, the capacitance per area was 3.8 nF / cm ² , and the porosity was 14% by volume.

Examples 14-16
Paste compositions C-14 to 16 were produced in the same manner as in Example 2 except that the resins and curing agents shown in Table 2 were used. Table 2 shows the results of producing a high dielectric composition and evaluating the dielectric characteristics. A high dielectric composition having a relative dielectric constant of 50 or more was obtained.

Example 19
323 parts by weight of barium titanate filler (manufactured by Sakai Chemical Co., Ltd., BT-05, average particle size: 0.5 μm) and 36 parts by weight of γ-butyrolactone were mixed and dispersed for 1 hour under ice-cooling using a homogenizer. A liquid A-5 was obtained. 12.8 parts by weight of epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EPPN502H), 7.8 parts by weight of phenol novolac resin (manufactured by Dainippon Ink Industries, Ltd., TD-2131), curing accelerator (Hokuko Chemical Co., Ltd.) ), Triphenylphosphine) 0.2 parts by weight and γ-butyrolactone 24.8 parts by weight were mixed to obtain an epoxy resin solution B-2. Dispersion A-5 and epoxy resin solution B-2 were mixed using a ball mill to prepare paste composition C-19. Table 3 shows the results of preparing a high dielectric composition based on the method of Example 1 and evaluating the dielectric properties. The relative dielectric constant was 73, the dielectric loss tangent was 3.4%, the capacitance per area was 4.3 nF / cm ² , and the porosity was 12% by volume.

Example 20
323 parts by weight of barium titanate (manufactured by Sakai Chemical Co., Ltd., BT-05, average particle size: 0.5 μm), dispersant (copolymer having an acid group having a phosphate ester skeleton: manufactured by BYK Chemie, BYK- W9010) 0.2 parts by weight and 36 parts by weight of γ-butyrolactone were kneaded using a homogenizer to obtain dispersion A-6. Dispersion A-6 and epoxy resin solution B-2 were mixed using a ball mill to prepare paste composition C-20. Table 3 shows the results of preparing a high dielectric composition based on the method of Example 1 and evaluating the dielectric properties. The relative dielectric constant was 95, the dielectric loss tangent was 3.1%, the capacitance per area was 8.4 nF / cm ² , and the porosity was 7% by volume.

Example 21
Epoxy resin (Nippon Kayaku Co., Ltd., NC3000) 15.3 parts by weight, phenol novolak resin (Nippon Kayaku Co., Ltd., “Kayahard” TPM (new name: “Kayahard” KTG-105)) 5.3 Part by weight, 0.2 part by weight of a curing accelerator (manufactured by Hokuko Chemical Co., Ltd., triphenylphosphine) and 24.7 parts by weight of γ-butyrolactone were mixed to obtain an epoxy resin solution B-3. Dispersion A-2 and epoxy resin solution B-3 were mixed using a ball mill to prepare paste composition C-21. Table 3 shows the results of producing a high dielectric composition based on the method of Example 1 and evaluating the dielectric characteristics. The relative dielectric constant was 76, the dielectric loss tangent was 2.8%, the capacitance per area was 5.6 nF / cm ² , and the porosity was 14% by volume.

Example 22
Barium titanate (manufactured by Sakai Chemical Co., Ltd., BT-05: average particle size 0.5 μm) 62.3 parts by weight, barium titanate (manufactured by TPL, Inc., HPB-1000: average particle size 0.059 μm) Using a homogenizer, 21.9 parts by weight, 15 parts by weight of γ-butyrolactone, and 0.8 parts by weight of a dispersant (a copolymer having an acid group having a phosphate ester skeleton, BYK-W9010 manufactured by BYK Japan Japan Co., Ltd.) The mixture was kneaded to obtain dispersion A-7. 2.2 parts by weight of epoxy resin (Nippon Kayaku Co., Ltd., EPPN502H), 1.4 parts by weight of phenol novolac resin (manufactured by Dainippon Ink Industries, Ltd., TD-2131), curing accelerator (Hokuko Chemical Co., Ltd.) ), Triphenylphosphine) 0.04 parts by weight and γ-butyrolactone 7.1 parts by weight were mixed to obtain an epoxy resin solution B-4. Dispersion A-7 and epoxy resin solution B-4 were mixed using a ball mill to prepare paste composition C-22. Table 6 shows the results of producing a high dielectric composition based on the method of Example 1 and evaluating the dielectric characteristics. The relative dielectric constant was 123, the dielectric loss tangent was 3.1, the capacitance was 10.9 nF / cm ² , and the porosity was 4% by volume.

