JP2003049092A - Filler, resin composition, and application thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a filler of high dielectric permittivity having good dispersibility, to provide a method for producing the same, to obtain a resin composition compounded with the filler of high dielectric permittivity having the good dispersibility, to obtain a resin varnish compounded with the filler, to provide an electronic part obtained by using the same, and to provide a method for producing the electronic part. SOLUTION: The filler comprises a barium titanate power the surfaces of which are treated with a silane coupling agent having a primary amino group. The surfaces of the powder are preferably treated with the silane coupling agent having the primary amino group in the presence of an organic acid. The resin composition to which the filler is added is used for forming an insulating layer of a circuit board, or the like.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a surface-treated filler, a resin composition containing the same, and a varnish thereof, a wiring board using the resin composition, a resin film, a semiconductor package, a wiring board mounted with a semiconductor package, and Wiring board material,
And their manufacturing methods.

[0002]

2. Description of the Related Art Due to the demand for high-density mounting of various parts on a wiring board, the wiring board has become multi-layered, and circuit layers (coil: L, capacitor: C, resistance: R) are formed in the inner layer. The use of boards is increasing. Therefore, as a resin layer forming an insulating layer, a low dielectric constant resin layer is used for a circuit section related to high-speed signal processing, and a high dielectric constant resin layer is used for a layer corresponding to a capacitor. Is being considered. In order to form the high dielectric constant resin layer, in addition to selection of the high dielectric constant resin material, an inorganic filler having a high dielectric constant such as barium titanate is blended.

[0003]

However, when such a high dielectric constant filler is blended, the dispersibility of the filler is poor and
Since the resin varnish aggregates, it cannot be blended in a large amount, and there is a problem that the target high dielectric constant cannot be achieved. In view of the above, it is an object of the present invention to provide a high dielectric constant filler having good dispersibility and a method for producing the same. Another object of the present invention is to provide a resin composition and a resin varnish in which a high-dielectric-constant filler having good dispersibility is blended, an electronic component material using the same, and a method for producing the same.

[0004]

To achieve the above object, the filler according to the present invention is obtained by treating the surface of barium titanate powder particles with a silane coupling agent having a primary amino group. . As described above, by using the silane coupling agent having a primary amino group, the surface coating effect of the barium titanate powder particles by the coupling agent can be improved as compared with other coupling agents. By coating the particle surfaces in this way, it is difficult for the particles to aggregate in the liquid resin or the resin varnish, and the dispersibility of the barium titanate powder is improved.

Another filler according to the present invention is obtained by treating the surface of barium titanate powder particles with a silane coupling agent having a primary amino group in the presence of an organic acid. When the surface treatment is performed in the presence of an organic acid, the organic acid acts as a reaction catalyst, so that the treatment time can be shortened and a highly dispersible filler can be efficiently provided.

The method for producing a surface-treated filler according to the present invention is a method in which a treatment liquid in which a silane coupling agent having a primary amino group is dispersed or dissolved in an organic solvent is contacted with barium titanate powder and the surface is treated. The processing is performed. As described above, by performing the wet method using an organic solvent, it is possible to efficiently obtain a filler having a high surface treatment effect.
Furthermore, by performing this treatment in the presence of an organic acid as a reaction catalyst, the treatment time can be shortened and the surface treatment can be efficiently performed, and since the organic acid dissolves in an organic solvent, There is an advantage that the catalyst can be easily removed. This is because if acid or alkali as a catalyst remains in the filler, the insulating property will deteriorate when the resin insulating layer or the like is formed using the filler.

The resin composition according to the present invention comprises a resin and the above-mentioned filler according to the present invention. The resin varnish according to the present invention contains a resin, the filler according to the present invention, and a solvent. As described above, by using the filler of the present invention, the resin composition or resin varnish of the present invention can be blended with a large amount of this high dielectric constant filler as compared with the conventional one. Then, by using them, it is possible to form a resin layer in which the filler is uniformly dispersed and electric characteristics are made uniform, and it is possible to provide an insulating layer having a desired high dielectric constant.

The resin film according to the present invention comprises the above resin composition according to the present invention. Therefore,
A film having any desired dielectric constant can be obtained by uniformly dispersing an arbitrary amount of high-dielectric-constant filler, and is suitably used as an insulating film for various electronic components, an adhesive film, or a prepreg for wiring boards. it can.

