KR20140027493A - Prepreg, laminated plate, semiconductor package, and method for producing laminated plate - Google Patents

Abstract

The prepreg 100 of this invention is obtained by impregnating the fiber base material 101 with the resin composition containing an epoxy resin and an epoxy resin hardening | curing agent. And nitrogen content in the prepreg 100 is 0.10 mass% or less, and the air permeability of the fiber base material 101 is 3.0 cm <3> / cm <2> / sec or more and 30.0 cm <3> / cm <2> / sec or less.

Description

Prepreg, laminated plate, semiconductor package and laminated plate manufacturing method {PREPREG, LAMINATED PLATE, SEMICONDUCTOR PACKAGE, AND METHOD FOR PRODUCING LAMINATED PLATE}

The present invention relates to a prepreg, a laminate, a semiconductor package, and a method for producing a laminate.

In recent years, with the demand for higher functional and lighter and shorter electronic devices, miniaturization of semiconductor devices used in these electronic devices is rapidly progressing.

On the other hand, when miniaturizing a semiconductor device, it is necessary to make the circuit board to be used high density, and the number of the through holes drilled for connection between circuits increases compared with the past, and hole density becomes high. As the hole density increases, the distance between the walls of the through-holes approaches, so that the metal ions move along the short fibers of the fiber base, and ion migration that short-circuits the circuit easily occurs. When this ion migration occurs, the insulation reliability of a circuit board will fall (for example, refer patent document 1, 2).

Patent Document 3 (Japanese Laid-Open Patent Publication No. 2004-149577) discloses a thermosetting material for a substrate having a ventilation ratio of 2 to 4 cm 3 / cm 2 / sec by performing at least one of flat and open processing on glass cloth. The prepreg which impregnates a resin composition and makes this thermosetting resin composition into a B stage state is described.

Since the impregnation with respect to the fiber base material of a thermosetting resin composition improves the laminated board using such a prepreg, the intensity | strength of a laminated board becomes uniform. Therefore, it is described that the inner wall of the hole formed by the drilling process can be formed smoothly, and the generation of ion migration can be suppressed even when the hole density becomes high and the distance between the walls of the through holes approaches.

In addition, it is described that glass fiber yarns are spatially enlarged by the carding treatment to improve the impregnation with the glass fibers, thereby reducing the voids, thereby suppressing the occurrence of migration.

Japanese Laid-open Patent Publication 2004-322364 Japanese Patent Laid-Open No. 6-316643 Japanese Laid-Open Patent Publication 2004-149577

However, when said flat processing and open | closing processing were performed with respect to fiber base materials, such as glass cloth, a fiber base material might have fluffed. When fluff is generated on the fibrous substrate, the strength of the fibrous substrate is reduced or resin pooling occurs at the projections of the fluff to roughen the surface of the prepreg.

Therefore, although the technique of processing the fiber base material like the said patent document 3 and improving the insulation reliability of a laminated board was effective in improving insulation reliability, there was still room for improvement in terms of yield.

Then, in this invention, it is a subject to provide the prepreg which can obtain the laminated board which is excellent in insulation reliability, and has a favorable yield.

The inventors earnestly studied the mechanism by which ion migration occurs. As a result, when the nitrogen content in a prepreg was reduced to 0.10 mass% or less, it discovered that ion migration resistance improved.

That is, according to the present invention,

As a prepreg obtained by impregnating a fiber base material with a resin composition containing an epoxy resin and an epoxy resin curing agent,

Nitrogen content in the said prepreg is 0.10 mass% or less,

A prepreg is provided in which the air permeability of the fiber base is 3.0 cm 3 / cm 2 / sec or more and 30.0 cm 3 / cm 2 / sec or less.

According to this invention, by using the said prepreg whose nitrogen content is 0.10 mass% or less, even if the fiber base material which has said air permeability is used, the ion migration resistance of a laminated board can be improved. Moreover, the fiber base material which has said air permeability can suppress generation | occurrence | production of a fluff, and can improve the yield of a prepreg.

Further, according to the present invention,

There is provided a laminate comprising a cured body of the prepreg.

Further, according to the present invention,

The semiconductor package which mounts a semiconductor element in the circuit board obtained by carrying out the circuit processing of the said laminated board is provided.

Further, according to the present invention,

A step of obtaining a prepreg by impregnating a resin substrate with an epoxy resin, an epoxy resin curing agent, and a solvent to a fiber base material;

Heating the prepreg to obtain a cured product of the prepreg,

Then,

As a manufacturing method of the laminated board which performs the process of forming a via by a laser,

The theoretical nitrogen content in the said resin varnish is 0.50 mass% or less,

Provided is a method for producing a laminate in which the air permeability of the fiber base is 3.0 cm 3 / cm 2 / sec or more and 30.0 cm 3 / cm 2 / sec or less.

According to this invention, the laminated board which is excellent in insulation reliability can be obtained, and the prepreg which is excellent in a yield can be provided.

The above-mentioned object and other objects, features, and advantages are further clarified by the preferred embodiments described below and the accompanying drawings.
1 is a cross-sectional view showing an example of the configuration of a prepreg in the present embodiment.
2 is a cross-sectional view showing an example of the configuration of a semiconductor package in the present embodiment.
3 is a cross-sectional view showing an example of the configuration of a semiconductor device in the present embodiment.

EMBODIMENT OF THE INVENTION Below, embodiment of this invention is described using drawing. In all the drawings, the same components are denoted by the same reference numerals, and description thereof is omitted as appropriate. In addition, the figure is a schematic diagram and does not necessarily correspond to an actual dimension ratio.

