JP6286820B2 - Prepreg, laminated board, multilayer printed wiring board, and semiconductor device - Google Patents

Description

  The present invention relates to a prepreg, a laminated board, a multilayer printed wiring board, and a semiconductor device.

Conventionally, a prepreg using a resin composition containing a filler (filler) such as calcium carbonate or talc has been used. For example, Patent Document 1 discloses a prepreg using a resin composition containing about 15% by mass of a glass filler.
In such a prepreg, since the filler content is low, the strength of the prepreg may be insufficient.

  Therefore, as shown in Patent Document 2, a prepreg using a resin composition having a relatively high filler content has been developed.

JP-A-5-222221 JP 2010-254819 A

However, it has been found that when a resin composition having a high filler content is used, an appearance abnormality is likely to occur when heat-press molding.
As a result of intensive studies by the present inventors, it was speculated that the appearance abnormality was caused by the following.
When hot pressing is performed, the filler and the resin move separately due to the difference in fluidity. And only a resin component flows along a fiber base material, the trace of this flow becomes a streak shape, and it becomes an appearance abnormality (molding stripe).

The present invention has been developed based on the above findings.
According to the present invention, a prepreg comprising a fiber base material and a thermosetting resin composition containing a filler, wherein the fiber base material is a glass cloth, a yarn bundle width A of the glass cloth, and a yarn The flatness, which is the ratio B / A to the bundle thickness B, is 0.07 or less, the content of the filler in the thermosetting resin composition is 35% by mass or more and 80% by mass or less, and JIS In accordance with Z 8741, a prepreg having a surface gloss of 30 or more measured at an incident angle of 60 ° is provided.

As described above, since the molding stripe is considered to be generated when the resin component and the filler flow separately, the present inventors make the familiarity between the filler and the resin component good. Therefore, it was thought that the generation of molding streaks could be prevented. And it discovered that the familiarity of a filler and a resin component and the glossiness of the surface of a prepreg were related, and the prepreg whose glossiness was more than a fixed value discovered that a molding stripe was hard to generate | occur | produce.
In the present invention, since it is a prepreg having a glossiness of 30 or more, generation of molding lines can be suppressed.

Furthermore, according to this invention, the laminated board which has the prepreg mentioned above and the metal layer provided on this prepreg can also be provided.
In addition, a multilayer printed wiring board having the laminated board, a semiconductor device having a multilayer printed wiring board, and a semiconductor element provided on the multilayer printed wiring board can also be provided.

  ADVANTAGE OF THE INVENTION According to this invention, the prepreg which can suppress the external appearance abnormality which generate | occur | produces when shape | molding, a laminated board, a multilayer printed wiring board, and a semiconductor device are provided.

  The above-described object and other objects, features, and advantages will become more apparent from the preferred embodiments described below and the accompanying drawings.

(A) is sectional drawing of a prepreg, (B) is a top view of a fiber base material. It is sectional drawing of the prepreg in a comparative example. (A) is a figure which shows the surface of the prepreg in Example 1, (B) is a figure which shows the surface of the prepreg in the comparative example 1.

Hereinafter, embodiments of the present invention will be described.
The prepreg of the present embodiment is a prepreg including a fiber base material and a thermosetting resin composition containing a filler, and the content of the filler in the thermosetting resin composition is 35% by mass or more. The glossiness of the surface measured at an incident angle of 60 ° in accordance with JIS Z 8741 is 30 or more.

  The fiber base material of the prepreg is not particularly limited, but glass fiber base materials (glass cloth) such as glass woven fabric and glass nonwoven fabric, polyamide resins such as polyamide resin fibers, aromatic polyamide resin fibers and wholly aromatic polyamide resin fibers Synthesis composed of woven or non-woven fabric mainly composed of resin fiber, polyester resin fiber, aromatic polyester resin fiber, polyester resin fiber such as wholly aromatic polyester resin fiber, polyimide resin fiber or fluororesin fiber Examples thereof include organic fiber base materials such as fiber base materials, kraft paper, cotton linter paper, or paper base materials mainly composed of linter and kraft pulp mixed paper. Any of these can be used. Among these, glass cloth is preferable. Thereby, a prepreg having low water absorption, high strength, and low thermal expansion can be obtained.

Examples of the glass constituting the glass cloth include E glass, C glass, A glass, S glass, D glass, NE glass, T glass, H glass, UT glass, L glass, and quartz glass. Among these, Any one or more of them can be used. Among these, any of E glass, T glass, S glass, NE glass, UT glass, L glass, and quartz glass is preferable. Thereby, the high elasticity of a prepreg can be achieved and the thermal expansion coefficient of a prepreg can be reduced.
When the fiber substrate is a glass cloth, it is preferable that the flatness ratio, which is the ratio B / A of the yarn bundle width A and the yarn bundle thickness B, is 0.07 or less.
By setting the flatness ratio to 0.07 or less, the glass fiber can be flattened, and a prepreg excellent in surface smoothness can be obtained. Moreover, it is preferable that the lower limit of an aspect ratio is 0.03 or more from a viewpoint of manufacturability.
Here, B / A calculates the average value of the three bundle yarns for each of the yarn bundle width and the yarn bundle thickness of the yarn constituting the glass cloth, and the average yarn bundle width A and the average yarn bundle thickness B The ratio B / A is obtained.

Furthermore, when the fiber substrate is a glass cloth, the weaving density is preferably 40 warps / 25 mm or more and 40 wefts / 25 mm or more. By using such a prepreg, a high-strength prepreg can be obtained.
The upper limit of the weaving density of the warp and weft is not particularly limited, but is preferably 110 pieces / 25 mm or less in consideration of the flatness. This depends on the yarn, but if the weaving density is too high, it tends to be difficult to open. That is, the upper limit of the flatness cannot be satisfied, and the surface smoothness of the prepreg is impaired. Especially, it is preferable that they are 50 warp / 25 mm or more and 50 weft / 25 mm or more.
Further, the ratio between the weaving density of the warp and the weaving density of the weft is not particularly limited, but from the viewpoint of the dimensional stability of the substrate, the weft weaving density / warp weaving density is preferably 0.90 to 1.10. .
The thickness of the fiber substrate is, for example, 10 μm or more and 140 μm or less, preferably 100 μm or less.