The wiring board according to the present invention comprises an insulating layer and a wiring conductor, and the insulating layer is treated with a resin and the surface of the barium titanate powder particles with a silane coupling agent having a primary amino group. It is composed of a resin composition containing a filler. That is, since the insulating layer is composed of the resin composition of the present invention, it is possible to easily form an insulating layer having a dielectric constant depending on the application by adjusting the composition. For example, by using this insulating layer as a resin layer corresponding to a capacitor, it is possible to provide a multilayer wiring board with a highly functional capacitor that has capacitors of various capacities that can supply a stable power supply voltage. Since it is not necessary to mount a large number of capacitive elements, it is possible to reduce the number of circuit elements to be mounted and further reduce the size of electronic components. Further, from the viewpoint of impedance matching, the wiring width can be reduced, and the line length can be shortened in a resonance circuit such as an antenna and a stub, which enables miniaturization. The wiring board of the present invention can be suitably used as a semiconductor mounting substrate for a semiconductor package. The structure of the wiring board may be a single layer or a multilayer.

The method for producing a wiring board according to the present invention comprises (1) a resin composition containing a resin and a filler obtained by treating the surface of barium titanate powder particles with a silane coupling agent having a primary amino group. It includes a step of forming a first insulating layer made of a material, and (2) a step of forming a first wiring conductor in the first insulating layer. In addition, by further including (3) a step of forming a second insulating layer on the first wiring conductor and (4) a step of forming a second wiring conductor on the second insulating layer, a multilayer wiring board Can be manufactured. The resin composition of the present invention can also be preferably used for forming the second insulating layer.

In a semiconductor package according to the present invention, a semiconductor mounting substrate and a semiconductor chip mounted on the semiconductor mounting substrate are sealed with a sealing resin, and the semiconductor mounting substrate is the wiring of the present invention. It consists of plates. Further, in another semiconductor package according to the present invention, the sealing resin comprises the resin composition of the present invention.

The method of manufacturing a semiconductor package according to the present invention includes (1) a step of mounting a semiconductor chip on a semiconductor mounting substrate, and (2) the semiconductor mounting substrate and the semiconductor chip with the resin composition according to the present invention. And a step of sealing. Another method of manufacturing a semiconductor package according to the present invention uses a resin varnish.
A process of mounting a semiconductor chip on a semiconductor mounting substrate,
(2) The step of sealing the semiconductor mounting substrate and the semiconductor chip with the resin varnish according to the present invention, and (3) the step of removing the solvent in the varnish.

The semiconductor package mounting wiring board according to the present invention is a wiring board according to the present invention in which a half package is mounted. Further, another semiconductor package mounting wiring board according to the present invention is one in which the semiconductor package according to the present invention is mounted on a wiring board. In addition, it is also preferable to use a wiring board according to the present invention, which is a combination of the both, as a semiconductor package mounting wiring board in which the semiconductor package according to the present invention is mounted.

The wiring board material according to the present invention is characterized in that it comprises a resin layer and a carrier film, and the resin layer comprises the resin composition according to the present invention.

The method of manufacturing a wiring board material according to the present invention is as follows.
(1) The step of applying the resin varnish according to the present invention to the carrier film, and (2) the step of removing the solvent in the varnish are included.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The filler according to the present invention is obtained by treating the surface of barium titanate powder particles with a silane coupling agent having a primary amino group. By such surface treatment, the amount of the filler compounded in the resin composition can be increased. In addition, in a resin system in which a polyol is cured with diisocyanate, the action of barium titanate causes gelation in 1 to 2 hours.
By coating the surface of the barium titanate particles, gelation is suppressed even for 7 days or longer, and the life (storage period) of the resin composition can be dramatically increased.

The barium titanate used is a liquid phase method,
It may be produced by any method such as a solid phase method and an alkoxide method, and its crystal structure is not particularly limited. Regarding the shape of the filler, any shape such as granular shape, amorphous shape, and flake shape can be used in any combination. Further, it is preferable to use one having a uniform particle size distribution, and the particle size (average particle size) thereof is preferably about 0.1 to 20 μm, and more preferably about 0.5 to 10 μm.

The silane coupling agent having a primary amino group is a silane coupling agent having a primary amino group at the terminal, specifically, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (Aminoethyl) -γ-aminopropyltrimethoxysilane, N-
β- (aminoethyl) -γ-aminopropyltriethoxysilane and the like can be mentioned. These may be used alone or in combination of two or more.

This filler is preferably produced by a method in which a silane coupling agent having a primary amino group is dispersed or dissolved in an organic solvent and a barium titanate powder is brought into contact with the treatment solution. can do. As the organic solvent (dispersion medium) used to disperse or dissolve the silane coupling agent, for example, methyl ethyl ketone, methyl isobutyl ketone and the like can be preferably used from the viewpoint of the drying rate. The silane coupling agent having a primary amino group is dissolved or dispersed in an organic solvent in an amount of about 1.5 to 3 times the amount required to cover the entire surface of the barium titanate powder from the viewpoint of coating efficiency. Preferably.