(Prepreg)

First, the structure of the prepreg in this embodiment is demonstrated. 1 is a cross-sectional view showing an example of the configuration of a prepreg in the present embodiment. The prepreg 100 is obtained by impregnating the fiber base material 101 with the resin composition P containing (A) epoxy resin and (B) epoxy resin hardening | curing agent.

The nitrogen content in the prepreg 100 is 0.10 mass% or less, Preferably it is 0.08 mass% or less, More preferably, it is 0.05 mass% or less. When nitrogen content in the prepreg 100 is below the said upper limit, the ion migration resistance of a laminated board can be improved. Therefore, in order to improve ion migration resistance, special processing, such as flat processing and carding processing, performed on a fiber base material can be suppressed. Therefore, generation | occurrence | production of fluff of a fiber base material can be suppressed, and the yield of a prepreg can be improved.

The reason why the ion migration resistance of the laminate is improved is not very clear, but is inferred as follows. When the nitrogen content in the prepreg 100 is reduced, the moisture resistance of the prepreg 100 improves. Therefore, moisture is less likely to adhere to the interior of the laminate obtained from the prepreg 100, in particular, the gap between the fibrous substrate and the resin, so that the ionization of the metal and the movement of the metal ions are less likely to occur. As a result, it is inferred that generation | occurrence | production of ion migration is suppressed.

Measurement of nitrogen content in the prepreg 100 may be measured by generally known methods, for example, thermal conductivity detector using an organic element analyzer was digested prepregs combustion, converts the generated gas to N ₂ It can be measured by.

Moreover, the air permeability of the fiber base material 101 in the prepreg 100 is 3.0 cm <3> / cm <2> / sec or more, More preferably, it is 3.5 cm <3> / cm <2> / sec or more, Especially preferably, it is 4.0 cm <3> / cm <2> / sec or more. . Since the prepreg 100 in this embodiment is excellent in ion migration resistance, the air permeability can use the fiber base material more than the said lower limit. In other words, in order to improve ion migration resistance, special processing, such as flat processing and carding processing, can be suppressed. Therefore, since occurrence of fluff of the fiber base 101 is suppressed, resin pools that are likely to occur in the projections of the fluff are not easily generated. Therefore, the yield of a prepreg can be improved.

Moreover, the air permeability of the fiber base material 101 is 30.0 cm <3> / cm <2> / sec or less, More preferably, it is 20.0 cm <3> / cm <2> / sec or less, More preferably, it is 15.0 cm <3> / cm <2> / sec or less, Especially preferably, it is 12.0 cm <3>. / Cm 2 / sec or less. When the air permeability of the fiber base material 101 is below the said upper limit, since the impregnation property of the resin composition with respect to the fiber base material improves, the intensity | strength of a laminated board can be made uniform. Therefore, the inner wall of the hole formed by the punching process can be formed smoothly, and generation | occurrence | production of ion migration can be suppressed even if the hole density becomes high and the inter-wall distance of a through hole approaches.

Here, the air permeability of the fiber base material 101 can be adjusted by processing, such as flat processing and carding processing.

In addition, the measurement of air permeability can be measured in accordance with JISR3420 method (flame mold method).

Then, the material which comprises the prepreg 100 is demonstrated in detail.

The prepreg 100 in this embodiment is obtained by impregnating the fiber base material 101 with the resin composition P containing (A) epoxy resin and (B) epoxy resin hardening | curing agent, and semi-curing after that. And a sheet material provided with the fiber base material 101 and the resin layers 103 and 104. The sheet-like material having such a structure is excellent in various characteristics such as dielectric properties, mechanical and electrical connection reliability under high temperature and high humidity, and is suitable for the manufacture of a laminate for a circuit board.

(Resin composition)

Hereinafter, as resin composition P which impregnates the fiber base material 101, if it contains (A) epoxy resin and (B) epoxy resin hardening | curing agent, it will not specifically limit, but it has a low linear expansion coefficient and a high elastic modulus, and is excellent in the reliability of thermal shock. It is preferable that it is.

(A) An epoxy resin is a compound which has one or more glycidyl groups in a molecule | numerator, A compound which hardens | cures by forming a three-dimensional network structure by glycidyl group reacting by heating. (A) It is preferable that epoxy resin contains two or more glycidyl groups in 1 molecule, because sufficient hardened | cured material characteristic cannot be exhibited even if it reacts only by the compound which has one glycidyl group.

Specific examples of the (A) epoxy resin include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol E type epoxy resins, bisphenol M type epoxy resins, bisphenol P type epoxy resins, and bisphenol Z. Bisphenol-type epoxy resins such as epoxy resins or derivatives thereof, novolak-type epoxy resins such as phenol novolak-type epoxy resins, cresol novolak-type epoxy resins, biphenyl-type epoxy resins, and biphenyl aralkyl-type epoxy resins Epoxy resins such as arylalkylene type epoxy resins, naphthalene type epoxy resins, anthracene type epoxy resins, phenoxy type epoxy resins, dicyclopentadiene type epoxy resins, norbornene type epoxy resins, adamantane type epoxy resins, and fluorene type epoxy resins Etc. can be mentioned. One type of these may be used alone or two or more types may be used in combination.

Although content of (A) epoxy resin is not specifically limited, It is preferable that they are 15 mass% or more and 80 mass% or less of the whole resin composition P. More preferably, they are 25 mass% or more and 60 mass% or less. Moreover, when using together liquid epoxy resins, such as a liquid bisphenol-A epoxy resin and a bisphenol F-type epoxy resin, since impregnation with respect to the fiber base material 101 can be improved, it is preferable. Content of liquid epoxy resin is more preferable in it being 3 mass% or more and 30 mass% or less of the whole resin composition P. Moreover, when using a solid bisphenol-A epoxy resin and a bisphenol F-type epoxy resin together, adhesiveness with respect to a conductor can be improved.