The thermosetting resin composition includes (A) a thermosetting resin and (B) a filler.
Although it does not specifically limit as a thermosetting resin, For example, an epoxy resin, a melamine resin, a urea resin, cyanate resin etc. are mention | raise | lifted. And one or more of these can be used. Among these, an epoxy resin or a cyanate resin is preferable.
Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol E type epoxy resin, bisphenol M type epoxy resin, bisphenol P type epoxy resin, and bisphenol Z type epoxy resin. Bisphenol type epoxy resin, phenol novolak type epoxy resin, novolac type epoxy resin such as cresol novolak type epoxy resin, biphenyl type epoxy resin, arylalkylene type epoxy resin such as phenol aralkyl type epoxy resin having biphenylene skeleton, naphthalene type epoxy resin, Anthracene type epoxy resin, phenoxy type epoxy resin, dicyclopentadiene type epoxy resin, norbornene type epoxy resin, adamant Emission type epoxy resins, such as epoxy resins and fluorene type epoxy resins. One of these can be used alone, or two or more can be used in combination.
Although it does not specifically limit as a kind of cyanate resin, For example, bisphenol-type cyanate resin, such as a novolak-type cyanate resin, a bisphenol A-type cyanate resin, a bisphenol E-type cyanate resin, a tetramethylbisphenol F-type cyanate resin, etc. can be mentioned. Among these, phenol novolac type cyanate resin is preferable from the viewpoint of low thermal expansion. Furthermore, other cyanate resins may be used alone or in combination of two or more, and are not particularly limited.

  (A) Although content of a thermosetting resin is not specifically limited, It is preferable that they are 15 mass% or more and 65 mass% or less of the whole thermosetting resin composition. More preferably, it is 18 mass% or more and 60 mass% or less. In addition, it is preferable to use a liquid epoxy resin such as a liquid bisphenol A type epoxy resin or a bisphenol F type epoxy resin because the impregnation property to the fiber base material can be improved. Moreover, when solid bisphenol A type epoxy resin and bisphenol F type epoxy resin are used in combination, adhesion to the conductor can be improved.

(B) The filler may be either an inorganic filler or an organic filler.
Examples of inorganic fillers include silicates such as talc, calcined clay, unfired clay, mica and glass, oxides such as titanium oxide, alumina, silica and fused silica, calcium carbonate, magnesium carbonate and hydrotalcite. Hydroxides such as carbonates, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, sulfates or sulfites such as barium sulfate, calcium sulfate, calcium sulfite, zinc borate, barium metaborate, aluminum borate, boric acid Examples thereof include borates such as calcium and sodium borate, nitrides such as aluminum nitride, boron nitride, silicon nitride, and carbon nitride, and titanates such as strontium titanate and barium titanate. One of these can be used alone, or two or more can be used in combination.

  Among these, silica is particularly preferable, and fused silica (especially spherical fused silica) is preferable in terms of excellent low thermal expansion. Its shape is crushed and spherical, but in order to reduce the melt viscosity of the thermosetting resin composition in order to ensure the impregnation of the fiber base material, there is a usage method that suits its purpose, such as using spherical silica. Adopted.

The average particle diameter of the inorganic filler is not particularly limited, but is preferably 0.01 μm or more and 5 μm or less, and particularly preferably 0.5 μm or more and 2 μm or less. By setting the particle size of the inorganic filler to 0.01 μm or more, the varnish can have a low viscosity and the fiber base material can be satisfactorily impregnated with the thermosetting resin composition. Moreover, sedimentation of an inorganic filler etc. can be suppressed in varnish by setting it as 5 micrometers or less. This average particle diameter can be measured by, for example, a particle size distribution meter (manufactured by Shimadzu Corporation, product name: laser diffraction particle size distribution measuring device SALD series).
In a prepreg using a small inorganic filler having an average particle size of 5 μm or less, molding streaks are likely to occur due to the difference in fluidity between the resin component and the inorganic filler, but it has a glossiness of a predetermined value or higher. Appearance abnormality during heating and pressurization can be suppressed.

  Further, the inorganic filler is not particularly limited, but an inorganic filler having a monodispersed average particle diameter can be used, and an inorganic filler having a polydispersed average particle diameter can be used. Furthermore, one type or two or more types of inorganic fillers having a monodispersed and / or polydispersed average particle size may be used in combination.

Furthermore, spherical silica (especially spherical fused silica) having an average particle size of 5 μm or less is preferred, and spherical fused silica having an average particle size of 0.5 μm or more and 2 μm or less is particularly preferred. Thereby, the filling property of an inorganic filler can be improved.
On the other hand, examples of the organic filler include fluororesins and aramid resin fibers.

Content of the (B) filler in a thermosetting resin composition is 35 mass% or more and 80 mass% or less. By setting it to 35% by mass or more, the strength of the prepreg can be ensured. Moreover, heat resistance is also securable by setting it as 35 mass% or more. On the other hand, the flow characteristics required for heat-pressure molding can be ensured by setting the content to 80% by mass or less, further 76% by mass or less, and particularly 70% by mass or less.
Especially, it is preferable that content of (B) filler shall be 40 mass% or more from a viewpoint of low thermal expansion, Most preferably, it is 50 mass% or more.

  The thermosetting resin composition preferably contains (C) a coupling agent. (C) The coupling agent improves the wettability of the interface between (A) the thermosetting resin and (B) the filler, so that (A) the thermosetting resin and (B ) It is possible to fix the filler uniformly and improve the heat resistance, particularly the solder heat resistance after moisture absorption.

  (C) Any coupling agent can be used as long as it is usually used. Specifically, an epoxy silane coupling agent, a cationic silane coupling agent, an amino silane coupling agent, a titanate coupling agent, and a silicone oil type. It is preferable to use one or more coupling agents selected from coupling agents. Thereby, the wettability with the interface of (B) filler can be made high, and thereby heat resistance can be improved more.