The method of contacting the silane coupling agent having a primary amino group with the barium titanate powder particles is not particularly limited, and the filler is put into the treatment liquid, stirred, and then filtered to remove the filler. Examples thereof include a method of drying and a method of drying the filler after spraying or pouring the treatment liquid on the filler. Regarding the temperature and time at that time, from the viewpoint of cost and safety, the temperature is from room temperature to the boiling point of the solvent, 3
It is preferably about 0 minutes to 8 hours. Also, stirring
A propeller stirrer, a kneader, a mixer, a bead mill, a shaker, etc. can be used for mixing.

The above contact treatment is preferably carried out in the presence of an organic acid. This is because the processing time can be significantly shortened. Examples of the organic acid include p-toluenesulfonic acid, salicylic acid, phenol, cresol, acetic acid and the like. Among them, p-toluenesulfonic acid is preferably used from the viewpoint of activity and safety. The organic acid is preferably one that dissolves in the dispersion medium, and a combination of the two is preferably selected from the viewpoint of solubility. The blending amount of these organic acids is 100 silane coupling agent having a primary amino group.
It is preferably 10 to 20 parts by weight with respect to parts by weight.

By carrying out the treatment in the presence of an organic acid as described above, the surface of another filler according to the present invention, that is, barium titanate powder particles, is treated in the presence of an organic acid with a primary amino group. It is possible to obtain a filler that is treated with a silane coupling agent having a group.

Next, the resin composition according to the present invention contains a resin (base resin) and the above-mentioned filler of the present invention. As the resin, one or more kinds of suitable thermosetting resins or thermoplastic resins can be used depending on the use of the composition, and among them, thermosetting resins can be preferably used. Specifically, a thermosetting resin that has been conventionally used by impregnating a glass cloth base material is preferable, and examples thereof include epoxy resin, bistriazine resin, polyimide resin, phenol resin, melamine resin, silicon resin, unsaturated polyester. Resins, cyanate ester resins, isocyanate resins, or modified resins thereof can be used. Above all, in improving the characteristics of the laminated plate,
In particular, epoxy resin, polyimide resin, or bistriazine resin is suitable.

Further, any epoxy resin may be used as long as it has an epoxy group in its molecule, such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type. Epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, salicylaldehyde novolac type epoxy resin, bisphenol F novolac type epoxy resin, alicyclic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoin type Epoxy resin, isocyanurate type epoxy resin,
1 selected from aliphatic cyclic epoxy resins, and their alkyl substitution products, halides, hydrogenated products, etc.
More than one can be used. Among them, bisphenol A novolac type epoxy resin and salicylaldehyde novolac type epoxy resin are preferable because they have excellent heat resistance.

As the curing agent for such a resin, those conventionally used for each resin can be used. When the resin is an epoxy resin, for example, one or more of dicyandiamide, bisphenol A, bisphenol F, polyvinyl phenol, novolac resin, bisphenol A novolac resin, and halides of these phenol resins can be used. Among them, bisphenol A novolac resin is preferable because it has excellent heat resistance.

The compounding amount of the curing agent is not particularly limited as long as the curing reaction can proceed. For example, in the case of an epoxy resin, it can be used preferably in the range of 0.01 to 5.0 equivalents, particularly preferably in the range of 0.8 to 1.2 equivalents, based on 1 mol of the epoxy group. A range of 2 to 100 parts by weight is preferable with respect to 100 parts by weight, and further, a range of 2 to 5 parts by weight is preferable for dicyandiamide and a range of 30 to 80 parts by weight is preferable for other curing agents.

Further, a curing accelerator can be used in the resin composition, and when the resin is an epoxy resin, an imidazole compound, an organic phosphorus compound, a tertiary amine, a quaternary ammonium salt or the like can be used. . The ratio of the curing accelerator to the resin may be a conventionally used ratio, preferably 0.01 to 20 parts by weight, more preferably 0.1 to 1.0 part by weight, based on 100 parts by weight of the resin. .

The curing reaction of the thermosetting resin may be carried out at any temperature as long as the reaction proceeds, but it is generally preferable to cure it at room temperature to 250 ° C. Further, this curing reaction can be performed under pressure, atmospheric pressure or reduced pressure.