Example 23
2.6 parts by weight of epoxy resin (manufactured by Nippon Kayaku Co., Ltd., NC-3000), phenol novolak resin (manufactured by Nippon Kayaku Co., Ltd., “Kayahard” TPM (new name: “Kayahard” KTG-105) 9 parts by weight, 0.04 part by weight of a curing accelerator (manufactured by Hokuko Chemical Co., Ltd., triphenylphosphine) and 7.1 parts by weight of γ-butyrolactone were mixed to obtain an epoxy resin solution B-5. -7 and epoxy resin solution B-5 were mixed using a ball mill to prepare paste composition C-23, and a high dielectric composition was prepared based on the method of Example 1, and the dielectric properties were evaluated. The results are shown in Table 6. The relative dielectric constant was 121, the dielectric loss tangent was 2.6%, the capacitance per area was 10.7 nF / cm ² , and the porosity was 4% by volume.

Example 24
A paste composition C-24 was produced in the same manner as in Example 23 except that the solvent was ethylene glycol diacetate. The boiling point of ethylene glycol diacetate is 190 ° C. Table 6 shows the results of producing a high dielectric composition based on the method of Example 1 and evaluating the dielectric characteristics. The relative dielectric constant was 95, the dielectric loss tangent was 3.1%, the capacitance per area was 8.4 nF / cm ² , and the porosity was 8% by volume.

Example 25
A paste composition C-25 was produced in the same manner as in Example 23 except that the solvent was diethyl malonate. The boiling point of diethyl malonate is 199 ° C. Further, based on the method of Example 1, a high dielectric composition was prepared and the dielectric characteristics were evaluated. The relative dielectric constant was 85, the dielectric loss tangent was 2.7%, the capacitance per area was 7.5 nF / cm ² , and the porosity was 9% by volume.

Example 26
A paste composition C-26 was produced in the same manner as in Example 23 except that the solvent was ethyl carbitol. The boiling point of ethyl carbitol is 202 ° C. Further, based on the method of Example 1, a high dielectric composition was prepared and the dielectric characteristics were evaluated. The relative dielectric constant was 99, the dielectric loss tangent was 2.9%, the capacitance per area was 8.8 nF / cm ² , and the porosity was 7% by volume.

Example 27
A paste composition C-27 was produced in the same manner as in Example 23 except that the solvent was 4-methylcyclohexanone. The boiling point of 4-methylcyclohexanone is 169 ° C. Table 6 shows the results of producing a high dielectric composition based on the method of Example 1 and evaluating the dielectric characteristics. The relative dielectric constant was 79, the dielectric loss tangent was 2.1%, the capacitance per area was 7.0 nF / cm ² , and the porosity was 12% by volume.

Example 28
A paste composition C-28 was produced in the same manner as in Example 23 except that the solvent was isophorone. The boiling point of isophorone is 215 ° C. Table 6 shows the results of producing a high dielectric composition based on the method of Example 1 and evaluating the dielectric characteristics. The relative dielectric constant was 76, the dielectric loss tangent was 2.2%, the capacitance per area was 6.7 nF / cm ² , and the porosity was 11% by volume.

Example 29
A paste composition C-29 was produced in the same manner as in Example 23 except that the solvent was diethylformamide. The boiling point of diethylformamide is 177 ° C. Table 6 shows the results of producing a high dielectric composition based on the method of Example 1 and evaluating the dielectric characteristics. The relative dielectric constant was 70, the dielectric loss tangent was 2.3%, the capacitance per area was 6.2 nF / cm ² , and the porosity was 15% by volume.