(B) Although it does not specifically limit as an epoxy resin hardening | curing agent, For example, a phenol type hardening | curing agent, an aliphatic amine, aromatic amine, dicyandiamide, a dihydrazide compound, an acid anhydride, etc. are mentioned. Among these, the organic compound which does not contain a nitrogen atom in a chemical formula is especially preferable, and the phenolic hardener and acid anhydride which do not contain a nitrogen atom in a chemical formula are especially preferable. When a phenol type hardening | curing agent and an acid anhydride are used, the prepreg whose nitrogen content is 0.10 mass% or less can be obtained more efficiently.

(B) The phenol type hardening | curing agent as an epoxy resin hardening | curing agent is a compound which has 2 or more of phenolic hydroxyl groups in 1 molecule. In the case of the compound which has one phenolic hydroxyl group in 1 molecule, since a crosslinked structure cannot be taken, hardened | cured material characteristic deteriorates and cannot be used.

As a phenol type hardening | curing agent, well-known conventional uses, such as a phenol novolak resin, an alkyl phenol novolak resin, bisphenol A novolak resin, a dicyclopentadiene type phenol resin, a xylox phenol resin, a terpene modified phenol resin, polyvinyl phenols, for example May be used alone or in combination of two or more thereof.

It is preferable that the compounding quantity of a phenol hardening | curing agent is (A) equivalent ratio (phenolic hydroxyl group equivalent / epoxy group equivalent) with an epoxy resin is 0.1 or more and 1.0 or less. Thereby, the remainder of an unreacted phenol hardening | curing agent disappears and moisture absorption heat resistance improves. When resin composition P uses an epoxy resin and cyanate resin together, the range of 0.2 or more and 0.5 or less is especially preferable. This is because the phenol resin not only acts as a curing agent but also promotes the curing of the cyanate group and the epoxy group.

(B) As an acid anhydride as an epoxy resin hardener, a phthalic anhydride, tetrahydro phthalic anhydride, a hexahydro phthalic anhydride, 4-methylhexahydro phthalic anhydride, an endomethylene tetrahydrophthalic anhydride, a dodecenyl succinic anhydride, a maleic anhydride, for example. And acid.

(B) As a dihydrazide compound as an epoxy resin hardening | curing agent, For example, carboxylic acids, such as adipic acid dihydrazide, a dodecanoic acid dihydrazide, an isophthalic acid dihydrazide, and p-oxybenzoic acid dihydrazide Dihydrazide and the like.

Moreover, you may use together the following (C) hardening catalyst to resin composition P so that the nitrogen content in the obtained prepreg 100 may not exceed 0.10 mass%. In addition, (C) hardening catalyst is a catalyst which has a function which accelerate | stimulates hardening reaction of (A) epoxy resin and (B) epoxy resin hardening | curing agent, and is distinguished from (B) epoxy resin hardening | curing agent.

For example, organometallic salts, such as zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, bisacetylacetonate cobalt (II), and trisacetyl acetonate cobalt (III), triethylamine, tributylamine, diadia Tertiary amines such as xabicyclo [2,2,2] octane, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 2-ethyl-4 Imidazoles such as -ethylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxyimidazole, and 2-phenyl-4,5-dihydroxyimidazole Onium salt compounds such as phenol compounds such as phenol, bisphenol A and nonylphenol, organic acids such as acetic acid, benzoic acid, salicylic acid and paratoluenesulfonic acid, and the like, or a mixture thereof. (C) As a curing catalyst, one type may be used independently including these derivatives, and it may also use two or more types together including these derivatives.

Content of (C) hardening catalyst will not be specifically limited if nitrogen content in the prepreg 100 obtained does not exceed 0.10 mass%. For example, 0.010 mass% or more of the whole resin composition P is preferable, and 0.10 mass% or more is especially preferable. (C) The effect of promoting hardening can fully be acquired as content of a hardening catalyst is more than the said lower limit. Moreover, 5.0 mass% or less of the whole resin composition P is preferable, and, as for content of (C) hardening catalyst, 2.0 mass% or less is especially preferable. (C) If content of a curing catalyst is below the said upper limit, the fall of the preservation of the prepreg 100 can be suppressed.

It is preferable that resin composition P contains (D) inorganic filler further. As the inorganic filler (D), for example, talc, calcined clay, unbaked clay, mica, silicates such as glass, oxides such as titanium oxide, alumina, silica, fused silica, calcium carbonate, magnesium carbonate, hydrotalcite, etc. Hydroxides such as carbonate, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, sulfates such as barium sulfate, calcium sulfate, calcium sulfite or sulfite, zinc borate, barium metaborate, aluminum borate, calcium borate, sodium borate, such as borate, aluminum nitride, Nitrides such as boron nitride, silicon nitride, carbon nitride, and titanates such as strontium titanate and barium titanate. One type of these may be used alone or two or more types may be used in combination.

Among these, silica is especially preferable, and fused silica (especially spherical fused silica) is preferable at the point which is excellent in low thermal expansion. The shape may be crushed or spherical. To lower the melt viscosity of the resin composition P in order to ensure impregnation with the fiber base 101, a use method suitable for the purpose is employed, such as using spherical silica.