  (C) Since the addition amount of the coupling agent depends on the specific surface area of the (B) filler, it is not particularly limited, but it is 0.05% by mass or more and 3% by mass or less with respect to 100 parts by mass of the (B) filler. Particularly preferred is 0.1% by mass or more and 2% by mass or less. By setting the content to 0.05% by mass or more, (B) the filler can be sufficiently covered, and the heat resistance can be improved. By setting it as 3 mass% or less, reaction advances favorably and it can prevent the fall of bending strength etc.

The thermosetting resin composition can further use (D) a phenolic curing agent. As the phenolic curing agent, known or commonly used phenol novolac resins, alkylphenol novolac resins, bisphenol A novolac resins, dicyclopentadiene type phenol resins, zyloc type phenol resins, terpene modified phenol resins, polyvinylphenols, etc. Can be used in combination.
(D) As for the compounding quantity of a phenol type hardening | curing agent, when an epoxy resin is contained in (A), the equivalent ratio (phenolic hydroxyl group equivalent / epoxy group equivalent) with an epoxy resin is 0.1-1.0. preferable. As a result, there remains no unreacted phenol curing agent, and the moisture absorption heat resistance is improved.

  In the thermosetting resin composition, (E) a curing catalyst may be used as necessary. (E) A well-known thing can be used as a curing catalyst. For example, organic metal salts such as zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, bisacetylacetonate cobalt (II), trisacetylacetonate cobalt (III), triethylamine, tributylamine, diazabicyclo [2,2 , 2] tertiary amines such as octane, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 2-ethyl-4-ethylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl Imidazoles such as -4-methyl-5-hydroxyimidazole and 2-phenyl-4,5-dihydroxyimidazole, triphenylphosphine, tri-p-tolylphosphine, tetraphenylphosphonium tetraphenylborate, triphenylphosphine Organic phosphorus compounds such as chlorotriphenylborane and 1,2-bis- (diphenylphosphino) ethane, phenolic compounds such as phenol, bisphenol A and nonylphenol, organic acids such as acetic acid, benzoic acid, salicylic acid and p-toluenesulfonic acid Or a mixture thereof. As the curing catalyst, one kind including these derivatives can be used alone, or two or more kinds including these derivatives can be used in combination.

  (E) Although content of a curing catalyst is not specifically limited, 0.05 mass% or more and 5 mass% or less of the whole thermosetting resin composition are preferable, and 0.2 mass% or more and 2 mass% or less are especially preferable.

  Thermosetting resin composition includes phenoxy resin, polyimide resin, polyamideimide resin, polyamide resin, polyphenylene oxide resin, polyethersulfone resin, polyester resin, polyethylene resin, polystyrene resin and other thermoplastic resins, styrene-butadiene copolymer , Polystyrene-based thermoplastic elastomers such as styrene-isoprene copolymers, thermoplastic elastomers such as polyolefin-based thermoplastic elastomers, polyamide-based elastomers, polyester-based elastomers, polybutadiene, epoxy-modified polybutadiene, acrylic-modified polybutadiene, methacryl-modified polybutadiene, etc. A diene elastomer may be used in combination. Any one or more of these can be used. Among these, heat resistant polymer resins such as phenoxy resin, polyimide resin, polyamideimide resin, polyamide resin, polyphenylene oxide resin, and polyethersulfone resin are preferable, and any one or more of them can be used. Thereby, the thickness uniformity of the prepreg is excellent, and as a wiring board, the heat resistance and the insulating property of the fine wiring are excellent. In addition, if necessary, the thermosetting resin composition includes pigments, dyes, antifoaming agents, leveling agents, ultraviolet absorbers, foaming agents, antioxidants, flame retardants, ion scavengers, and the like. These additives may be added.

Next, the manufacturing method of the above prepreg is demonstrated.
The above-described prepreg can be obtained by impregnating the fiber base material with the above-described thermosetting resin composition.
More specifically, the thermosetting resin composition is dissolved in a solvent to obtain a resin varnish.
The solvent used in the resin varnish is desirably one that dissolves the resin component in the thermosetting resin composition well, but a poor solvent may be used as long as it does not adversely affect the resin varnish. Examples of the solvent exhibiting good solubility include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene glycol, cellosolve, and carbitol. Any one or more of these can be used.

Here, after mixing the thermosetting resin composition and the solvent, the mixture is aged for a predetermined time or more while heating. For example, the resin varnish is set to 40 to 80 ° C. and stirred for 2 hours or longer, preferably 5 hours or longer and 12 hours or shorter. Alternatively, the resin varnish after being prepared at room temperature is set to 40 to 80 ° C. and left at this temperature for 2 hours or more, preferably 20 hours or more and 48 hours or less. By appropriately adjusting the temperature and aging time of the resin varnish, the above-described glossy prepreg can be obtained.
By performing aging as described above, it is speculated that the moisture adhering to the surface of the filler is removed and dispersed in the resin component, so that the familiarity between the filler and the thermosetting resin can be improved. It is considered that a prepreg having gloss can be obtained.
The resin varnish thus obtained is impregnated with a fiber base material and then dried at, for example, 90 ° C. or higher and 220 ° C. or lower to obtain a prepreg.

Examples of the method of impregnating the fiber base material with the resin varnish include a method of immersing the fiber base material in the resin varnish, a method of applying the resin varnish to the fiber base material with various coaters, and spraying the resin varnish on the fiber base material. One of the spraying methods is mentioned.
The prepreg thermosetting resin composition is a fiber base material impregnated with a resin varnish and dried, and the thermosetting resin composition film is not attached to the fiber base material. Absent. Further, the surface of the prepreg is not a surface pressed by another member. Therefore, the arithmetic average surface roughness Ra based on JIS B 0601 is 0.15 μm or more, particularly 0.20 μm or more. The upper limit value of the arithmetic average surface roughness Ra is not particularly defined, but is, for example, 2 μm or less.
The solid content of the resin varnish is not particularly limited, but the solid content of the thermosetting resin composition is preferably 20% by mass to 85% by mass, and particularly preferably 50% by mass to 75% by mass. Thereby, the impregnation property to the fiber base material of the resin varnish can further be improved. The thickness of the prepreg is preferably 20 μm or more and 100 μm or less from the viewpoint of reducing the thickness of the semiconductor device. Especially, it is preferable that the thickness of a prepreg is 60 micrometers or less. In addition, the thermosetting resin of the prepreg is in a B-stage (semi-cured) state.
In this embodiment, the resin layer comprised with the thermosetting resin composition has coat | covered the front and back of a fiber base material. For example, the thickness of the prepreg is 1.1 to 2.5 times the thickness of the fiber base material.

