TW201315767A - Prepreg, laminated board, semiconductor package, and method for manufacturing laminated board - Google Patents

Abstract

This prepreg (100) is obtained by impregnating a fiber base material (101) with a resin composition comprising an epoxy resin and an epoxy resin curing agent. The amount of nitrogen contained in the prepreg (100) is at most 0.10 mass%, and the air permeability of the fiber base material (101) is 3.0-30.0 cm3/cm2/sec.

Description

Prepreg, laminated board, semiconductor package, and method for manufacturing laminated board

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

With the recent demand for high functionality and lightness and thinness of electronic devices, the miniaturization of semiconductor devices used in such electronic devices is rapidly progressing.

On the other hand, in order to downsize the semiconductor device, it is necessary to increase the density of the circuit board to be used. Therefore, the number of via holes opened for connection between circuits is increased as compared with the prior art, and the hole density is increased. If the pore density becomes high, the distance between the walls of the through holes is close, and thus metal ions migrate along the single fibers of the fiber substrate, and ions which are short-circuited by the circuit are easily caused to migrate. When this ion migration occurs, the insulation reliability of the circuit board is lowered (for example, refer to Patent Documents 1 and 2).

Japanese Patent Publication No. 2004-149577 discloses a prepreg in which a thermosetting resin composition is impregnated with at least one of flat processing and fiber opening processing of a glass cloth. The substrate having a gas permeability of 2 to 4 cm ³ /cm ² /sec is formed, and the thermosetting resin composition is brought into a B-stage state.

There is a case where the laminate of the prepreg is used because the impregnation property of the thermosetting resin composition on the fibrous base material is improved, so that the strength of the laminated sheet is made uniform. Therefore, the inner wall of the hole formed by the hole processing can be smoothly formed, and even if the hole density becomes high so that the distance between the walls of the through hole is close, the generation of ion migration can be suppressed.

In addition, it is described that the glass fiber filament is three-dimensionally developed by the fiber opening treatment, the impregnation property to the glass fiber is improved, and the void is reduced, so that the occurrence of migration can be suppressed.

Patent Document 1: Japanese Laid-Open Patent Publication No. 2004-322364

Patent Document 2: Japanese Laid-Open Patent Publication No. Hei 6-316643

Patent Document 3: Japanese Laid-Open Patent Publication No. 2004-149577

However, when the above-mentioned flat processing or fiber opening processing is performed on a fiber base material such as glass cloth, the fiber base material may be raised. When fluff is generated on the fibrous base material, the strength of the fibrous base material is lowered, or resin is accumulated in a portion of the pile projection to roughen the surface of the prepreg.

Therefore, the technique of improving the insulation reliability of the laminated board by the processed fiber base material of the above-mentioned Patent Document 3 is effective in improving the insulation reliability, but there is still room for improvement in terms of productivity.

Therefore, an object of the present invention is to provide a laminate having excellent insulation reliability and to provide a prepreg having a good yield.

The present inventors conducted an effort to study the mechanism of generating ion migration. As a result, it was found that when the nitrogen content in the prepreg is reduced to 0.10% by mass or less, the ion mobility resistance is improved.

That is, according to the present invention, there is provided a prepreg obtained by impregnating a resin substrate containing a resin composition of an epoxy resin and an epoxy resin hardener, wherein the nitrogen content in the prepreg is 0.10% by mass. Hereinafter, the air permeability of the fibrous base material is 3.0 cm ³ /cm ² /sec or more and 30.0 cm ³ /cm ² /sec or less.

According to the present invention, by using the above-mentioned prepreg having a nitrogen content of 0.10% by mass or less, even if a fiber base material having the above air permeability is used, the ion mobility resistance of the laminated plate can be improved. Further, the fibrous base material having the above air permeability can suppress the generation of fluff and improve the yield of the prepreg. Further, according to the present invention, there is provided a laminated board comprising the cured body of the prepreg. Furthermore, according to the present invention, there is provided a semiconductor package in which a semiconductor element is mounted on a circuit board obtained by circuit-processing the laminated board.