Although the average particle diameter of (D) inorganic filler is not specifically limited, 0.01 micrometer or more and 3 micrometers or less are preferable, and 0.02 micrometer or more and 1 micrometer or less are especially preferable. (D) By making the particle diameter of an inorganic filler into 0.01 micrometer or more, a varnish can be made into low viscosity and the fiber base material 101 can be made to impregnate the resin composition P favorably. Moreover, sedimentation of (D) inorganic filler etc. can be suppressed in a varnish by setting it as 3 micrometers or less. This average particle diameter can be measured, for example by a particle size distribution meter (The Shimadzu Corporation make, product name: laser diffraction type particle size distribution analyzer SALD series).

The inorganic filler (D) is not particularly limited, but an inorganic filler having a monodispersed average particle size may be used, or an inorganic filler having a polydisperse average particle diameter may be used. Moreover, one type or two types or more can also be used together with the inorganic filler whose average particle diameter is monodispersion and / or polydispersion.

Furthermore, spherical silica (especially spherical fused silica) with an average particle diameter of 3 micrometers or less is preferable, and spherical fused silica with an average particle diameter of 0.02 micrometer or more and 1 micrometer or less is especially preferable. Thereby, the filling property of (D) inorganic filler can be improved.

Although content of (D) inorganic filler is not specifically limited, 2 mass% or more and 70 mass% or less of the whole resin composition P are preferable, and 5 mass% or more and 60 mass% or less are especially preferable. If content is in the said range, it can be made especially low thermal expansion and low absorption.

Moreover, although it does not specifically limit to resin composition P, It is preferable to contain (E) coupling agent further. The coupling agent (E) improves the interfacial wettability of the (A) epoxy resin and the (D) inorganic filler, thereby uniformly fixing the (A) epoxy resin and the (D) inorganic filler to the fiber base material, thereby providing heat resistance, in particular moisture absorption. The subsequent solder heat resistance can be improved.

(E) Any coupling agent can be used as long as it is commonly used, and specifically, it is selected from an epoxy silane coupling agent, a cationic silane coupling agent, an aminosilane coupling agent, a titanate coupling agent and a silicone oil type coupling agent. It is preferable to use at least one coupling agent. Thereby, wettability with the interface of (D) inorganic filler can be improved, and heat resistance can be improved more by it.

The addition amount of the (E) coupling agent is not particularly limited because it depends on the specific surface area of the (D) inorganic filler, but is preferably 0.05% by mass or more and 5% by mass or less, particularly 0.1% by mass based on 100 parts by mass of the (D) inorganic filler. % And 3 mass% or less are preferable. By making content into 0.05 mass% or more, (D) inorganic filler can fully be coat | covered and heat resistance can be improved. By setting it as 5 mass% or less, reaction advances favorably and the fall of bending strength etc. can be prevented.

Moreover, the resin composition P may contain thermosetting resins other than epoxy resins, such as melamine resin, urea resin, and cyanate resin, and it is preferable to use cyanate resin together especially.

Although it does not specifically limit as a kind of cyanate resin, For example, Bisphenol-type cyanate, such as novolak-type cyanate resin, bisphenol-A cyanate resin, bisphenol-E cyanate resin, tetramethyl bisphenol F-type cyanate resin, etc. Resin and the like. Among these, a phenol novolak-type cyanate resin is preferable at the point which is low thermal expansion. Moreover, since another cyanate resin can also use together one type or two types or more, it is not specifically limited. It is preferable that cyanate resin is 8 mass% or more and 20 mass% or less of the whole resin composition P.

Moreover, in resin composition P, thermoplastic resins, such as a phenoxy resin, a polyimide resin, a polyamideimide resin, a polyamide resin, a polyphenylene oxide resin, a polyether sulfone resin, a polyester resin, a polyethylene resin, and a polystyrene resin, Thermoplastic elastomers such as polystyrene-based thermoplastic elastomers such as butadiene copolymers and styrene-isoprene copolymers, polyolefin-based thermoplastic elastomers, polyamide-based elastomers, and polyester-based elastomers, polybutadiene, epoxy-modified polybutadiene, and acrylic-modified polybutadiene and meta You may use together diene elastomers, such as a krill modified polybutadiene. Among these, heat resistant polymer resins such as phenoxy resin, polyimide resin, polyamideimide resin, polyamide resin, polyphenylene oxide resin and polyether sulfone resin are preferable. Thereby, the thickness uniformity of the prepreg 100 is excellent, and as a wiring board, it is excellent in heat resistance and the insulation of a micro wiring. Moreover, you may add additives other than the said component, such as a pigment, dye, an antifoamer, a leveling agent, a ultraviolet absorber, a foaming agent, antioxidant, a flame retardant, and an ion trapping agent, to this resin composition P as needed.

Although the fiber base material 101 which impregnates the resin composition P is not specifically limited, Glass fiber base materials, such as glass cloth, a glass woven fabric, and a glass nonwoven fabric, carbon fiber base materials, such as carbon cloth and a carbon fiber fabric, lock wool, etc. Polyamide resin fibers such as artificial mineral base materials, polyamide resin fibers, aromatic polyamide resin fibers, wholly aromatic polyamide resin fibers, polyester resin fibers, aromatic polyester resin fibers, and all aromatic polyester resin fibers Synthetic fiber base material composed of woven or nonwoven fabric mainly composed of ester resin fiber, polyimide resin fiber, fluorine resin fiber, etc., kraft paper, cotton linter paper, paper base material mainly composed of blender of linter and kraft pulp, etc. Organic fiber base material, etc. are mentioned. Among these, glass fiber base materials are preferable. Thereby, the prepreg which is low water absorption, high strength, and low thermal expansion can be obtained.