  The prepreg obtained as described above has a filler content of 35% by mass or more and 80% by mass or less. In such a prepreg having a high filling rate of the filler, molding stripes are likely to occur at the outer peripheral portion of the molded body after heating and pressing when performing heat molding in multilayer lamination or the like. In order to ensure the strength of the prepreg, it is necessary to add a certain amount or more of the filler. However, since a prepreg having a high filling rate of the filler is likely to cause molding streaks, it has been conventionally possible to prevent abnormal appearance and prevent prepreg. It was very difficult to achieve both strength and security. In particular, this tendency was conspicuous as the proportion of the thermosetting resin composition including the inorganic filler constituting the prepreg (hereinafter abbreviated as RC) decreases.

As a result of investigations by the present inventors, it has been found that a molding line is generated when the resin component and the filler flow separately. Therefore, if the familiarity between the filler and the resin component is good, it is considered that the generation of molding lines can be suppressed.
As a result of examining the degree of familiarity between the filler and the resin component, it was found that the degree of familiarity between the filler and the resin component is related to the glossiness of the surface of the prepreg. In the prepreg having a high glossiness on the surface of the prepreg, the filler is not exposed on the surface, and the familiarity between the filler and the resin component is good. Thus, in the prepreg having a glossiness of 30 or more with good compatibility between the resin component and the filler, it was found that the generation of molding streaks can be suppressed even when the filler content is 35% by mass or more. . Thereby, it is possible to achieve both the prevention of the appearance abnormality and the securing of the strength of the prepreg. In particular, when RC is 0.50 to 0.85 (preferably 0.55 or more), it is possible to achieve both the prevention of appearance abnormality and the securing of the strength of the prepreg.
RC is calculated | required by the formula shown below here.
(Prepreg mass-fiber base mass) / Mass of prepreg Note that the prepreg having a surface glossiness of less than 30, particularly less than 10, has a filler exposed on the surface, and the filler has repelled the resin component, The familiarity between the filler and the resin component is poor. For this reason, the resin component and the filler are easily separated and flowed when heat forming is performed, for example, in multi-layer lamination.

Among these, from the viewpoint of reliably suppressing the formation of molding lines, the glossiness of the surface measured at an incident angle of 60 ° in accordance with JIS Z 8741 is preferably 65 or more. The upper limit of the glossiness of the surface measured at an incident angle of 60 ° is not particularly limited, but is preferably 100 or less.
The incident angle is an angle formed by a line (perpendicular) orthogonal to the prepreg surface and the optical axis.
Further, it is preferable that the glossiness of the surface measured at an incident angle of 20 ° is 25 or more in accordance with JIS Z 8741. By doing in this way, generation | occurrence | production of a forming stripe can be suppressed more reliably. According to JIS Z 8741, the upper limit of the glossiness of the surface measured at an incident angle of 20 ° is not particularly limited, but is preferably 100 or less.
The glossiness can be measured using IG-331 manufactured by HORIBA.
Furthermore, the prepreg having a high glossiness as described above can improve the insulation reliability under high humidity. When the glossiness is high, it is difficult to absorb moisture, so that the insulation reliability under high humidity can be improved.

Moreover, it is preferable that the filler is not exposed to the surface of the prepreg of this embodiment. This point will be described with reference to FIGS. Reference numeral 1 denotes a prepreg of the present embodiment, reference numeral 11 denotes a fiber base material of the present embodiment, and reference numeral 12 denotes a resin layer, which is composed of the thermosetting resin composition of the present embodiment. Reference symbol F indicates the filler of the present embodiment. FIG. 1A is a cross-sectional view in a direction orthogonal to the surface of the prepreg, and FIG. 1B is a plan view of a fiber base material and shows a state where warp yarns and weft yarns intersect. Reference B indicates a basket hole. The resin layer 12 is impregnated into the fiber base material 11 and covers one surface and the other surface of the fiber base material 11. The filler F is disposed along the swell formed on the surface of the prepreg 1, but is covered with resin and is not exposed from the surface of the prepreg 1.
Here, when an arbitrary part of the prepreg surface is observed at 3.50 μm × 2.85 μm and 3500 times by SEM, 90% of the number of the observed fillers F may not be exposed. It is preferred that all observed fillers F are not exposed. Furthermore, it is preferable that the filler F is not exposed from the entire surface of the prepreg surface.
When the filler F and the resin component are compatible, the filler F is hardly exposed from the prepreg surface. Therefore, such a prepreg is unlikely to generate molding lines.
As shown in the prepreg 900 of FIG. 2, when the filler F is exposed from the surface of the prepreg, the light hitting the surface of the filler is irregularly reflected and the glossiness tends to be lowered.

The prepreg produced as described above has a storage elastic modulus at a temperature of 25 ° C. when measured at a frequency of 1 Hz after being cured at 200 ° C. for 60 minutes (heated for 60 minutes after reaching 200 ° C.). E ′ (25 ° C.) is 13 GPa or more and 50 GPa or less, and the storage elastic modulus E ′ (260 ° C.) at 260 ° C. when measured at a frequency of 1 Hz after curing at 200 ° C. for 60 minutes is 5 GPa or more. 20 GPa or less is preferable.
In order to obtain such an elastic modulus, the amount of the filler and the amount of the resin composition in the prepreg may be appropriately adjusted.
The storage elastic modulus E ′ (25 ° C.) and the storage elastic modulus E ′ (260 ° C.) are measured with a dynamic viscoelasticity measuring apparatus. The storage elastic modulus E ′ (25 ° C.) and the storage elastic modulus E ′ (260 ° C.) were each applied with a tensile load on a prepreg cured at 200 ° C. for 60 minutes, with a frequency of 1 Hz and a heating rate of 5-10 ° C./min. It is the value of the storage elastic modulus at 25 ° C. and 260 ° C. when measured from −50 ° C. to 300 ° C.