As the thermoplastic resin, polyethylene, polypropylene, polyolefin resin such as 4-methylpentene-1 resin, polybutene-1 resin and high-pressure ethylene copolymer, styrene resin, polyvinyl chloride,
Polyvinylidene chloride, polyvinyl alcohol, polyacrylonitrile, polyacrylic acid-based plastic, diene-based plastic, polyamide, polyester, polycarbonate, polyacetal, fluororesin, polyurethane-based plastic, and polystyrene-based thermoplastic elastomer, polyolefin-based thermoplastic elastomer,
Examples include polyurethane-based thermoplastic elastomers,
These may be used alone or in combination of two or more.

The blending amount of the filler of the present invention with respect to the resin is
It may be appropriately set depending on the required dielectric constant, but from the viewpoint of moldability and the like, 100 to 10 parts by weight of the resin is used.
It is preferably contained in an amount of 00 parts, and more preferably in the range of 200 to 500 parts by weight. As described above, in the present invention, it is possible to mix a large amount of high-dielectric-constant filler about twice or more as compared with the conventional one, and to give a desired high to low dielectric constant to the obtained resin layer. You can For example, in the case of using each of large-capacity, medium-capacity, and small-capacity capacitors, the relative permittivity of the resin composition after curing is preferably 50, 20, 10 (normal temperature, 1 MHz) or higher, respectively. .

In a preferred embodiment, this resin composition may contain other optional components (additives). Further, the additional component is a filler other than the filler of the present invention, for example, barium titanate not surface-treated, high dielectric constant filler other than barium titanate (strontium titanate, calcium titanate, Lead titanate, barium zirconate, calcium zirconate, barium stannate, calcium stannate, etc., or fillers that do not have a high dielectric constant (silica, alumina, titanium dioxide,
Zirconia, mullite, cordierite, magnesia, clay, talc, barium sulfate, etc.).

As other components, for example, a coupling agent may be blended in order to improve the interfacial bonding between different materials, particularly with a copper foil. A silane coupling agent is preferable as the coupling agent. Such silane coupling agents include γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ
-Ureidopropyltriethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane and the like can be used. The amount of the coupling agent blended is preferably 0.05 to 10 parts by weight, and more preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the resin.

When the resin composition of the present invention is used as a prepreg, a ceramic type whisker can be added. Such a ceramic whisker preferably has an elastic modulus of 200 GPa or more from the viewpoint of providing sufficient rigidity when used as a wiring board material or a wiring board. For example, one or more selected from aluminum borate, wollastonite, potassium titanate, basic magnesium sulfate, silicon nitride, and α-alumina can be used.

Further, the resin composition may optionally contain an appropriate amount of commonly used additives such as a catalyst, an elastomer, a flame retardant, a release agent, an adhesiveness-imparting agent, a stress relaxation agent and a coloring agent. An ion scavenger may be blended in order to improve the insulation reliability when absorbing moisture.

The resin composition is prepared by adding a solvent as described below to the above components when the resin is not in a liquid state,
It can be prepared by uniformly mixing with a mixer or the like by a known method. All of the various components may be added at the same time, but the order of addition may be appropriately set, and if necessary, some of the components may be pre-kneaded in advance.

Next, the resin varnish of the present invention contains the above resin composition and a solvent. This solvent can be appropriately selected according to the type of resin and the use of the composition. For example, acetone, methyl ethyl ketone, toluene, xylene, methyl isobutylene, ethyl acetate, ethylene glycol monomethyl ether, methanol, ethanol, N, N-dimethylformamide, N, N-dimethylacetamide and the like can be used alone or in combination of two or more. The resin varnish can be produced by adding a filler to a varnish composed of a resin and a solvent, and an optional additive as necessary, mixing and stirring by an arbitrary method, and uniformly dispersing the filler and the like in the varnish. .

The ratio of this solvent to the resin composition can be appropriately set according to the type of resin, the blending amount of the filler, the coating method and the like. From the viewpoint of moldability and workability, the resin composition 100 is used. The range of 40 to 900 parts by weight is preferable, and the range of 100 to 600 parts by weight is more preferable.

The resin film of the present invention is obtained from the resin composition of the present invention, and when the resin composition is in a liquid state, it can be formed by an arbitrary method as it is or by adding a solvent to form a resin varnish. . For example, it can be formed by applying a resin varnish (or a liquid resin composition) on one surface of a base material such as a copper foil, and removing the solvent by heating and drying. The coating method of varnish can be such as blade coater, rod coater, knife coater, squeeze coater, reverse roll coater, transfer roll coater, etc., in which a shearing force can be applied in a plane direction parallel to the base material, or a vertical direction to the base material A coating method that can apply a compressive force in any direction can be adopted. Drying is 2 to 30 at about 130 to 150 ° C.
It is preferable to carry out the treatment for about a minute so that the thermosetting resin is in a semi-cured state without stickiness.