As glass which comprises a glass fiber base material, E glass, C glass, A glass, S glass, D glass, NE glass, T glass, H glass, etc. are mentioned, for example. Among these, E glass or T glass is preferable. Thereby, high elasticity of a prepreg can be achieved and the thermal expansion coefficient of a prepreg can be made small.

As a fiber base material used by this embodiment, it is preferable that a basis weight (mass of the fiber base material per 1 m <2>) is 145 g / m <2> or more and 300 g / m <2>, More preferably, it is 160 g / m <2> or more and 230 g / m <2> or less. More preferably, they are 190 g / m <2> or more and 205 g / m <2> or less.

When basis weight is below the said upper limit, the impregnation property of the resin composition in a fiber base material can improve, and the fall of a strand void and insulation reliability can be suppressed. Moreover, the formation of the through hole by lasers, such as a carbon dioxide gas, UV, and an excimer, may become easy. Moreover, if basis weight is more than the said lower limit, the intensity | strength of a glass cloth and a prepreg will improve. As a result, handling property may improve, preparation of a prepreg may become easy, and the curvature reduction effect of a board | substrate may improve.

Although the thickness of a fiber base material is not specifically limited, It is preferable that they are 50 micrometers or more and 300 micrometers or less, More preferably, they are 80 micrometers or more and 250 micrometers or less, More preferably, they are 100 micrometers or more and 200 micrometers or less. By using the fiber base material which has such thickness, the handling property at the time of prepreg manufacture is further improved, and the curvature reduction effect is remarkable especially.

If the thickness of a fiber base material is below the said upper limit, the impregnation property of the resin composition in a fiber base material can improve, and the fall of strand void and insulation reliability can be suppressed. Moreover, the formation of the through hole by lasers, such as a carbon dioxide gas, UV, and an excimer, may become easy. Moreover, if basis weight is more than the said lower limit, the intensity | strength of a glass cloth and a prepreg will improve. As a result, handling property may improve, preparation of a prepreg may become easy, and the curvature reduction effect of a board | substrate may improve.

Moreover, the number of sheets of use of a fiber base material is not limited to one sheet, It can also be used, superimposing a plurality of sheets of thin fiber bases. In the case where a plurality of fibrous substrates are used by overlapping, the total thickness may satisfy the above range.

Next, the manufacturing method of the prepreg 100 is demonstrated in detail.

The prepreg 100 in this embodiment is obtained by impregnating the fiber base material 101 with the resin composition P containing (A) epoxy resin and (B) epoxy resin hardening | curing agent, and semi-curing after that. .

The method of impregnating the resin composition P in the fiber base material 101 is, for example, by preparing the resin varnish V using the resin composition P, the method of immersing the fiber base material 101 in the resin varnish V, the resin by various coaters The method of apply | coating varnish V, the method of spraying resin varnish V by spraying, the method of laminating the resin layer with a support base material on a fiber base material, etc. are mentioned. Among these, the method of immersing the fiber base material 101 in resin varnish V, and the method of laminating the resin layer with a support base material on a fiber base material are preferable. The method of immersing the fiber base material 101 in the resin varnish V can improve the impregnation property of the resin composition P with respect to the fiber base material 101. In addition, when the fiber base material 101 is immersed in resin varnish V, the normal impregnation coating equipment can be used.

In particular, when the thickness of the fiber base material 101 is 0.1 mm or less, the method of laminating the resin layer with a support base material on a fiber base material is preferable. Thereby, the impregnation amount of the resin composition P with respect to the fiber base material 101 can be adjusted freely, and the moldability of a prepreg can be improved further. In addition, when laminating a film-form resin layer, it is more preferable to use a vacuum laminating apparatus etc.

Although the solvent used for the resin varnish V shows favorable solubility with respect to the resin component in resin composition P, you may use a poor solvent in the range which does not adversely affect. Solvents showing good solubility include, for example, alcohols such as methanol and ethanol, toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, tetrahydrofuran, dimethylformamide and dimethylacetamide. And dimethyl sulfoxide, ethylene glycol, cellosolve, carbitol and the like.

Among these, the organic compound which does not contain a nitrogen atom in a chemical formula as a solvent is especially preferable, and alcohols, methyl ethyl ketone, and toluene are especially preferable. By using the organic compound which does not contain a nitrogen atom in chemical formula, the prepreg whose nitrogen content is 0.10 mass% or less can be obtained more efficiently.

Although solid content of resin varnish V is not specifically limited, 20 mass% or more and 90 mass% or less of solid content of resin composition P are preferable, and 50 mass% or more and 80 mass% or less are especially preferable. Thereby, the impregnation with respect to the fiber base material 101 of resin varnish V can be improved further. Although the predetermined temperature which impregnates the resin composition P in the fiber base material 101 is not specifically limited, For example, the prepreg 100 can be obtained by drying at 90 degreeC or more and 220 degrees C or less. It is preferable that the thickness of the prepreg 100 is 20 micrometers or more and 100 micrometers or less.

Moreover, the theoretical nitrogen content in resin varnish V is 0.50 mass% or less, Preferably it is 0.20 mass% or less, More preferably, it is 0.10 mass% or less. If the theoretical nitrogen content in resin varnish V is below the said upper limit, the prepreg whose nitrogen content is 0.10 mass% or less can be obtained more efficiently.

In addition, the theoretical nitrogen content in resin varnish V is a value calculated on the assumption that nitrogen contained in resin varnish V originates only from the component which contains a nitrogen atom in chemical formula. Specifically, the nitrogen content contained in each component is calculated from the molecular weight and the number of nitrogen atoms, and the value obtained by dividing the total weight by the weight of the whole resin varnish is displayed as%.