By setting the storage elastic modulus E ′ (25 ° C.) to 13 GPa or more, the strength of the prepreg can be ensured. Moreover, there exists an effect that a stress can be relieved because storage elastic modulus E '(25 degreeC) shall be 50 GPa or less.
By setting the storage elastic modulus E ′ (260 ° C.) to 5 GPa or more, it is possible to prevent warping of the prepreg during heating, for example, when performing reflow or the like. In addition, by setting the storage elastic modulus E ′ (260 ° C.) to 20 GPa or less, it is possible to relieve stress generated during heating, for example, when performing reflowing, and prevent cracks from occurring.

  A prepreg having a storage elastic modulus E ′ (25 ° C.) of 13 GPa or more and a storage elastic modulus E ′ (260 ° C.) of 5 GPa or more generally tends to have a relatively high filler amount. Then, the forming streaks occurred remarkably. When trying to obtain a storage elastic modulus of a predetermined value or more while suppressing the generation of molding lines, it is conceivable to reduce the content of the filler and the ratio of the resin composition to the fiber substrate. . However, in this case, the circuit embeddability may be deteriorated.

On the other hand, in this embodiment, since the glossiness of the surface of the prepreg is 30 or more, the filler content is 35% by mass or more, the storage elastic modulus E ′ (25 ° C.) is 13 GPa or more, and the storage elastic modulus. Even when E ′ (260 ° C.) is set to 5 GPa or more, the generation of molding streaks can be suppressed. Thereby, it is possible to achieve both prevention of appearance abnormality and high elastic modulus. Moreover, since the content of the filler can be made relatively high at 35% by mass or more, the storage elastic modulus E ′ (25 ° C.) is 13 GPa or more without reducing the ratio of the resin composition to the fiber base material. In addition, a high elastic modulus with a storage elastic modulus E ′ (260 ° C.) of 5 GPa or more can be secured.
For example, the RC of the prepreg can be as high as 0.50 to 0.85 (preferably 0.55 or more) as described above. Thereby, it can be set as the prepreg excellent in the embedding property of a circuit, and can be set as the prepreg for buildup layers.
Especially, it is preferable that storage elastic modulus E '(25 degreeC) is 15 GPa or more and 40 GPa or less. The storage elastic modulus E ′ (260 ° C.) is preferably 7 GPa or more and 16 GPa or less.

A laminate can be formed using the prepreg as described above.
A metal layer can be provided on the prepreg and heated and pressurized to cure the prepreg and obtain a laminate. It is good also as a laminated board which provided the metal layer in the outermost layer, after laminating | stacking the said multiple prepreg.
Examples of the metal layer include copper, aluminum, and stainless steel.
A multilayer printed wiring board can be obtained using the laminated board obtained as described above.
For example, the laminated plate is previously drilled or irradiated with a laser such as a carbon dioxide laser or a YAG laser to form a through hole, and further plated in the through hole to electrically connect the front and back sides. Thereafter, the metal layer of the laminated board is etched to form a circuit, thereby forming an inner circuit board (core layer).

  Next, the prepreg is disposed on the front and back surfaces of the inner circuit board, and a metal layer is disposed on the outermost layer, followed by heat and pressure molding. Thereby, hardening of a prepreg advances. Thereafter, vias are formed in the prepreg outside the inner layer circuit board, and plating is performed to electrically connect the inner layer circuit and the outermost metal layer. Further, an outer layer circuit is formed on the prepreg surface. As described above, a multilayer printed wiring board can be obtained. Thereafter, a semiconductor device can be obtained by mounting a semiconductor element on the multilayer printed wiring board.

It should be noted that the present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention.
This application claims the priority on the basis of the JP Patent application 2011-257093 for which it applied on November 25, 2011, and takes in those the indications of all here.
Hereinafter, examples of the reference form will be added.
1.
A prepreg comprising a fiber substrate and a thermosetting resin composition containing a filler,
The filler content in the thermosetting resin composition is 35% by mass or more and 80% by mass or less,
A prepreg having a surface glossiness of 30 or more measured at an incident angle of 60 ° in accordance with JIS Z 8741.
2.
1. In the prepreg described in
A prepreg obtained by impregnating the fiber base material with the varnish of the thermosetting resin composition.
3.
1. Or 2. In the prepreg described in
After curing at 200 ° C. for 60 minutes, the storage elastic modulus E ′ at 25 ° C. when measured at a frequency of 1 Hz is 13 GPa or more and 50 GPa or less, and
A prepreg having a storage elastic modulus E ′ at 260 ° C. of 5 GPa or more and 20 GPa or less when measured at a frequency of 1 Hz after being cured at 200 ° C. for 60 minutes.
4).
1. To 3. In the prepreg according to any one of
A prepreg having a thickness of 20 μm or more and 100 μm or less.
5.
1. To 4. In the prepreg according to any one of
The filler is an inorganic filler,
A prepreg having an average particle size of the inorganic filler of 5 μm or less.
6).
1. To 5. In the prepreg according to any one of
The fiber substrate is a glass cloth;
A prepreg having a flatness ratio which is a ratio B / A between the yarn bundle width A and the yarn bundle thickness B of 0.07 or less.
7).
1. To 6. In the prepreg according to any one of
The fiber substrate is a glass cloth,
A prepreg having a weaving density of 40 warps / 25 mm or more and 40 wefts / 25 mm or more.
8).
1. To 7. In the prepreg according to any one of
The said fiber base material is a glass cloth, The said glass cloth is a prepreg comprised by the glass chosen from E glass, T glass, S glass, NE glass, UT glass, L glass, and quartz glass.
9.
1. To 8. In the prepreg according to any one of
A prepreg having a value (RC) indicated by (prepreg mass−fiber substrate mass) / mass of prepreg is 0.5 or more and 0.85 or less.
10.
1. To 9. A laminate having the prepreg according to any one of the above and a metal layer provided on the prepreg.
11.
10. The multilayer printed wiring board which has a laminated board of description.
12
11. A semiconductor device comprising the multilayer printed wiring board according to 1 and a semiconductor element provided on the multilayer printed wiring board.