When a resin film is used as a prepreg, a resin varnish is impregnated into a commonly used base material such as glass cloth or paper, and the solvent is volatilized by drying the resin varnish and the resin is cured to a certain extent to obtain a B stage state. (Semi-cured state in which resin is melted and softened by pressing) is preferable.

Next, electronic parts using the resin composition or resin varnish of the present invention will be described with reference to the drawings. FIG. 1 is a sectional view schematically showing an embodiment of a wiring board according to the present invention. The wiring board (1) includes an insulating layer or a first insulating layer (11) and a wiring conductor or a first wiring conductor (21), and the insulating layer (11) is a resin.
The resin composition of the present invention comprises a barium titanate powder particle having a surface treated with a silane coupling agent having a primary amino group. Although not shown in the drawing, the wiring conductor (21) may be formed on both surfaces of the insulating layer (11).

FIG. 2 is a sectional view schematically showing another embodiment of the wiring board according to the present invention. The wiring board (2) is a multilayer wiring board including a first insulating layer (11), a first wiring conductor (21), a second insulating layer (12), and a second wiring conductor (22). Insulating layer (11) and second insulating layer (12)
At least one of them is composed of the above-mentioned resin composition of the present invention. Although not shown in the figure, further insulating layers such as third, fourth, fifth, etc. and wiring conductors may be alternately laminated.

In the case of a multilayer wiring board, at least any one of the insulating layers may be composed of the resin composition of the present invention, and the present invention having various dielectric constants for a plurality of layers. The resin composition of can also be used. On the other hand, in the resin layer corresponding to the circuit portion, a resin having a low dielectric constant, such as polyphenylene oxide resin, polybutadiene resin,
It is also possible to use a fluororesin or the like to form a high-density mounted multilayer board.

The manufacture of the wiring board includes a step of forming the first insulating layer (11) and a step of forming the first wiring conductor (21) on at least one surface of the first insulating layer (11). In the case of a multi-layer delivery board, the step of forming the second insulating layer (12) on the first wiring conductor (21) and the second insulating layer (1).
2) and the step of forming the second wiring conductor (22). The insulating layer can be formed by any known method, and a resin varnish may be applied and dried, or a resin film may be laminated and pressed.

As the wiring conductor, any conductor such as copper, silver, gold, aluminum, chromium, tungsten and molybdenum can be used. These can be used as a metal foil or can be formed on an insulating layer by vapor deposition, plating, etc., an inner layer circuit is formed by a subtractive method or an additive method, and interconnected by through holes, and each is wired. It can function as a layer, a ground layer, and a power layer. The wiring structure may be single-sided wiring, double-sided wiring, or multilayer wiring, and can be selected as necessary. The wiring board may be used for mounting a semiconductor package, or may be used as a mounting board for a semiconductor chip in a semiconductor package.

FIG. 3 is a sectional view schematically showing an embodiment of a semiconductor package according to the present invention. The semiconductor package (3) comprises a semiconductor mounting substrate (10) and a semiconductor chip (30) mounted on the semiconductor mounting substrate (10) sealed with a sealing resin (40). here,
Whether the semiconductor mounting substrate (10) is a wiring board using the resin composition according to the present invention (that is, a wiring board according to the present invention),
Alternatively, the sealing resin (40) is configured to be the resin composition according to the present invention. Alternatively, it is also preferable that both the semiconductor mounting substrate (10) and the sealing resin (40) use the resin composition of the present invention. The semiconductor chip may be a semiconductor chip of an individual device or a semiconductor chip as a monolithic IC. In the latter case, a semiconductor chip having a passive element and an active element mounted thereon can be used.

The semiconductor package manufacturing method includes a step of mounting a semiconductor chip on a semiconductor mounting substrate, and a step of encapsulating a sealing resin (resin composition of the present invention) to seal the substrate and the semiconductor chip. , Is included. When a resin varnish is used as the sealing resin, the step of mounting the semiconductor chip on the semiconductor mounting substrate and the sealing resin varnish (the resin varnish of the present invention) are sealed to seal the substrate and the semiconductor chip. And a step of removing the solvent in the varnish. Each step can be performed by a conventionally known method. The transfer molding method is the most general method for sealing the element, but the injection molding method,
A compression molding method or the like may be used. The molding conditions can be appropriately set according to the application, but it is preferable that the molding temperature is 160 to 220 ° C., the molding pressure is 2 to 12 MPa, and the molding time is 1 to 10 minutes.

FIG. 4 is a sectional view schematically showing an embodiment of a wiring board for mounting a semiconductor package according to the present invention.
The semiconductor package mounting wiring board (4) is obtained by mounting the semiconductor package (3) on the wiring board (2),
At least one of the wiring board and the semiconductor package is the wiring board according to the present invention or the semiconductor package according to the present invention. Although a multilayer wiring board is shown in the figure, a single-layer wiring board may be used.