The prepreg 100 may be centered on the fiber base material 101, and the thickness of the resin layer 103 and the resin layer 104 may be substantially the same as or different from the center of the fiber base material 101. In other words, the prepreg 100 may shift the center of the thickness direction of a fiber base material, and the center of the thickness direction of a prepreg.

(Laminated board)

Next, the structure of the laminated board in this embodiment is demonstrated. The laminated board in this embodiment contains the hardened | cured material of the prepreg obtained by hardening | curing said prepreg 100.

(Manufacturing Method of Laminated Plates)

Next, the manufacturing method of the laminated board using the prepreg 100 obtained above is demonstrated. Although the manufacturing method of the laminated board using a prepreg is not specifically limited, For example, it is as follows.

One or more prepregs are superimposed and metal foils are superimposed on the upper and lower sides or one side of the outside thereof, and the lamination apparatus and the becquerel apparatus are bonded to each other under high vacuum conditions, or the metal foils are placed on the upper and lower sides or one side of the prepreg outside as it is. Overlap

Next, the laminated board can be obtained by heating, pressurizing, or heating with a dryer by which the metal foil was superimposed on the prepreg by a vacuum press.

The thickness of metal foil is 1 micrometer or more and 35 micrometers or less, for example. More preferably, they are 2 micrometers or more and 25 micrometers or less. If the thickness of this metal foil is more than the said lower limit, the mechanical strength at the time of manufacturing a laminated board can fully be ensured. Moreover, when thickness is below the said upper limit, it can make it easy to form and process a fine circuit.

Examples of the metal constituting the metal foil include copper and copper alloys, aluminum and aluminum alloys, silver and silver alloys, gold and gold alloys, zinc and zinc alloys, nickel and nickel alloys, tin and tin alloys, And Fe-Ni-based alloys such as iron and iron-based alloys, Cobal (trade name), 42 alloys, Invar or Super Invar, and W or Mo. Moreover, the electrolytic copper foil with a carrier can also be used.

Although it does not specifically limit as said method of heat processing, For example, it can carry out using a hot air drying apparatus, an infrared heating apparatus, a heating roll apparatus, a flat plate | plate hot press apparatus, etc. In the case of using a hot air drying device or an infrared heating device, the bonding can be performed without substantially applying pressure. Moreover, when using a heating roll apparatus or a flat plate | plate hot press apparatus, it can carry out by making a predetermined pressure apply | action to the said bonding.

Although the temperature at the time of heat processing is not specifically limited, It is preferable to set it as the temperature range where resin to be used melt | dissolves and the hardening reaction of resin does not advance rapidly. The temperature at which the resin is melted is preferably at least 120 ° C, more preferably at least 150 ° C. Moreover, as temperature which hardening reaction of resin does not advance rapidly, Preferably it is 250 degrees C or less, More preferably, it is 230 degrees C or less.

Moreover, since time to heat-process differs according to the kind of resin to be used, etc., it does not specifically limit, For example, it can carry out by processing for 30 minutes or more and 300 minutes or less.

Moreover, although the pressure to pressurize is not specifically limited, For example, 0.2 Mpa or more and 6 Mpa or less are preferable, and 2 Mpa or more and 5 Mpa or less are more preferable.

Moreover, you may laminate | stack a film on at least one surface of the laminated board in this embodiment instead of metal foil. Examples of the film include polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polyimide, and fluorine resin.

(Semiconductor package)

Then, the semiconductor package 200 in this embodiment is demonstrated.

The obtained laminated board can be used for the semiconductor package 200 shown in FIG. As a manufacturing method of the semiconductor package 200, there exists the following method, for example.

The through hole 215 for interlayer connection is formed in the laminated board 213, and a wiring layer is produced by the subtractive method, the semiadditive process, etc. Thereafter, build-up layers (not shown in Fig. 2) are laminated as necessary, and the process of forming interlayer connections and circuits by the additive method is repeated. Then, the solder resist layer 201 is laminated as necessary and the circuit is formed by the method described above to obtain a circuit board. Here, some or all of the buildup layers and the solder resist layer 201 may or may not contain a fiber base material.

Next, after apply | coating photoresist on the whole surface of the soldering resist layer 201, a part of photoresist is removed and a part of soldering resist layer 201 is exposed. In addition, a resist having a function of a photoresist may be used for the solder resist layer 201. In this case, the photoresist coating step can be omitted. Next, the exposed solder resist layer is removed to form the opening 209.

Subsequently, the reflow process is performed to fix the semiconductor element 203 on the connection terminal 205 which is a part of the wiring pattern via the solder bumps 207. Then, the semiconductor package 200 shown in FIG. 2 is obtained by sealing the semiconductor element 203, the solder bump 207, etc. with the sealing material 211. FIG.

(Semiconductor device)

Then, the semiconductor device 300 in this embodiment is demonstrated.

The semiconductor package 200 can be used for the semiconductor device 300 shown in FIG. It does not specifically limit as a manufacturing method of the semiconductor device 300, For example, there exists the following method.

First, solder paste is supplied to the opening 209 of the solder resist layer 201 of the obtained semiconductor package 200, and the solder bump 301 is formed by reflow process. The solder bumps 301 can also be formed by attaching the solder balls produced in advance to the openings 209.

Next, by connecting the connection terminal 305 of the mounting board 303 and the solder bump 301, the semiconductor package 200 is mounted on the mounting board 303, and the semiconductor device 300 shown in FIG. 3 is obtained. .