Further, according to the present invention, there is provided a method for producing a laminated board, which comprises subjecting a resin varnish containing an epoxy resin, an epoxy resin curing agent and a solvent to a fiber base material to obtain a prepreg; and heating the above Precuring the body to obtain a hardened body of the prepreg; then forming a passage by laser; the theoretical nitrogen content in the resin varnish is 0.50% by mass or less; and the air permeability of the fiber substrate is 3.0 cm ³ /cm ² / sec or more and 30.0 cm ³ /cm ² /sec or less.

According to the present invention, a laminate having excellent insulation reliability can be obtained and a prepreg having a good yield can be provided.

The above and other objects, features and advantages of the present invention will become more apparent from

Hereinafter, embodiments of the present invention will be described using the drawings. Furthermore, In all the drawings, the same constituent elements are given the same reference numerals, and the description is omitted as appropriate. Moreover, the figure is a schematic view, and does not necessarily coincide with the actual size ratio.

(prepreg)

First, the configuration of the prepreg in the present embodiment will be described. Fig. 1 is a cross-sectional view showing an example of a configuration of a prepreg in the embodiment. The prepreg 100 is obtained by impregnating the fiber substrate 101 with the resin composition P containing the (A) epoxy resin and the (B) epoxy resin curing agent.

The nitrogen content in the prepreg 100 is 0.10% by mass or less, preferably 0.08% by mass or less, and more preferably 0.05% by mass or less. When the nitrogen content in the prepreg 100 is at most the above upper limit value, the ion mobility resistance of the laminated plate can be improved. Therefore, it is possible to suppress a special processing such as flat processing or fiber opening processing for the fiber base material in order to improve ion migration resistance. Therefore, the occurrence of fuzzing of the fibrous substrate can be suppressed, and the yield of the prepreg can be improved.

Although the reason why the ion mobility resistance of the laminated board is improved is not clear, it is presumed that if the nitrogen content in the prepreg 100 is reduced, the moisture resistance of the prepreg 100 is improved. Therefore, it becomes difficult for water to adhere to the inside of the laminate obtained from the prepreg 100, in particular, the gap between the fiber substrate and the resin, and it becomes difficult to cause ionization of metal or migration of metal ions. As a result, the generation of ion migration can be suppressed.

The measurement of the nitrogen content in the prepreg 100 can be generally carried out by a known method. For example, an organic element analysis device can be used to decompose the prepreg, convert the generated gas to N ₂ , and perform the thermal conductivity detector. Determination.

Further, the air permeability of the fibrous base material 101 in the prepreg 100 is 3.0 cm ³ /cm ² /sec or more, more preferably 3.5 cm ³ /cm ² /sec or more, and particularly preferably 4.0 cm ³ /cm ² /sec. the above. Since the prepreg 100 of the present embodiment is excellent in ion migration resistance, a fiber base material having a gas permeability of at least the above lower limit value can be used. In other words, it is possible to suppress a special processing such as flat processing or fiber opening processing for the fiber base material in order to improve ion migration resistance. Therefore, the occurrence of fluffing of the fiber base material 101 is suppressed, so that it is difficult to generate resin which is likely to be generated in the protruding portion of the pile. Therefore, the yield of the prepreg can be improved.

Further, the air permeability of the fibrous base material 101 is 30.0 cm ³ /cm ² /sec or less, more preferably 20.0 cm ³ /cm ² /sec or less, still more preferably 15.0 cm ³ /cm ² /sec or less, and particularly preferably 12.0 cm ³ /cm ² /sec or less. When the air permeability of the fiber base material 101 is at most the above upper limit value, the impregnation property of the resin composition to the fiber base material can be improved, so that the strength of the laminated plate can be made uniform. Therefore, the inner wall of the hole formed by the opening can be smoothly formed, and even if the hole density becomes high so that the distance between the walls of the through hole is close, the generation of ion migration can be suppressed.