Next, examples of the present invention will be described.
<Manufacturing process>
Example 1
(Varnish formulation)
28 parts by mass of a phenol aralkyl type epoxy resin having a biphenylene skeleton (manufactured by Nippon Kayaku Co., Ltd., NC-3000), 12 parts by mass of a novolac type cyanate resin (manufactured by Lonza Japan Co., Ltd., PT-30), spherical fused silica (Admatex) SO-25R, average particle size 0.5 μm) 60 parts by mass, organophosphorus compound (Hokuko Chemical Co., TPP-S) 0.2 parts by mass, epoxysilane coupling agent (Shin-Etsu Chemical Co., Ltd., KBM- 403E) 0.5 parts by mass was dissolved and mixed in methyl ethyl ketone. Subsequently, it stirred for 6 hours at 45 degreeC of internal temperature using the high-speed stirring apparatus, and prepared the resin varnish A with a non-volatile content of 72 mass%.
The average particle size of the inorganic filler is dispersed by subjecting the inorganic filler to ultrasonic treatment for 1 minute in water, and a particle size distribution meter (manufactured by Shimadzu Corporation, product name: laser diffraction particle size distribution measuring device SALD series). (D50) measured by the above. The same applies to the following examples and comparative examples.

(Manufacture of prepreg)
As a fiber substrate, glass woven fabric (manufactured by Nitto Boseki Co., Ltd., T glass woven fabric, WTX-1027, basis weight 20 g / m ² , thickness 20 μm, flatness 0.036, warp weaving density of 75/25 mm, weft yarn Weaving density 75/25 mm, weft weaving density / warp weaving density 1.00) is impregnated with glass woven fabric into varnish A prepared as described above, excess varnish is removed with a coater, and 2 in a heating furnace at 180 ° C. The prepreg having a thickness of 0.04 mm and RC of 0.73 was obtained by partial drying.
As described above, the flatness is calculated by calculating an average value of three bundle yarns for each of the yarn bundle width and the yarn bundle thickness of the yarns constituting the glass cloth, and calculating the average yarn bundle width A and the average yarn bundle. It is obtained by the ratio B / A with the thickness B. The same applies to examples and comparative examples described later.

(Manufacture of copper-clad plates)
12 μm copper foil (manufactured by Mitsui Kinzoku Mining Co., Ltd.) is stacked on both sides of the prepreg obtained above, and pressure molding is performed at a pressure of 3 MPa and a temperature of 200 ° C. for 60 minutes (after reaching 200 ° C., heating for 60 minutes). As a result, a copper clad plate having copper foil on both sides was obtained.

(Manufacture of multilayer laminates)
An inner layer substrate (manufactured by Sumitomo Bakelite Co., Ltd., ELC-4785GS, 0.15 mm) provided with copper foil on the front and back surfaces was prepared. Then, the surface of each copper foil of the inner layer substrate was processed with L / S = 30 μm / 30 μm and a residual copper ratio of 70% to roughen the surface of the copper circuit. The prepreg obtained above was overlaid on each copper circuit, and a 12 μm copper foil (Mitsui Mining & Mining Co., Ltd.) was overlaid on each of the prepregs, and the pressure was 3 MPa and the temperature was 200 ° C. for 60 minutes (200 ° C. was reached). Thereafter, heating and pressing were performed for 60 minutes. As a result, a multilayer laminate having a size of 530 mm × 530 mm was obtained.

(Example 2)
As a fiber substrate, a glass woven fabric (manufactured by Nitto Boseki Co., Ltd., T glass woven fabric, WTX-1037, basis weight 23 g / m ² , thickness 25 μm, flatness 0.037, warp weaving density of 69/25 mm, weft yarn The varnish was adjusted in the same procedure as in Example 1 except that weaving density 72 yarns / 25 mm, weft weaving density / warp weaving density 1.04). .67 prepreg, copper-clad plate and multilayer laminate were obtained.

(Example 3)
As a fiber base material, a glass woven fabric (manufactured by Nitto Boseki Co., Ltd., T glass woven fabric, WTX-1078, basis weight 48 g / m ² , thickness 45 μm, flatness 0.046, weft density of warp 53/25 mm, weft yarn The varnish was adjusted in the same manner as in Example 1 except that 53 weave density / 25 mm, weft weave density / warp weave density 1.00) was used. .58 prepreg, copper-clad plate and multilayer laminate were obtained.

Example 4
After stirring for 6 hours at a varnish internal temperature of 25 ° C. at room temperature, the varnish was prepared in the same procedure as in Example 1 except that it was left in a 50 ° C. environment for 24 hours (referred to as resin varnish B). In the same manner, a prepreg having a thickness of 0.04 mm and RC 0.73, a copper clad plate, and a multilayer laminate plate were obtained.

(Example 5)
20 parts by mass of a phenol aralkyl type epoxy resin having a biphenylene skeleton (manufactured by Nippon Kayaku Co., Ltd., NC-3000FH), 5 parts by mass of a naphthalene type epoxy resin (manufactured by DIC Corporation, HP4032D), a naphthol type cyanate resin (manufactured by Tohto Kasei Co., Ltd.) , SN485 derivative) 17 mass, bismaleimide resin (manufactured by Keiai Kasei Kogyo Co., Ltd., BMI-70) 7.5 mass%, silica particles (NSS-5N produced by Tokuyama Corporation, average particle size 70 nm) 7 mass parts, spherical fused silica (Admatechs SO-25R, average particle size 0.5 μm) 35.5 parts by mass, silicone particles (Shin-Etsu Chemical Co., Ltd., KMP600, average particle size 5 μm) 7.5 parts by mass, zinc octylate 0.01 Mass, epoxy silane type coupling agent (Shin-Etsu Chemical Co., Ltd., KBM-403E) 0.5 mass, methyl ethyl A varnish (resin varnish C) was prepared in the same procedure as in Example 1 except that it was dissolved and mixed in tons. Using this resin varnish C, the thickness was 0 as in Example 1. A prepreg of 0.04 mm and RC 0.73, a copper clad plate, and a multilayer laminate were obtained.