Example 30
A paste composition C-30 was produced in the same manner as in Example 23 except that the solvent was dimethylacetamide. The boiling point of dimethylacetamide is 165 ° C. Further, based on the method of Example 1, a high dielectric composition was prepared and the dielectric characteristics were evaluated. The relative dielectric constant was 79, the dielectric loss tangent was 2.3%, the capacitance per area was 7.0 nF / cm ² , and the porosity was 11% by volume.

Synthesis Example 1; Dispersion X-1
Barium titanate filler (manufactured by Sakai Chemical Industry Co., Ltd., BT-05, average particle size: 0.5 μm) 5328 parts by weight, barium titanate filler (TPL, Inc., HPB-1000, average particle size: 0) 0.059 μm) 1872 parts by weight, 928 parts by weight of γ-butyrolactone, 72 parts by weight of a dispersant (copolymer having an acid group having a phosphate ester skeleton: BYK-W9010, manufactured by BYK-W9010) using a homogenizer, Under ice cooling, the mixture was dispersed for 1 hour to obtain dispersion X-1.

Synthesis Example 2; Dispersion X-2
Barium titanate filler (manufactured by Sakai Chemical Industry Co., Ltd., BT-05, average particle size: 0.5 μm) 5328 parts by weight, barium titanate filler (manufactured by Cabot Corp., K-Plus16, average particle size: 0.06 μm) ) 1872 parts by weight, 928 parts by weight of γ-butyrolactone, 72 parts by weight of a dispersant (copolymer having an acid group having a phosphate ester skeleton: BYK-W9010, manufactured by BYK-Japan Co., Ltd.) using a homogenizer and ice-cooling Then, the mixture was dispersed for 1 hour to obtain dispersion X-2.

Synthesis Example 3; Dispersion X-3
Barium titanate filler (manufactured by Sakai Chemical Industry Co., Ltd., BT-02, average particle size: 0.18 μm) 5328 parts by weight, barium titanate filler (manufactured by TPL, Inc., HPB-1000, average particle size: 0.001). 059 μm) 1872 parts by weight, 928 parts by weight of γ-butyrolactone, 72 parts by weight of a dispersant (copolymer having an acid group having a phosphate ester skeleton: BYK-W9010, manufactured by BYK-Japan Japan Co., Ltd.) using a homogenizer The mixture was dispersed for 1 hour under cooling to obtain a dispersion X-3.

Synthesis Example 4; Dispersion X-4
Barium titanate filler (manufactured by Sakai Chemical Industry Co., Ltd., BT-03, average particle size: 0.28 μm) 5328 parts by weight, barium titanate filler (TPL, Inc., HPB-1000, average particle size: 0.001) 059 μm) 1872 parts by weight, 928 parts by weight of γ-butyrolactone, 72 parts by weight of a dispersant (copolymer having an acid group having a phosphate ester skeleton: BYK-W9010, manufactured by BYK-Japan Japan Co., Ltd.) using a homogenizer The mixture was dispersed for 1 hour under cooling to obtain a dispersion X-4.

Synthesis Example 5: Dispersion X-5
Barium titanate filler (manufactured by Kyoritsu Material Co., Ltd., BT-HP3, average particle size: 1.2 μm) 5328 parts by weight, barium titanate filler (manufactured by TPL, Inc., HPB-1000, average particle size: 0.059 μm) ) 1872 parts by weight, 928 parts by weight of γ-butyrolactone, 72 parts by weight of a dispersant (copolymer having an acid group having a phosphate ester skeleton: BYK-W9010, manufactured by BYK-Japan Co., Ltd.) using a homogenizer and ice-cooling Then, the mixture was dispersed for 1 hour to obtain a dispersion X-5.

Synthesis Example 6; Dispersion X-6
Barium titanate filler (manufactured by Kyoritsu Material Co., Ltd., BT-SA, average particle size: 2.1 μm) 5328 parts by weight, barium titanate filler (TPL, Inc., HPB-1000, average particle size: 0.059 μm) ) 1872 parts by weight, 928 parts by weight of γ-butyrolactone, 72 parts by weight of a dispersant (copolymer having an acid group having a phosphate ester skeleton: BYK-W9010, manufactured by BYK-Japan Co., Ltd.) using a homogenizer and ice-cooling The mixture was mixed and dispersed for 1 hour to obtain a dispersion X-6.