Here, the air permeability of the fiber base material 101 can be adjusted, for example, by processing such as flat processing or fiber opening processing.

Further, the measurement of the air permeability can be measured in accordance with JIS R3420 (Frazier Type method).

Next, the material constituting the prepreg 100 will be described in detail.

In the prepreg 100 of the present embodiment, the resin composition P containing (A) epoxy resin and (B) epoxy resin hardener is impregnated into the fiber substrate. 101, and then a sheet-like material having the fiber base material 101 and the resin layers 103 and 104 obtained by semi-hardening. The sheet material having such a structure is excellent in various characteristics such as dielectric properties under high temperature and high humidity, and electrical connection reliability, and is suitable for manufacturing a laminate for a circuit board.

(resin composition)

In the following, the resin composition P containing the stain on the fibrous base material 101 is not particularly limited as long as it contains the (A) epoxy resin and the (B) epoxy resin hardener, and preferably has a low coefficient of linear expansion. And high elastic modulus and excellent thermal shock reliability.

(A) The epoxy resin is a compound having one or more epoxy propyl groups in the molecule, and is formed by a reaction of a glycidyl group by heating to form a three-dimensional network structure and harden. The (A) epoxy resin preferably contains two or more epoxy propyl groups per molecule because the use of a compound having one epoxy propyl group does not exhibit sufficient cured product characteristics even in the case of the reaction. .

Specific examples of the (A) epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol E type epoxy resin, and bisphenol M type. Bisphenol type epoxy resin such as epoxy resin, bisphenol P type epoxy resin, bisphenol Z type epoxy resin or the like; phenol novolac type epoxy resin, cresol novolac ( A phenolic varnish type epoxy resin such as cresol novolac); an aryl alkylene type epoxy resin such as a biphenyl type epoxy resin or a biphenyl aralkyl type epoxy resin; a naphthalene type epoxy resin and a fluorene type ring An epoxy resin such as an oxy-resin, a phenoxy-type epoxy resin, a dicyclopentadiene type epoxy resin, a norbornene type epoxy resin, an adamantane type epoxy resin, or a fluorene type epoxy resin. Can be used alone One of these may be used in combination of two or more types.

The content of the epoxy resin (A) is not particularly limited, but is preferably 15% by mass or more and 80% by mass or less based on the entire resin composition P. More preferably, it is 25 mass% or more and 60 mass% or less. Further, when a liquid epoxy resin such as a liquid bisphenol A type epoxy resin or a bisphenol F type epoxy resin is used in combination, the impregnation property to the fiber base material 101 can be improved, which is preferable. The content of the liquid epoxy resin is more preferably 3% by mass or more and 30% by mass or less based on the entire resin composition P. Further, when a solid bisphenol A type epoxy resin or a bisphenol F type epoxy resin is used in combination, the adhesion to the conductor can be improved.

The (B) epoxy resin curing agent is not particularly limited, and examples thereof include a phenol curing agent, an aliphatic amine, an aromatic amine, dicyanodiamine, a dioxane compound, and an acid anhydride. Among these, an organic compound containing no nitrogen atom in the chemical formula is particularly preferable, and a phenol-based curing agent and an acid anhydride containing no nitrogen atom in the chemical formula are particularly preferable. When a phenolic curing agent or an acid anhydride is used, a prepreg having a nitrogen content of 0.10% by mass or less can be obtained more efficiently.

The phenolic curing agent as the (B) epoxy resin curing agent is a compound having two or more phenolic hydroxyl groups in one molecule. In the case of a compound having one phenolic hydroxyl group in one molecule, since the crosslinked structure cannot be obtained, the properties of the cured product are deteriorated and cannot be used.

As the phenolic curing agent, for example, a phenol novolak resin, an alkylphenol novolak resin, a bisphenol A novolak resin, a dicyclopentadiene type phenol resin, a phenol aralkyl type phenol resin, a terpene modified phenol can be used. A known one or a combination of a resin or a polyvinyl phenol is used alone or in combination of two or more.