(Example 6)
(Varnish formulation)
The amount of each component in varnish A used in Example 1 was different from that of varnish A. Specifically, it is as follows.
21 parts by mass of a phenol aralkyl type epoxy resin having a biphenylene skeleton (manufactured by Nippon Kayaku Co., Ltd., NC-3000), 9 parts by mass of a novolak type cyanate resin (manufactured by Lonza Japan Co., Ltd., PT-30), spherical fused silica (Admatex) Company SO-25R, average particle size 0.5 μm) 95 parts by mass, organophosphorus compound (made by Hokuko Chemical Co., TPP-S) 0.15 parts by mass, epoxy silane type coupling agent (Shin-Etsu Chemical Co., Ltd., KBM- 403E) 1.3 parts by mass was dissolved and mixed in methyl ethyl ketone. Subsequently, it stirred for 6 hours at 45 degreeC of internal temperature using the high-speed stirring apparatus, and prepared the resin varnish F with a non volatile matter content of 70 mass%.
Using this varnish F, in the same manner as in Example 1, a prepreg having a thickness of 0.04 mm and RC 0.73, a copper clad plate, and a multilayer laminate plate were obtained.

(Example 7)
(Varnish formulation)
The amount of each component in varnish A used in Example 1 was different from that of varnish A. Specifically, it is as follows.
56 parts by mass of a phenol aralkyl type epoxy resin having a biphenylene skeleton (manufactured by Nippon Kayaku Co., Ltd., NC-3000), 24 parts by mass of a novolak type cyanate resin (manufactured by Lonza Japan Co., Ltd., PT-30), spherical fused silica (Admatex) SO-25R, average particle size 0.5 μm) 55 parts by mass, organophosphorus compound (made by Hokuko Chemical Co., TPP-S) 0.15 parts by mass, epoxy silane type coupling agent (Shin-Etsu Chemical Co., Ltd., KBM- 403E) 0.15 part by mass was dissolved and mixed in methyl ethyl ketone. Subsequently, it stirred for 6 hours at 45 degreeC of internal temperature using the high-speed stirring apparatus, and prepared the resin varnish G of 70 mass% of non volatile matters.
Using this varnish G, in the same manner as in Example 1, a prepreg having a thickness of 0.04 mm and RC 0.73, a copper clad plate, and a multilayer laminate plate were obtained.

(Comparative Example 1)
A varnish was prepared (resin varnish D) in the same procedure as in Example 1 except that stirring was performed at room temperature at 25 ° C. for 6 hours at room temperature, and this resin varnish D was used as in Example 1. Further, a prepreg having a thickness of 0.04 mm and RC 0.73, a copper-clad plate, and a multilayer laminate plate were obtained.

(Comparative Example 2)
As a fiber base material, a glass woven fabric (manufactured by Nitto Boseki Co., Ltd., T glass woven fabric, WTX-1078, basis weight 48 g / m ² , thickness 45 μm, flatness 0.046, weft density of warp 53/25 mm, weft yarn The varnish was adjusted in the same procedure as in Comparative Example 1 except that 53 weaving density / 25 mm, weft weaving density / warp weaving density 1.00), 0.06 mm thickness, RC0.58 prepreg, copper-clad board, A multilayer laminate was obtained.

(Comparative Example 3)
52 parts by mass of phenol aralkyl type epoxy resin (Nippon Kayaku Co., Ltd., NC-3000) having a biphenylene skeleton, 23 parts by mass of novolac type cyanate resin (manufactured by Lonza Japan Co., Ltd., PT-30), spherical fused silica (Admatex) SO-25R, average particle size 0.5 μm) 25 parts by mass, organophosphorus compound (Hokuko Chemical Co., TPP-S) 0.35 parts by mass, epoxy silane coupling agent (Shin-Etsu Chemical Co., Ltd., KBM- 403E) A varnish was prepared in the same procedure as in Example 1 except that 0.2 mass was used (referred to as resin varnish E). Using resin varnish E, the thickness was 0.06 mm as in Example 1. RC0.73 prepreg, copper-clad plate, and multilayer laminate were obtained.

(Comparative Example 4)
The amount of each component was the same as in Varnish F of Example 6, but each component was dissolved and mixed in methyl ethyl ketone, and then stirred at an internal temperature of 35 ° C. for 2 hours using a high-speed stirrer. Thereby, a resin varnish H having a nonvolatile content of 70% by mass was prepared.
Thereafter, using this varnish H, a prepreg having a thickness of 0.06 mm and RC 0.73, a copper clad plate, and a multilayer laminate plate were obtained in the same manner as in Example 1.

<Evaluation method>
(Glossiness measurement)
The surface glossiness of the prepreg obtained above was measured according to JIS Z 8741 using IG-331 (incidence angles 60 ° and 20 °) manufactured by HORIBA. In addition, the measurement took the average value of the value each measured in the direction of the warp direction and the weft direction with respect to the direction of the fiber of a glass woven fabric at the same location of a prepreg.

(Surface condition)
The surface state of the prepreg obtained above (= whether the filler (filler) was exposed) was observed with a SEM (electron microscope) at a magnification of 3500 times. The observed part is a part corresponding to the center part in the fiber substrate width direction when the varnish of the thermosetting resin composition is impregnated with the fiber substrate, and the range of 3.5 μm × 2.85 μm is observed. did.

(Storage modulus)
Using a DMA device (DMA 983 manufactured by TA Instruments), measurement was performed under conditions of a frequency of 1 Hz and a temperature increase rate of 5 ° C./min, and storage elastic moduli E ′ at 25 ° C. and 260 ° C. were measured.
In addition, the evaluation sample was used after cutting and removing the copper foil of the copper clad plate obtained above (prepreg heated at 200 ° C. for 60 minutes) to a predetermined size.

(Maximum forming stripe length)
The outer peripheral part of the multilayer laminated board of 530 mm × 530 mm size obtained in each example and each comparative example was cut to 500 mm × 500 mm size, and the outer layer copper foil was removed by etching. Next, the maximum length of the forming stripes found on the outer peripheral portion was measured with a straight scale.