Synthesis Example 7; Dispersion X-7
Barium titanate filler (manufactured by Sakai Chemical Industry Co., Ltd., BT-05, average particle size: 0.5 μm) 6067 parts by weight, strontium titanate filler (manufactured by TPL, Inc., HPS-2000, average particle size: 0.00). 045 μm) 1613 parts by weight, 1523 parts by weight of γ-butyrolactone, 77 parts by weight of a dispersant (copolymer having an acid group having a phosphate ester skeleton: BYK-W9010, manufactured by BYK Japan Japan Co., Ltd.) using a homogenizer The mixture was dispersed for 1 hour under cooling to obtain dispersion X-7.

Synthesis Example 8; Dispersion X-8
Barium titanate filler (manufactured by Sakai Chemical Industry Co., Ltd., BT-05, average particle size: 0.5 μm) 5261 parts by weight, titanium oxide filler (manufactured by Toho Titanium Co., Ltd., HT0514, average particle size: 0.2 μm) 2419 parts by weight, 1523 parts by weight of γ-butyrolactone, 77 parts by weight of a dispersant (copolymer having an acid group having a phosphate ester skeleton: BYK-W9010, manufactured by BYK-Chemie Japan Co., Ltd.) using a homogenizer under ice cooling And mixed for 1 hour to obtain dispersion X-8.

Synthesis Example 9; Dispersion X-9
6695 parts by weight of lead filler (manufactured by Ferro, Y5V183U, average particle size: 0.9 μm), 1145 parts by weight of barium titanate filler (manufactured by TPL, Inc., HPB-1000, average particle size: 0.059 μm), γ -1722 parts by weight of butyrolactone and 78 parts by weight of a dispersant (copolymer having an acid group having a phosphate ester skeleton: BYK-W9010, manufactured by BYK-Chemie Japan Co., Ltd.) were mixed for 1 hour under ice cooling using a homogenizer. Dispersion was performed to obtain dispersion X-9.

Synthesis Example 10; Dispersion X-10
Barium titanate filler (manufactured by Sakai Chemical Industry Co., Ltd., BT-05, average particle size: 0.5 μm) 7200 parts by weight, γ-butyrolactone 928 parts by weight, dispersant (copolymer having phosphate ester acid group: 72 parts by weight of BYK-W9010 manufactured by Big Chemie Japan Co., Ltd. was mixed and dispersed for 1 hour under ice-cooling using a homogenizer to obtain a dispersion X-10.

Synthesis Example 11; Dispersion X-11
Barium titanate filler (manufactured by Kyoritsu Material Co., Ltd., BTHP-8YF, average particle size: 7 μm) 5328 parts by weight, barium titanate filler (manufactured by Sakai Chemical Industry Co., Ltd., BT-05, average particle size: 0.5 μm) ) 1872 parts by weight, 928 parts by weight of γ-butyrolactone, 72 parts by weight of a dispersant (copolymer having an acid group having a phosphate ester skeleton: BYK-W9010, manufactured by BYK-Japan Co., Ltd.) using a homogenizer and ice-cooling Then, the mixture was dispersed for 1 hour to obtain a dispersion X-11.

Synthesis Example 12; Dispersion X-12
Barium titanate filler (manufactured by Kyoritsu Material Co., Ltd., BT-SA, average particle size: 2.1 μm) was dispersed in an acrylic resin binder using a ball mill, and then primary particles were aggregated and solidified using a spray dryer. The next particles were granulated. Next, this was fired in the atmosphere at 1200 ° C. for 6 hours, and then pulverized in a mortar, followed by classification with a sieve of 500 mesh and 300 mesh, to obtain a barium titanate filler A having an average particle size of 40 μm. For the measurement of the average particle size, a dynamic scattering type particle size distribution measuring device (LB-500 manufactured by Horiba, Ltd.) was used. 5328 parts by weight of this barium titanate filler A, 1872 parts by weight of barium titanate filler B (manufactured by Kyoritsu Material Co., Ltd., BT-SA, average particle size: 2.1 μm), 928 parts by weight of γ-butyrolactone, dispersant ( 72 parts by weight of a copolymer having an acid group having a phosphate ester skeleton: BYK-W9010 manufactured by Big Chemie Japan Co., Ltd. was mixed and dispersed for 1 hour under ice cooling using a homogenizer, and dispersion X-12 was dispersed. Obtained.