Equivalent ratio of blending amount of phenol hardener to (A) epoxy resin (phenolic hydroxyl The base equivalent/epoxy equivalent weight) is preferably 0.1 or more and 1.0 or less. Thereby, the unreacted phenol curing agent is not left, and the moisture absorption heat resistance is improved. In the case where the epoxy resin and the cyanate resin are used in combination with the resin composition P, it is particularly preferably in the range of 0.2 or more and 0.5 or less. The reason for this is that the phenol resin acts not only as a curing agent but also to harden the cyanate group and the epoxy group.

Examples of the acid anhydride of the (B) epoxy resin curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and 4-methylhexahydrophthalic anhydride. Endomethyltetrahydrophthalic anhydride, dodecyric anhydride, maleic anhydride, and the like.

Examples of the diterpene compound as the (B) epoxy resin curing agent include diammonium adipate, dinonyl dodecanoate, diterpene isophthalate, dihydroxyp-hydroxybenzoate, and the like. Dicarboxylic acid dioxime and the like.

Further, in the resin composition P, the nitrogen content in the obtained prepreg 100 may not exceed 0.10% by mass, and the following (C) curing catalyst may be used. Further, the (C) curing catalyst refers to a catalyst having a function of promoting the curing reaction of the (A) epoxy resin and the (B) epoxy resin curing agent, and is different from the (B) epoxy resin curing agent.

For example, zinc naphthenate, cobalt naphthenate, stannous octoate, cobalt octoate, cobalt (II) acetoacetate, cobalt (III) triacetate, and the like; triethylamine, tributyl a tertiary amine such as a base amine or a diazabicyclo[2,2,2]octane; 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 2-ethyl-4-ethylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxyimidazole, 2-phenyl-4,5-dihydroxyimidazole, etc. Imidazoles; phenolic compounds such as phenol, bisphenol A, nonylphenol; An organic acid such as acetic acid, benzoic acid, salicylic acid or p-toluenesulfonic acid; an onium salt compound or the like or a mixture thereof. As the (C) curing catalyst, one type of the derivative may be used alone, or two or more types including the above-mentioned derivatives may be used in combination.

The content of the (C) curing catalyst is not particularly limited as long as the nitrogen content in the obtained prepreg 100 is not more than 0.10% by mass. For example, the resin composition P is preferably contained in an amount of 0.010% by mass or more, and more preferably 0.10% by mass or more. When the content of the (C) curing catalyst is at least the above lower limit value, the effect of promoting hardening can be sufficiently obtained. Further, the content of the (C) curing catalyst is preferably 5.0% by mass or less, and particularly preferably 2.0% by mass or less based on the entire resin composition P. When the content of the (C) curing catalyst is at most the above upper limit value, the deterioration of the preservability of the prepreg 100 can be suppressed.

More preferably, the resin composition P contains (D) an inorganic filler. Examples of the (D) inorganic filler include talc, calcined clay, uncalcined clay, mica, glass, and the like; oxides such as titanium oxide, aluminum oxide, cerium oxide, and molten cerium oxide; calcium carbonate, Carbonate such as magnesium carbonate or hydrotalcite; hydroxide such as aluminum hydroxide, magnesium hydroxide or calcium hydroxide; sulfate or sulfite such as barium sulfate, calcium sulfate or calcium sulfite; zinc borate, barium metaborate and boric acid Boric acid such as aluminum, calcium borate or sodium borate; nitride such as aluminum nitride, boron nitride, tantalum nitride or carbon nitride; titanate such as barium titanate or barium titanate. One of these may be used alone, or two or more of them may be used in combination.

Among these, cerium oxide is particularly preferable, and in view of excellent low thermal expansion property, molten cerium oxide (especially spherical molten cerium oxide) is preferable. Its shape is pulverized or spherical, and it can be used to reduce the resin composition. The melt viscosity of P is a method of using a spherical cerium oxide or the like in accordance with the purpose thereof to ensure impregnation with the fibrous base material 101.