FIG. 5 is a sectional view schematically showing an embodiment of a wiring board material according to the present invention. The wiring board material (5) includes a carrier film (50) and a resin layer (11) made of the resin composition according to the present invention. As the wiring board material, the resin composition of the present invention may be applied to a carrier film, or the resin film of the present invention may be laminated and pressed. When the resin varnish of the present invention is used, it includes a step of applying the resin varnish to the carrier film and a step of removing the solvent in the varnish. Each step can be performed by a conventionally known method.

In addition to the above description, the resin composition of the present invention can be used as a single electronic component such as a film capacitor, LCR, filter and oscillator.

[0050]

EXAMPLES In the following examples, "part" means "part by weight".
Represents [Examples 1 to 5 and Comparative Examples 1 to 9] 1. Surface Treatment of Barium Titanate Powder Particles Barium titanate powder particles were surface-treated using the components shown in Table 1 to produce fillers A to F. Filler A,
E and F, each component is 60 ℃ using a propeller stirrer
The mixture was stirred for 8 hours, washed with methyl ethyl ketone three times, and dried. Each of the fillers B to D was stirred at room temperature for 1 hour using a propeller stirrer, washed three times with methyl ethyl ketone, and then dried. In addition, untreated barium titanate powder was used as the filler G.

The compounds in the table are as follows. BT-100M: barium titanate powder (Fujititanium Co., Ltd., average particle size: 1.5 μm) / MEK: methyl ethyl ketone / A-1100: γ-aminopropyltriethoxysilane (Nippon Unicar Co., Ltd.) / A-9669 : N
-Phenyl-γ-aminopropyltrimethoxysilane (Nippon Unicar Co., Ltd.) / A-187: γ-glycidoxypropyltrimethoxysilane (Nippon Unicar Co., Ltd.)
/ KR-TTS: Iropropyltriisostearoyl titanate (Ajinomoto Co., Inc.) / AL-M: acetoalkoxyaluminum diisopropylate (Ajinomoto Co., Inc.) /
p-TSA: p-toluenesulfonic acid

[0052]

[Table 1]

2. Evaluation of coating effect of surface treatment Resin varnish A for evaluating coating effect of surface treatment
As a phenoxy resin (YP-5 manufactured by Tohto Kasei Co., Ltd.)
0) A mixture of 100 parts by weight, 15 parts by weight of masked isocyanate (a compound of isophorone diisocyanate and a phenol novolac resin) and 173 parts by weight of a solvent (N, N-dimethylacetamide) was used. Barium titanate (untreated surface) accelerates the dissociation reaction of masked isocyanate, and the resulting isophorone diisocyanate and the phenoxy resin undergo a crosslinking reaction, so that the resin composition gels at room temperature for about 2 hours. Therefore, the coating effect of the surface treatment of the barium titanate powder can be evaluated by measuring the viscosity increase of the resin composition.

Each of the fillers A to G having the composition shown in Table 2 was mixed with the resin varnish A, and using a bead mill, 500 ml of alumina container, 150 ml of alumina beads, sample 15
The resin compositions of Examples 1 and 2 and Comparative Examples 1 to 5 were obtained by mixing at 0 ml and 1000 rpm for 1 hour at room temperature. The obtained resin composition was measured for viscosity at 25 ° C. immediately after mixing, after being left at room temperature for 1 day and after being left at room temperature for 5 days with a B-type viscometer. The results are also shown in Table 2.

[0055]

[Table 2]

In each of the compositions of Examples, the increase in viscosity after standing was small, and it was as good as 120% after 5 days.
On the other hand, it was found that the composition of Comparative Example had a problem in practical use because the composition had a remarkable increase in viscosity and had a short life (storage period). In particular, the compositions using the filler F treated with the aluminum-based coupling agent and the filler G not subjected to the surface treatment (Comparative Examples 4 and 5) were gelated after 2 hours.