Synthesis Example 13; Dispersion X-13
A barium titanate filler C having an average particle size of 20 μm was prepared in the same manner as the barium titanate filler A of Synthesis Example 12 except that 1000 and 600 mesh sieves were used. 5328 parts by weight of this barium titanate filler C, 1872 parts by weight of barium titanate filler B (manufactured by Kyoritsu Material Co., Ltd., BT-SA, average particle size: 2.1 μm), 928 parts by weight of γ-butyrolactone, dispersant ( 72 parts by weight of a copolymer having an acid group having a phosphate ester skeleton: BYK-W9010 manufactured by Big Chemie Japan Co., Ltd. was mixed and dispersed for 1 hour under ice-cooling using a homogenizer, and dispersion X-13 was prepared. Obtained.

Synthesis Example 14; epoxy resin solution Y-1
400 parts by weight of epoxy resin (manufactured by Nippon Kayaku Co., Ltd., “Phenolite” EPPN-502H), 400 parts by weight of phenol novolac resin (manufactured by Dainippon Ink and Chemicals, TD-2131), 1000 parts by weight of γ-butyrolactone Parts were mixed to obtain a resin solution Y-1.

Synthesis Example 15: Epoxy resin solution Y-2
Epoxy resin (Nippon Kayaku Co., Ltd., NC-3000) 600 parts by weight, phenol novolac resin (Nippon Kayaku Co., Ltd., “Kayahard” TPM (new name: “Kayahard” KTG-105)) 200 parts by weight Then, 8 parts by weight of a curing accelerator (manufactured by Hokuko Chemical Co., Ltd.) and 1000 parts by weight of γ-butyrolactone were mixed to obtain a resin solution Y-1.

Example 31
In a container equipped with a stirrer, 82 parts by weight of the dispersion X-1 was charged, 18 parts by weight of the resin solution Y-1 was gradually added, and mixed using the let-down method, and then further for 1 hour in a ball mill. The paste composition was obtained by stirring. At this time, when the total amount of the inorganic filler and the resin was 100% by volume, the inorganic filler content was about 61% by volume.

  Next, this paste composition is applied onto an aluminum substrate and a copper substrate using a spin coater, dried at 120 ° C. for 10 minutes using an oven, and then cured at 175 ° C. for 1 hour to obtain a dielectric. A composition was obtained. As a result of measuring the stress change due to the temperature of the dielectric composition formed on these two types of substrates using a stress measuring device Flexus manufactured by Tencor, and calculating the linear expansion coefficient of the dielectric composition from the rate of change, The value was 18 ppm / ° C., which was a good value almost corresponding to copper (17 ppm / ° C.).

Further, an aluminum electrode is formed on the surface of the dielectric composition on the aluminum substrate by vapor deposition, and the impedance characteristics (HP4284A, HP16451B, manufactured by Hewlett-Packard Co., Ltd.) are used to determine the dielectric characteristics at 1 MHz using the aluminum of the substrate as an electrode. The relative dielectric constant was 55, the dielectric loss tangent was 3.3%, and the capacitance per area was 4.9 nF / cm ² .

  Moreover, as a result of performing a pressure cooker test (PCT test, 100% RH, 121 ° C., 2 atm, 100 hours later) on the dielectric composition on the copper substrate, no abnormality was observed by microscopic observation, and a cross-cut tape In the test by the method (JIS K5400), the evaluation score was 10 points, which was good.

  In all measurements of the linear expansion coefficient, dielectric characteristics, and PCT test, the film thickness of the dielectric composition was evaluated at three levels of 5, 10, and 20 μm, but there was no difference depending on the film thickness. Therefore, Table 9 summarizes the results at 10 μm.