The average particle diameter of the inorganic filler (D) is not particularly limited, but is preferably 0.01 μm or more and 3 μm or less, and more preferably 0.02 μm or more and 1 μm or less. By setting the particle diameter of the (D) inorganic filler to 0.01 μm or more, the varnish can be made to have a low viscosity, and the resin composition P can be satisfactorily impregnated into the fiber base material 101. Moreover, by setting it as 3 micrometer or less, precipitation of the (D) inorganic filler in varnish, etc. can be suppressed. The average particle diameter can be measured, for example, by a particle size distribution meter (manufactured by Shimadzu Corporation, product name: laser diffraction type particle size distribution measuring apparatus SALD series).

Further, the inorganic filler (D) is not particularly limited, and an inorganic filler having a uniform particle diameter and a single dispersion may be used, and an inorganic filler having a large average particle diameter may be used. Further, one or two or more kinds of inorganic fillers which are monodisperse and/or polydisperse in average particle diameter may be used in combination.

Further, spherical cerium oxide (especially spherical molten cerium oxide) having an average particle diameter of 3 μm or less is preferable, and spherical molten cerium oxide having an average particle diameter of 0.02 μm or more and 1 μm or less is particularly preferable. Thereby, the filling property of (D) inorganic filler can be improved.

(D) The content of the inorganic filler is not particularly limited, but is preferably 2% by mass or more and 70% by mass or less, and particularly preferably 5% by mass or more and 60% by mass or less based on the entire resin composition P. When the content is within the above range, in particular, it is possible to form low thermal expansion and low water absorption.

Further, although not particularly limited, it is preferred that the resin composition P further contains (E) a coupling agent. (E) coupling agent can be improved by (A) epoxy resin The wettability at the interface with the (D) inorganic filler causes the (A) epoxy resin and the (D) inorganic filler to be uniformly fixed to the fiber substrate to improve heat resistance, particularly solder heat resistance after moisture absorption.

As the (E) coupling agent, any one may be used as long as it is a usual user. Specifically, it is preferably selected from the group consisting of an epoxy decane coupling agent, a cationic decane coupling agent, an amino decane coupling agent, and a titanate system. One or more coupling agents of a coupling agent and a polyoxygenated oil type coupling agent. Thereby, the wettability at the interface with the (D) inorganic filler can be improved, and the heat resistance can be further improved by this.

The amount of the (E) coupling agent to be added is not particularly limited as long as it depends on the specific surface area of the inorganic filler (D), and is preferably 0.05% by mass or more and 5% by mass based on 100 parts by mass of the (D) inorganic filler. Hereinafter, it is particularly preferably 0.1% by mass or more and 3% by mass or less. By setting the content to 0.05% by mass or more, the inorganic filler can be sufficiently coated (D), and heat resistance can be improved. When it is 5% by mass or less, the reaction can be favorably performed to prevent a decrease in bending strength or the like.

Further, the resin composition P may contain a thermosetting resin other than an epoxy resin such as a melamine resin, a urea resin or a cyanate resin, and it is particularly preferable to use a cyanate resin in combination.

The type of the cyanate resin is not particularly limited, and examples thereof include a novolac type cyanate resin, a bisphenol A type cyanate resin, a bisphenol E type cyanate resin, and a tetramethylbisphenol F type. A bisphenol type cyanate resin such as a cyanate resin. Among these, a phenol novolac type cyanate resin is preferred in terms of low thermal expansion. Further, one or two or more kinds of other cyanate resins may be used in combination, and are not particularly limited. The cyanate resin is preferably The resin composition P is 8 mass% or more and 20 mass% or less in total.