(Board yield)
The sample for which the maximum forming stripe length was measured was cut into a size of 50 mm × 50 mm and separated into 100 pieces. The number of samples mixed with molding stripes was counted in the singulated sample, and the sample containing stripes was determined as NG, and the substrate yield was determined.

(Solder heat resistance)
The multilayer laminate obtained above was exposed to a PCT environment of 121 ° C./100%/2 atm / 2 hr, and then immersed in a solder bath at 288 ° C. for 30 seconds to check for swelling of the copper foil / insulating layer. Observed. In addition, the evaluation sample cut | disconnected and used the laminated board which has copper foil on both surfaces obtained above by the predetermined | prescribed magnitude | size.

Table 2 below shows the results of Examples 1 to 7 and Comparative Examples 1 to 4.
In addition, when the surface of the prepreg obtained in all the examples was measured with the optical surface roughness meter, surface roughness Ra was 0.15 micrometer or more. The prepreg of Example 1 had an arithmetic average surface roughness Ra of 0.6 μm, and the prepreg of Example 3 had an arithmetic average surface roughness Ra of 1.2 μm. In Example 2, the arithmetic average surface roughness Ra was a value between 0.6 μm and 1.2 μm.
The surface roughness (arithmetic average surface roughness Ra) was measured according to JIS B0601: 2001 with a laser microscope (Veeco, WYKO NT1100, conditions: sampling 808.15 nm, observation field plane 594 μm × 452 μm).

In Examples 1 to 7 in which the varnish having a high filler content in the resin composition was heated, the glossiness of the prepreg surface measured at an incident angle of 60 ° was 30 or more. The four-layer laminate formed by multilayer molding using these prepregs resulted in a short molding stripe and a high substrate yield. In addition, it has excellent solder heat resistance, and it has been possible to prevent both abnormal appearance and solder heat resistance. Since these prepregs have a high content of the filler in the constituent resin composition, the strength of the prepreg itself is ensured because of its high elastic modulus. Therefore, it is a prepreg excellent in the prevention of abnormal appearance and the balance of strength.
A multilayer printed wiring board made using these prepregs also has a high elastic modulus, is considered to be excellent in strength, and can suppress warpage during heating such as reflow.
Further, in the prepregs of Examples 1 to 7 where the glossiness of the prepreg surface measured at an incident angle of 60 ° was 30 or more, when the surface state was observed, the filler was not exposed on the prepreg surface and was observed. The entire surface of the filler was covered with the resin component. FIG. 3A shows a view of the surface of the prepreg produced in Example 1 observed by SEM (3500 times). As shown in FIG. 3A, it can be seen that the filler is not exposed.

On the other hand, in Comparative Examples 1 and 2 in which the varnish having a high filler content in the resin composition was not heated, the glossiness of the prepreg surface measured at an incident angle of 60 ° was low, and molding As a result, the streaks were long, the substrate yield was poor, and it was impossible to achieve both the prevention of abnormal appearance and soldering heat resistance, and the prevention of abnormal appearance and ensuring strength.
Further, in Comparative Example 3 in which the filler content was as low as about 25% by mass, the elastic modulus was low and the solder heat resistance was poor.
Moreover, in Comparative Example 4, the glossiness of the prepreg surface measured at an incident angle of 60 ° is less than 30, the molding streak is long, the substrate yield is poor, both appearance abnormality prevention and solder heat resistance are compatible, and appearance abnormality prevention As a result, it was impossible to achieve both strength and strength.
In addition, in the prepregs of Comparative Examples 1, 2, and 4 where the glossiness of the prepreg surface measured at an incident angle of 60 ° is less than 30, most of the fillers (90% of the observed number of fillers on the surface). The above was exposed, and the filler was not covered with the resin component. The figure which observed the surface of the prepreg manufactured by the comparative example 1 in FIG.3 (B) by SEM is shown (3500 times). As shown in FIG. 3B, it can be seen that the filler is exposed.

1 Prepreg 11 Fiber substrate 12 Resin layer F Filler B Basket hole 900 Prepreg

Claims (11)

A prepreg comprising a fiber substrate and a thermosetting resin composition containing a filler,
The fiber substrate is a glass cloth;
The flatness, which is the ratio B / A between the yarn bundle width A and the yarn bundle thickness B of the glass cloth, is 0.07 or less,
The filler content in the thermosetting resin composition is 35% by mass or more and 80% by mass or less,
A prepreg having a surface glossiness of 30 or more measured at an incident angle of 60 ° in accordance with JIS Z 8741. The prepreg according to claim 1,
A prepreg obtained by impregnating the glass cloth with a varnish of the thermosetting resin composition. The prepreg according to claim 1 or 2,
After curing at 200 ° C. for 60 minutes, the storage elastic modulus E ′ at 25 ° C. when measured at a frequency of 1 Hz is 13 GPa or more and 50 GPa or less, and
A prepreg having a storage elastic modulus E ′ at 260 ° C. of 5 GPa or more and 20 GPa or less when measured at a frequency of 1 Hz after being cured at 200 ° C. for 60 minutes. The prepreg according to any one of claims 1 to 3,
A prepreg having a thickness of 20 μm or more and 100 μm or less. The prepreg according to any one of claims 1 to 4,
The filler is an inorganic filler,
A prepreg having an average particle size of the inorganic filler of 5 μm or less. The prepreg according to any one of claims 1 to 5,
A prepreg in which the weaving density of the glass cloth is 40 warps / 25 mm or more and 40 wefts / 25 mm or more. The prepreg according to any one of claims 1 to 6,
The glass cloth is a prepreg composed of glass selected from E glass, T glass, S glass, NE glass, UT glass, L glass, and quartz glass. The prepreg according to any one of claims 1 to 7,
A prepreg having a value (RC) represented by (prepreg mass−fiber substrate mass) / mass of prepreg is 0.67 or more and 0.85 or less.   A laminate comprising the prepreg according to claim 1 and a metal layer provided on the prepreg.   A multilayer printed wiring board comprising the laminated board according to claim 9.   A semiconductor device comprising the multilayer printed wiring board according to claim 10 and a semiconductor element provided on the multilayer printed wiring board.

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