3. Preparation of resin composition As resin varnish B, phenoxy resin (Toto Kasei Co., Ltd.)
YP-50 manufactured by Sumitomo Chemical Co., Ltd., mask isocyanate (compound of isophorone diisocyanate and phenol novolac resin) 15 parts by weight, epoxy resin (YD8125 manufactured by Toto Kasei Co., Ltd.) 24 parts by weight, epoxy resin (ESCN195 manufactured by Sumitomo Chemical Co., Ltd.) ) 12 parts by weight and a solvent (N, N-dimethylacetamide) 173 parts by weight. 100 parts by weight of this resin varnish B was mixed with the fillers B, C and E in the proportions shown in Table 3 and mixed in the same manner as described above, and the resin compositions of Examples 3 to 5 and Comparative Examples 6 to 9 were mixed. Got

The resin composition thus obtained was dried on a polyethylene terephthalate release film to give a film thickness of 200.
Apply using an applicator so that
It was dried in a drying oven at 0 ° C. for 10 minutes. The surface of the obtained coating film was visually observed to evaluate the separated state of the resin and the filler. Furthermore, the minimum melt viscosity of the obtained coating film at 150 ° C.
Measured using an I-cone plate viscometer, 100 Pa
The moldability of less than s was regarded as good, and the moldability of 100 Pa · s or more was regarded as poor. In addition, the relative dielectric constant of 1 MHz of the coating film is measured by an LCR meter (HP manufactured by Agilent Technology Co., Ltd.).
4275A). The results are shown together in Table 3.

[0059]

[Table 3]

As is clear from Examples 3 to 5, even when 184 parts by weight of the filler B of the present invention was blended, both dispersibility and moldability were good. On the other hand, as seen in Comparative Examples 6 to 9, the filler C could be blended up to 128 parts by weight, and the filler E could be blended up to 92 parts by weight, and a coating film having a high dielectric constant could not be obtained. As described above, in the examples containing the filler of the present invention, the filler was uniformly dispersed in the coating film, the appearance was good, and the moldability was good even if a large amount of the filler was blended, which was excellent. Dispersibility was shown. As a result, a coating film having a high dielectric constant could be obtained. On the other hand, in the comparative example not containing the filler of the present invention, the resin and the filler were separated in the coating film, and when mixed in a large amount, the fluidity was deteriorated and molding failure was caused.

[0061]

The filler of the present invention is one in which the surface of barium titanate powder particles is treated with a silane coupling agent having a primary amino group, so that aggregation in the resin composition is suppressed. Excellent dispersibility. Therefore,
It is possible to obtain a resin composition containing this filler in a larger amount and more uniformly than in the conventional case, and to provide an insulating resin layer having a desired high dielectric constant. It can be used as a semiconductor package or the like to provide a compact and high-density electronic component having excellent functionality.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an embodiment of a wiring board of the present invention.

FIG. 2 is a sectional view showing another embodiment of the wiring board of the present invention.

FIG. 3 is a sectional view showing an embodiment of a semiconductor package of the present invention.

FIG. 4 is a cross-sectional view showing one embodiment of a wiring board for mounting a semiconductor package of the present invention.

FIG. 5 is a cross-sectional view showing an embodiment of a wiring board material of the present invention.

[Explanation of symbols]

1 wiring board 2 wiring board 11 insulating layer 21 wiring conductor 3 Semiconductor package 4 Semiconductor package mounted wiring board 5 Materials for wiring boards

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 101/00 C08L 101/00 4M109 C09C 3/08 C09C 3/08 5E346 3/12 3/12 C09D 7 / 12 C09D 7/12 201/00 201/00 H01L 23/29 H05K 1/03 610R 23/31 3/46 T H05K 1/03 610 H01L 23/30 R 3/46 (72) Inventor Yasushi Shimada Ibaraki Shimodate City Oita 1500 Ogawa Hitachi Chemical Co., Ltd. Research Institute (72) Inventor Kazuhisa Otsuka Ibaraki Prefecture Shimodate City Ogawa 1500 Ogawa Hitachi Research Institute Research Institute (72) Inventor Yoshiki Hirata Ibaraki Shimodate City Ogawa 1500, Hitachi Chemical Co., Ltd. Research Institute (72) Inventor, Kazunori Yamamoto 1500 Ogawa, Shimodate, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Institute within the F-term (reference) 4F006 AA35 AB32 AB34 AB74 BA06 CA08 DA04 4F071 AA02 AA03 AA12 AA14 AA21 AA22 AA24 AA25 AA26 AA29 AA31 AA34 AA40 AA41 AA42 AA43 AA49 AA50 AA53 AA54 AA58 AA60 AB20 AC16 AE22 AH13 BA03 BB02 BC01 BC02 4J002 AC021 BB031 BB121 BB171 BC021 BD041 BD101 BD121 BE021 BG001 BG101 CB001 CC031 CC181 CD021 CD051 CD061 CD081 CD131 CD141 CF001 CF211 CG001 CK021 CL001 CM021 CM041 CP031 DE186 KA08 MA06 LA06 EA08 EA08 EA06 EA15 EA15 EA15 EA15 EA15 EA23 CB15 FF15 FF21 CB15 FF15 FF15 CB206 CB206 CB206 CB23 NA25 NA26 PB09 PC02 4M109 AA01 EA01 EB06 EB11 EB18 5E346 AA12 AA15 BB01 CC08 CC16 DD01 EE31 GG02 HH01