Further, in the resin composition P, a phenoxy resin, a polyimine resin, a polyamide amide resin, a polyamide resin, a polyphenylene ether resin, a polyether oxime resin, a polyester resin, or a polyethylene may be used in combination. Thermoplastic resin such as resin or polystyrene resin; polystyrene-based thermoplastic elastomer such as styrene-butadiene copolymer or styrene-isoprene copolymer; polyolefin-based thermoplastic elastomer; and polyamine-based elastomer A thermoplastic elastomer such as a polyester elastomer; a diene elastomer such as polybutadiene, epoxy modified polybutadiene, acrylic modified polybutadiene, or methacrylic modified polybutadiene. Among these, a heat-resistant polymer resin such as a phenoxy resin, a polyimine resin, a polyamidoximine resin, a polyamide resin, a polyphenylene ether resin or a polyether oxime resin is preferable. Thereby, the thickness of the prepreg 100 can be made uniform, and the wiring board is excellent in heat resistance and insulation of the fine wiring. Further, as the resin composition P, additives other than the above components such as a pigment, a dye, an antifoaming agent, a leveling agent, an ultraviolet absorber, a foaming agent, an antioxidant, a flame retardant, and an ion scavenger may be added as needed. .

The fiber base material 101 containing the resin composition P is not particularly limited, and examples thereof include glass fiber substrates such as glass cloth, glass woven fabric, and glass nonwoven fabric; carbon fiber substrates such as carbon cloth and carbon fiber woven fabric; and artificial mineral substrates such as rock wool. Polyammonium resin fiber such as polyamide resin fiber, aromatic polyamide resin fiber, or wholly aromatic polyamide resin fiber; polyester resin fiber, aromatic polyester resin fiber, and wholly aromatic polyester resin fiber Polyester-based resin fiber; synthetic fiber substrate composed of woven or non-woven fabric containing polyimine resin fiber, fluororesin fiber or the like as a main component; kraft paper, cotton linters An organic fiber base material such as a paper base material as a main component, such as paper, cotton velvet, and kraft pulp mixed papermaking. Among these, a glass fiber substrate is preferred. Thereby, a prepreg having low water absorption and high strength and low thermal expansion property can be obtained.

Examples of the glass constituting the glass fiber substrate include E glass, C glass, A glass, S glass, D glass, NE glass, T glass, and H glass. Among these, E glass or T glass is preferable. Thereby, the high elasticity of the prepreg can be achieved, and the thermal expansion coefficient of the prepreg can be made small.

As a fiber base material used in the present embodiment, preferably a basis weight (mass per 1m ² of the fibrous base material) of 145g / m ² or more, 300g / m ² or less persons, more preferably 160g / m ² or more, 230g / m ² or less, and still more preferably 190g / m ² or more, 205g / m ² or less.

When the basis weight is at most the above upper limit value, the impregnation property of the resin composition in the fiber base material is improved, and the reduction in strand voids or insulation reliability can be suppressed. Further, it is sometimes possible to easily form a via hole by using a laser such as carbon dioxide, UV, or excimer. Further, when the basis weight is at least the above lower limit value, the strength of the glass cloth or the prepreg is improved. As a result, there is a case where the operability is improved, the production of the prepreg is facilitated, or the effect of reducing the warpage of the substrate is improved.

The thickness of the fiber base material is not particularly limited, but is preferably 50 μm or more and 300 μm or less, more preferably 80 μm or more and 250 μm or less, and still more preferably 100 μm or more and 200 μm or less. By using the fibrous base material having such a thickness, the workability in the production of the prepreg can be further improved, and in particular, the effect of reducing the warpage is remarkable.

When the thickness of the fiber base material is at most the above upper limit value, the impregnation property of the resin composition in the fiber base material is improved, and the strand gap or the insulation can be suppressed. Reduced by the nature. Sometimes, it is easy to use a laser such as carbon dioxide, UV, or excimer to form a via hole. Further, when the basis weight is at least the above lower limit value, the strength of the glass cloth or the prepreg is improved. As a result, there is a case where the operability is improved, the production of the prepreg is facilitated, or the effect of reducing the warpage of the substrate is improved.

Further, the number of sheets of the fibrous base material used is not limited to one sheet, and a plurality of thin fiber base materials may be stacked and used. Further, in the case where a plurality of fibrous base materials are used in combination, the total thickness thereof may satisfy the above range.