As described above, according to the present embodiment, the prepreg 100 for the laminated sheet 213 having excellent insulation reliability can be provided. And the circuit board using the laminated board 213 is excellent in insulation reliability. Therefore, the laminated board 213 in this embodiment can be used suitably for the use which further requires insulation reliability, such as a printed wiring board which requires high density and high multilayer.

As mentioned above, although embodiment of this invention was described, these can adopt various structures of that excepting the above as an illustration of this invention. For example, in this embodiment, although the case where the prepreg is one layer was shown, you may produce a laminated board using what laminated | stacked the prepreg 100 one or more layers.

Moreover, the structure which further laminated | stacked the buildup layer on the laminated board in this embodiment can also be taken. Moreover, you may use the prepreg 100 in this embodiment also for the prepreg used for a buildup layer and a soldering resist layer. In this case, the semiconductor package 200 and the semiconductor device 300 which are more excellent in insulation reliability can be obtained.

Example

Hereinafter, although an Example and a comparative example demonstrate this invention, this invention is not limited to these. In addition, in an Example, a part shows a mass part unless there is particular notice. In addition, each thickness is represented by the average film thickness.

In the Example and the comparative example, the following raw materials are used.

(1) Brominated bisphenol A epoxy resin (Mitsubishi Chemical Corporation make, 5047, epoxy equivalent 560)

(2) Bisphenol A type epoxy resin (Mitsubishi Chemical Corporation make, 828, epoxy equivalent 190)

(3) Bisphenol F type epoxy resin (made by DIC Corporation, 830S, epoxy equivalent 170)

(4) 1,1,2,2-tetrakis (glycidylphenyl) ethane type epoxy resin (manufactured by Mitsubishi Chemical Corporation, 1031, epoxy equivalent 220)

(5) phenol novolac resin (manufactured by DIC Corporation, TD-2090, hydroxyl equivalent 105)

(6) phenol aralkyl resin (made by Mitsui Chemicals, XLC-LL, hydroxyl equivalent 175)

(7) bisphenol A novolac resin (manufactured by DIC Corporation, VH-4170, hydroxyl equivalent 115)

(8) 2-phenylimidazole (manufactured by Shikoku Chemical Co., Ltd.)

(9) Epoxysilane (Shin-Etsu Silicone Co., Ltd., KBM-403)

(10) Fused Silica (manufactured by Admatex Co., Ltd., SO-E2, average particle size 0.5 µm)

(11) Aluminum Hydroxide (manufactured by Nippon Light Metal Co., Ltd., BE-033, average particle diameter of 3.0 mu m)

(12) Dicyandiamide (manufactured by Degussa Co., Ltd.)

(13) 4,4'-diaminodiphenylmethane (made by Tokyo Chemical Co., Ltd.)

(Example 1)

The laminated board in this invention was produced using the following procedures.

1. Varnish preparation of resin composition

28.1 parts by mass of a brominated bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, 5047, epoxy equivalent 560), 20.0 parts by mass of a bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Company, 828, epoxy equivalent 190), and a phenol novolak resin (DIC Corporation) 16.3 mass parts of manufacture, TD-2090, hydroxyl equivalent 105), 0.03 mass part of 2-phenylimidazole (made by Shikoku Kasei Chemical Co., Ltd.), 0.8 mass part of epoxy silane (made by Shin-Etsu Silicone Co., Ltd., KBM-403), and melting 1.5 mass parts of silica (made by Admatex, SO-E2, average particle diameter: 0.5 micrometer), aluminum hydroxide (made by Nippon Light Metal Co., Ltd., BE-033, average particle diameter: 3.0 micrometers) to 33.3 mass parts, and 28.0 mass of methyl ethyl ketone Part was added, and it stirred using the high speed stirring apparatus, and obtained the resin varnish whose resin composition is 78 mass% on the basis of solid content. Moreover, the theoretical nitrogen content mentioned above was computed. In addition, in Example 1, the component containing a nitrogen atom in chemical formula is 2-phenylimidazole.

2. Preparation of prepreg

Using the varnish mentioned above, it is 192.0 mass with solid content of a resin composition with respect to 208.0 mass parts of glass woven fabrics (thickness 0.16 mm, basis weight 208.0 g / m <2>, breathability 5.1 cm <3> / cm <2> / sec, the product made by Nitto Macao) It was impregnated and dried for 5 minutes in a 180 degreeC drying furnace, and the prepreg of 48.0 mass% of resin composition contents was produced.

The air permeability of the glass woven fabric cuts the sample into 200 mm x 500 mm, and uses a pre-quality measuring instrument (AP-360S manufactured by Taisei Scientific Co., Ltd.) for one second per square cm when the pressure drop of water is 1.27 cm. It was calculated | required as the amount of air which passes through a cloth.

3. Manufacture of laminate

Four sheets of the above prepregs were laminated, and 18 µm thick electrolytic copper foils (manufactured by Koga Circuit Foil Co., Ltd., GTSMP) were stacked on top of each other, heated and press-molded at a pressure of 4 MPa and a temperature of 200 ° C. for 180 minutes to form a double side of 0.8 mm in thickness. A copper clad laminate was obtained.