Example 32
In a container equipped with a stirrer, 86 parts by weight of the dispersion X-1 was charged, 11 parts by weight of the resin solution Y-1 and 3 parts by weight of γ-butyrolactone were gradually added and mixed using the letdown method. After that, the mixture was further stirred for 1 hour with a ball mill to obtain a paste composition. At this time, when the total amount of the inorganic filler and the resin was 100% by volume, the inorganic filler content was about 72% by volume.

  Using the paste composition thus obtained, a dielectric composition was obtained in the same manner as in Example 31, and the results of measuring the linear expansion coefficient, dielectric characteristics, and PCT test are shown in Table 9.

Example 33
In a container equipped with a stirrer, 88 parts by weight of the dispersion X-1 was charged, and 7 parts by weight of the resin solution Y-1 and 5 parts by weight of γ-butyrolactone were gradually added and mixed using the letdown method. After that, the mixture was further stirred for 1 hour with a ball mill to obtain a paste composition. At this time, when the total amount of the inorganic filler and the resin was 100% by volume, the inorganic filler content was about 79% by volume. Using the paste composition thus obtained, a dielectric composition was obtained in the same manner as in Example 31, and the results of measuring the linear expansion coefficient, dielectric characteristics, and PCT test are shown in Table 9.

Example 34
In a container equipped with a stirrer, 89 parts by weight of the dispersion X-1 was charged, and 4 parts by weight of the resin solution Y-1 and 7 parts by weight of γ-butyrolactone were gradually added and mixed using the letdown method. After that, the mixture was further stirred for 1 hour with a ball mill to obtain a paste composition. At this time, the inorganic filler content was about 86% by volume when the total amount of the inorganic filler and the resin was 100% by volume. Using the paste composition thus obtained, a dielectric composition was obtained in the same manner as in Example 31, and the results of measuring the linear expansion coefficient, dielectric characteristics, and PCT test are shown in Table 9.

Example 35
In a container equipped with a stirrer, 90 parts by weight of the dispersion X-1 was charged, and 2 parts by weight of the resin solution Y-1 and 8 parts by weight of γ-butyrolactone were gradually added and mixed using the letdown method. After that, the mixture was further stirred for 1 hour with a ball mill to obtain a paste composition. At this time, the inorganic filler content was about 91% by volume when the total amount of the inorganic filler and the resin was 100% by volume. Using the paste composition thus obtained, a dielectric composition was obtained in the same manner as in Example 31, and the results of measuring the linear expansion coefficient, dielectric characteristics, and PCT test are shown in Table 9.

Example 36
In a container equipped with a stirrer, 91 parts by weight of dispersion X-1 was charged, 1 part by weight of resin solution Y-1 and 8 parts by weight of γ-butyrolactone were gradually added, and mixed using a letdown method. After that, the mixture was further stirred for 1 hour with a ball mill to obtain a paste composition. At this time, the inorganic filler content was about 93% by volume when the total amount of the inorganic filler and the resin was 100% by volume. Using the paste composition thus obtained, a dielectric composition was obtained in the same manner as in Example 31, and the results of measuring the linear expansion coefficient, dielectric characteristics, and PCT test are shown in Table 9.

Examples 37-43
Into a container equipped with a stirrer, 88 parts by weight of the dispersion shown in Table 5 was charged, and 7 parts by weight of the resin solution shown in Table 5 and 5 parts by weight of γ-butyrolactone were gradually added to perform the letdown method. After using and mixing, the mixture was further stirred with a ball mill for 1 hour to obtain a paste composition. At this time, when the total amount of the inorganic filler and the resin was 100% by volume, the inorganic filler content was about 79% by volume. Using the paste composition thus obtained, a dielectric composition was obtained in the same manner as in Example 31, and the results of measuring the linear expansion coefficient, dielectric characteristics, and PCT test are shown in Tables 9 and 10. It was.

Example 44
In a container equipped with a stirrer, 93 parts by weight of the dispersion X-7 was charged, and 7 parts by weight of the resin solution Y-1 was gradually added and mixed using the let-down method. The mixture was stirred for a time to obtain a paste composition. At this time, the inorganic filler content was adjusted to about 79% by volume when the total amount of the inorganic filler and the resin was 100% by volume. Using the paste composition thus obtained, a dielectric composition was obtained in the same manner as in Example 31, and the results of measuring the linear expansion coefficient, dielectric characteristics, and PCT test are shown in Table 10.