Claims (22)

[Claims] 1. A filler obtained by treating the surface of barium titanate powder particles with a silane coupling agent having a primary amino group. 2. A filler obtained by treating the surface of barium titanate powder particles with a silane coupling agent having a primary amino group in the presence of an organic acid. 3. The filler according to claim 2, wherein the organic acid is p-toluenesulfonic acid. 4. A method for producing a surface-treated filler, which comprises contacting a treatment liquid obtained by dispersing or dissolving a silane coupling agent having a primary amino group in an organic solvent with barium titanate powder, A method of manufacturing a filler to be treated. 5. The method for producing a filler according to claim 4, wherein the treatment liquid and the barium titanate powder are contacted with each other in the presence of an organic acid. 6. The method for producing a filler according to claim 5, wherein the organic acid is p-toluenesulfonic acid. 7. A resin composition comprising a resin and a filler obtained by treating the surface of barium titanate powder particles with a silane coupling agent having a primary amino group. 8. The resin composition according to claim 7, wherein the filler is contained in an amount of 100 to 1000 parts by weight based on 100 parts by weight of the resin. 9. A resin varnish containing a resin, a filler obtained by treating the surface of barium titanate powder particles with a silane coupling agent having a primary amino group, and a solvent. 10. The resin varnish according to claim 9, wherein the solvent is contained in an amount of 40 to 900 parts by weight with respect to a total of 100 parts by weight of the resin and the filler. 11. A resin film comprising a resin composition comprising a resin and a filler obtained by treating the surface of barium titanate powder particles with a silane coupling agent having a primary amino group. 12. A wiring board comprising an insulating layer and a wiring conductor, wherein the insulating layer is a resin and the surface of barium titanate powder particles is treated with a silane coupling agent having a primary amino group. A wiring board comprising a resin composition containing an agent. 13. A step of forming a first insulating layer comprising a resin composition comprising a resin and a filler obtained by treating the surface of barium titanate powder particles with a silane coupling agent having a primary amino group. And a step of forming a first wiring conductor on the first insulating layer. 14. The method for manufacturing a wiring board according to claim 13, further comprising: a step of forming a second insulating layer on the first wiring conductor; and a step of forming a second wiring conductor on the second insulating layer. . 15. A semiconductor package comprising a semiconductor mounting substrate and a semiconductor chip mounted on the semiconductor mounting substrate sealed with a sealing resin, the semiconductor mounting substrate including an insulating layer and wiring. A semiconductor package comprising a conductor, and a resin composition in which the insulating layer comprises a resin and a filler obtained by treating the surface of barium titanate powder particles with a silane coupling agent having a primary amino group. . 16. A semiconductor package in which a semiconductor mounting substrate and a semiconductor chip mounted on the semiconductor mounting substrate are sealed with a sealing resin, wherein the sealing resin is a resin and titanium. A semiconductor package, which is a resin composition containing a filler obtained by treating the surface of barium acid powder particles with a silane coupling agent having a primary amino group. 17. A resin comprising a step of mounting a semiconductor chip on a semiconductor mounting substrate, a resin, and a filler obtained by treating the surface of barium titanate powder particles with a silane coupling agent having a primary amino group. A method of manufacturing a semiconductor package, comprising a step of sealing the semiconductor mounting substrate and a semiconductor chip with a composition. 18. A step of mounting a semiconductor chip on a semiconductor mounting substrate, a resin, a filler obtained by treating the surface of barium titanate powder particles with a silane coupling agent having a primary amino group, and a solvent. A method of manufacturing a semiconductor package, comprising: a step of sealing the semiconductor mounting substrate and a semiconductor chip with a resin varnish containing: and a step of removing the solvent. 19. A semiconductor-package-mounted wiring board comprising a semiconductor package mounted on the wiring board according to claim 12. 20. A semiconductor package mounting wiring board comprising the semiconductor package according to claim 15 mounted on a wiring board. 21. A wiring board material comprising a resin layer and a carrier film, wherein the resin layer is treated with a resin and the surface of barium titanate powder particles is treated with a silane coupling agent having a primary amino group. A wiring board material comprising a resin composition containing a filler. 22. A resin for a carrier film, and a filler obtained by treating the surface of barium titanate powder particles with a silane coupling agent having a primary amino group,
A method of manufacturing a wiring board material, comprising: a step of applying a resin varnish containing a solvent; and a step of removing the solvent.