4. Manufacturing of printed wiring board

After through-hole processing was performed to the double-sided copper clad laminated board obtained above using a 65-micrometer drill bit, it was immersed for 5 minutes in 70 degreeC swelling liquid (Atotech Japan company make, swelling deep security P), Furthermore, after immersing in 80 degreeC aqueous potassium permanganate solution (Atotech Japan Co., Concentrate compact CP) for 15 minutes, it neutralized and performed the desmear process in a through hole. Next, after etching the surface of the electrolytic copper foil layer by flash etching about 1 m, electroless copper plating was formed with a thickness of 0.5 m, the resist layer for electrolytic copper plating was formed with a thickness of 18 m, pattern copper plating was carried out, and the temperature was 200 deg. It heated for minutes and post-cure. Subsequently, the plating resist was peeled off and the entire surface was flash etched to form a pattern of L / S = 75/75 mu m. Finally, the soldering resist (PSR4000 / AUS308 by Taiyo Ink Corporation) was formed in 20 micrometers in thickness, and the double-sided printed wiring board was obtained.

(Examples 2-9 and Comparative Examples 1-8)

Except having prepared the resin varnish according to the compounding table of Table 1 and Table 2, the resin varnish was prepared like Example 1, and the prepreg, the laminated board, and the printed wiring board were produced.

Moreover, the following each evaluation was performed about the prepreg and printed wiring board obtained by each Example and the comparative example. The evaluation results are shown in Table 1.

1. Evaluation of Prepregs

(1) The outbreak situation of balance pool

The development | generation situation of the resin pool on the surface of the prepreg obtained by each Example and each comparative example was visually evaluated. The thing which no resin pool was confirmed was made into "no abnormality", and the thing in which the resin pool was confirmed on the surface of a prepreg by the fluff of glass woven fabric was made into "it exists."

(2) Measurement of nitrogen content in prepreg

The nitrogen content in the prepreg was measured by the following method.

Nitrogen content was measured as follows using the organic element analyzer (Perkin Elmer 2400 IICHNS). 20 mg of prepreg was taken, wrapped in a tin board, set in an apparatus, dropped into a combustion tube, burned in oxygen at 1000 DEG C, and the generated nitrogen gas was detected by a thermal conductivity detector.

2. Evaluation of the printed wiring board

(1) Solder heat resistance

After cutting the printed wiring board obtained by the said Example and the comparative example by 50 mm x 50 mm with a grinder saw, and processing 96 hours at 85 degreeC 85%, after immersing a sample in 260 degreeC solder tank for 30 second, an external appearance The condition of abnormality was investigated.

Evaluation criteria: no abnormality

          : Swelling (there is a swelling point overall)

(2) My migration ability

50 V was applied to the through-hole part of the printed wiring board obtained by the said Example and the comparative example on 85 degreeC 85% conditions, and the insulation resistance after 300-hour process was measured. Further, the wall-to-wall distance between the through hole and the through hole is 0.35 m. Here, what was insulation-degraded to ^10-8 ohms or less was made into "insulation deterioration."

3. Evaluation result

As is apparent from Table 1, Examples 1-9 did not have resin pooling, and were excellent in the solder heat resistance and the migration resistance of a printed wiring board.

Since the comparative example 1 used the thing with small air permeability of a glass cloth, resin pooling generate | occur | produced.

Since the comparative examples 2 and 3 used the thing containing nitrogen in a solvent, solder heat resistance and migration resistance deteriorated.

Since the comparative examples 4, 6, and 7 used the thing containing nitrogen in a hardening | curing agent, migration resistance worsened.

Since the comparative example 5 used the thing with small air permeability of a glass cloth, what used nitrogen was contained in the hardening | curing agent, but the migration did not generate | occur | produce. However, resin pooling occurred because a small air permeability of the glass cloth was used.

In Comparative Example 8, since the air permeability of the glass woven fabric exceeded 30 cm 3 / cm 2 / sec, the migration resistance deteriorated.

This application claims the priority based on Japanese Patent Application No. 2011-142630 for which it applied on June 28, 2011, and accepted all of the indication here.

Claims (11)

As a prepreg obtained by impregnating a fiber base material with a resin composition containing an epoxy resin and an epoxy resin curing agent,
Nitrogen content in the said prepreg is 0.10 mass% or less,
The air permeability of the said fiber base material is 3.0 cm <3> / cm <2> / sec or more and 30.0 cm <3> / cm <2> / sec or less. The method of claim 1,
The resin composition further contains a curing catalyst. 3. The method of claim 2,
The prepreg in which the said curing catalyst contains an imidazole compound. 4. The method according to any one of claims 1 to 3,
The prepreg whose basis weight of the said fiber base material is 145 g / m <2> or more and 300 g / m <2> or less. 5. The method according to any one of claims 1 to 4,
The prepreg whose thickness of the said fiber base material is 50 micrometers or more and 300 micrometers or less. 6. The method according to any one of claims 1 to 5,
The prepreg, wherein the fiber base material is a glass fiber base material. The laminated board containing the hardened | cured material of the prepreg of any one of Claims 1-6. The semiconductor package which mounts a semiconductor element in the circuit board obtained by carrying out the circuit processing of the laminated board of Claim 7. A step of obtaining a prepreg by impregnating a resin substrate with an epoxy resin, an epoxy resin curing agent, and a solvent to a fiber base material;
Heating the prepreg to obtain a cured product of the prepreg,
Then,
As a manufacturing method of the laminated board which performs the process of forming a via by a laser,
The theoretical nitrogen content in the said resin varnish is 0.50 mass% or less,
The manufacturing method of the laminated board whose air permeability of the said fiber base material is 3.0 cm <3> / cm <2> / sec or more and 30.0 cm <3> / cm <2> / sec or less. The method of claim 9,
The said epoxy resin hardener is an organic compound which does not contain a nitrogen atom in chemical formula, The manufacturing method of the laminated board. 11. The method according to claim 9 or 10,
The said solvent is an organic compound which does not contain a nitrogen atom in chemical formula, The manufacturing method of the laminated board.

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