Example 45
In a container equipped with a stirrer, 93 parts by weight of the dispersion X-8 was charged, 7 parts by weight of the resin solution Y-1 was gradually added and mixed using the let-down method. The mixture was stirred for a time to obtain a paste composition. At this time, the content of the inorganic filler when the total amount of the inorganic filler and the resin was 100% by volume was adjusted to about 81% by volume. Using the paste composition thus obtained, a dielectric composition was obtained in the same manner as in Example 31, and the results of measuring the linear expansion coefficient, dielectric characteristics, and PCT test are shown in Table 10.

Example 46
In a container equipped with a stirrer, 93 parts by weight of the dispersion X-9 was charged, 7 parts by weight of the resin solution Y-1 was gradually added, and mixed using the let-down method. The mixture was stirred for a time to obtain a paste composition. At this time, when the total amount of the inorganic filler and the resin was 100% by volume, the inorganic filler content was adjusted to about 86% by volume. Using the paste composition thus obtained, a dielectric composition was obtained in the same manner as in Example 31, and the results of measuring the linear expansion coefficient, dielectric characteristics, and PCT test are shown in Table 10.

Comparative Example 4
A dielectric composition was obtained in the same manner as in Example 31 except that the epoxy resin solution of Synthesis Example 14 was used and the inorganic filler dispersion was not used, and the results of measurement of the linear expansion coefficient, dielectric characteristics, and PCT test are shown. This is shown in FIG.

Comparative Example 5
In a container equipped with a stirrer, 88 parts by weight of the dispersion X-10 was charged, and 7 parts by weight of the resin solution Y-1 and 5 parts by weight of γ-butyrolactone were gradually added and mixed using the letdown method. After that, the mixture was further stirred for 1 hour with a ball mill to obtain a paste composition. At this time, when the total amount of the inorganic filler and the resin was 100% by volume, the inorganic filler content was about 79% by volume. Using the paste composition thus obtained, a dielectric composition was obtained in the same manner as in Example 31, and the results of measuring the linear expansion coefficient, dielectric characteristics, and PCT test are shown in Table 10.

Comparative Example 6
In a container equipped with a stirrer, 88 parts by weight of the dispersion X-11 was charged, and 7 parts by weight of the resin solution Y-1 and 5 parts by weight of γ-butyrolactone were gradually added and mixed using the letdown method. After that, the mixture was further stirred for 1 hour with a ball mill to obtain a paste composition. In this paste composition, the filler was liable to settle upon standing. At this time, when the total amount of the inorganic filler and the resin was 100% by volume, the inorganic filler content was about 79% by volume. Using the paste composition thus obtained, a dielectric composition was obtained in the same manner as in Example 31 and an attempt was made to measure dielectric properties. However, the measured values were not stable and could be measured. There wasn't.

Comparative Example 7
In a container equipped with a stirrer, 88 parts by weight of dispersion X-12 was charged, and 7 parts by weight of resin solution Y-1 and 5 parts by weight of γ-butyrolactone were gradually added and mixed using the letdown method. After that, the mixture was further stirred for 1 hour with a ball mill to obtain a paste composition. In this paste composition, the filler was liable to settle upon standing. At this time, when the total amount of the inorganic filler and the resin was 100% by volume, the inorganic filler content was about 79% by volume. Using the paste composition thus obtained, a dielectric composition was obtained in the same manner as in Example 31 and an attempt was made to measure dielectric properties. However, the measured values were not stable and could be measured. There wasn't.

Comparative Example 8
In a container equipped with a stirrer, 8893 parts by weight of dispersion X-13 was charged, 7 parts by weight of resin solution Y-1 and 5 parts by weight of γ-butyrolactone were gradually added, and mixed using the letdown method. After that, the mixture was further stirred for 1 hour with a ball mill to obtain a paste composition. In this paste composition, the filler was liable to settle upon standing. At this time, when the total amount of the inorganic filler and the resin was 100% by volume, the inorganic filler content was about 79% by volume. Using the paste composition thus obtained, a dielectric composition was obtained in the same manner as in Example 31 and an attempt was made to measure dielectric properties. However, the measured values were not stable and could be measured. There wasn't.

Comparative Example 9
Barium titanate filler (manufactured by Sakai Chemical Industry Co., Ltd., BT-05, average particle size: 0.5 μm) is a barium titanate filler (TPL, Inc., HPB-1000, average particle size) which is a large particle size filler. : 0.059 μm), barium titanate filler (manufactured by TPL, Inc., HPB-1000, average particle size: 0.059 μm), which is a small particle size filler, was replaced with strontium titanate filler (manufactured by TPL, Inc., An attempt was made to prepare a dispersion in the same manner as in Synthesis Example 3 except that the dispersion was changed to HPS-2000, average particle size: 0.045 μm). Could not get.

Claims (16)

A paste composition comprising an inorganic filler, an epoxy resin, and a solvent, the solvent having at least one solvent having a boiling point of 160 ° C. or higher, and an inorganic filler having an average particle diameter of 5 μm or less. And the total amount of the solvent is 25% by weight or less of the total amount of the paste composition. Inorganic fillers are barium titanate, barium zirconate titanate, strontium titanate, calcium titanate, bismuth titanate, magnesium titanate, barium neodymium titanate, barium tin titanate, magnesium niobate Barium, magnesium barium tantalate, lead titanate, lead zirconate, lead zirconate titanate, lead niobate, lead magnesium niobate, lead nickel niobate, lead tungstate, tungstic acid The paste composition according to claim 1, wherein the paste composition is at least one selected from calcium, lead magnesium tungstate, and titanium dioxide. The inorganic filler includes an inorganic filler having at least two kinds of average particle diameters, the maximum average particle diameter among the average particle diameters is 0.1 to 5 μm, and the maximum average particle diameter with respect to the minimum average particle diameter The paste composition according to claim 1, wherein the diameter is 3 times or more. The paste composition according to claim 1, comprising at least one solvent having an ester structure. The paste composition according to claim 1, comprising at least one solvent having a lactone structure. The paste composition according to claim 1, comprising a compound having a phosphate ester skeleton. A dielectric composition obtained by removing the solvent and solidifying the paste composition according to any one of claims 1 to 6 , wherein the amount of the inorganic filler is 85 to 85% of the total solid content contained in the dielectric composition. A dielectric composition having 99% by weight and a porosity of 30% by volume or less. A film shape, thickness is 0.5μm or more 20μm or less claim 7 Yuden composition described. A dielectric composition having an inorganic filler and a resin, wherein the inorganic filler has at least two types of average particle diameters, and the maximum average particle diameter of the average particle diameters is 0.1 to 5 μm, and the minimum the relative average particle diameter, the largest average particle size is not less 3 times or more, the dielectric composition porosity characterized der Rukoto than 30 vol%. Inorganic filler is titanium dioxide, barium titanate, barium zirconate titanate, strontium titanate, calcium titanate, bismuth titanate, magnesium titanate, barium neodymium titanate, barium tin titanate , Barium magnesium niobate, barium magnesium tantalate, lead titanate, lead zirconate, lead zirconate titanate, lead niobate, lead magnesium niobate, lead nickel niobate, lead tungstate 10. The dielectric composition according to claim 9 , wherein the dielectric composition is at least one selected from the group consisting of calcium, tungstate, and lead magnesium tungstate. The dielectric composition according to claim 9 , wherein a ratio Vf of the total volume of the inorganic filler to the total volume of the inorganic filler and the total volume of the resin solid satisfies 50% or more and 95% or less. The dielectric composition according to claim 9, wherein the resin contains a thermosetting resin. The dielectric composition according to claim 9 , wherein the resin is an epoxy resin. The dielectric composition according to claim 9, comprising a compound having a phosphate ester skeleton. Capacitors using claim 1 or 9 paste composition according or dielectric composition. Optical wiring using claim 1 or 9 paste composition according or dielectric composition.