Next, the manufacturing method of the prepreg 100 will be described in detail.

In the prepreg 100 of the present embodiment, the resin composition P containing the (A) epoxy resin and the (B) epoxy resin curing agent is impregnated into the fibrous base material 101 and then semi-hardened.

A method of impregnating the fiber base material 101 with the resin composition P, for example, a resin varnish V is prepared by using the resin composition P, and the fiber base material 101 is immersed in the resin varnish V, and the resin is coated by various coaters. A method of varnish V, a method of spraying resin varnish V by spraying, a method of laminating a resin layer with a supporting substrate on a fiber base material, or the like. Among these, a method of immersing the fibrous base material 101 in the resin varnish V and a method of laminating the resin substrate with the support substrate on the fibrous base material are preferred. The method of immersing the fiber base material 101 in the resin varnish V improves the impregnation property of the resin composition P with respect to the fiber base material 101. Further, in the case where the fibrous base material 101 is immersed in the resin varnish V, a usual impregnation coating apparatus can be used.

In particular, when the thickness of the fibrous base material 101 is 0.1 mm or less, a method of laminating a resin layer with a support substrate to a fibrous base material is preferred. Thereby, the impregnation of the resin substrate P with the fibrous substrate 101 can be freely adjusted. The amount can further improve the formability of the prepreg. Further, in the case of laminating a film-like resin layer, a vacuum lamination device or the like is more preferably used.

The solvent used for the resin varnish V preferably has a good solubility in the resin component in the resin composition P, but a poor solvent can be used in a range which does not cause an adverse effect. Examples of the solvent having good solubility include alcohols such as methanol and ethanol, toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, tetrahydrofuran, and dimethylformamidine. Amine, dimethylacetamide, dimethyl hydrazine, ethylene glycol, cellosolve, carbitol, and the like.

Among these, as the solvent, an organic compound containing no nitrogen atom in the chemical formula is particularly preferable, and an alcohol, methyl ethyl ketone or toluene is particularly preferable. When an organic compound containing no nitrogen atom in the chemical formula is used, a prepreg having a nitrogen content of 0.10% by mass or less can be obtained more efficiently.

The solid content of the resin varnish V is not particularly limited, and the solid content of the resin composition P is preferably 20% by mass or more and 90% by mass or less, and more preferably 50% by mass or more and 80% by mass or less. Thereby, the impregnation property of the resin varnish V with respect to the fiber base material 101 can be further improved. The specific temperature at which the resin composition P is impregnated into the fibrous base material 101 is not particularly limited. For example, the prepreg 100 can be obtained by drying at 90 ° C or higher and 220 ° C or lower. The thickness of the prepreg 100 is preferably 20 μm or more and 100 μm or less.

Further, the theoretical nitrogen content in the resin varnish V is 0.50% by mass or less, preferably 0.20% by mass or less, and more preferably 0.10% by mass or less. When the theoretical nitrogen content in the resin varnish V is at most the above upper limit, a prepreg having a nitrogen content of 0.10% by mass or less can be obtained more efficiently.

In addition, the theoretical nitrogen content in the resin varnish V is a value calculated by assuming that the nitrogen contained in the resin varnish V is only a component derived from a nitrogen atom in the chemical formula. Specifically, the nitrogen content contained in each component is calculated from the molecular weight and the number of nitrogen atoms, and the total weight is divided by the weight of the entire resin varnish, and the obtained value is expressed in %.

The prepreg 100 is 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 or may be different from the center of the fiber base material 101. In other words, the center of the fiber substrate in the thickness direction of the prepreg 100 and the center of the thickness direction of the prepreg may also be offset.

(Laminated board)

Next, the configuration of the laminated board in the present embodiment will be described. The laminated plate in the present embodiment contains a cured body of the prepreg obtained by curing the prepreg 100.

(Manufacturing method of laminated board)

Next, a method of manufacturing the laminate using the prepreg 100 obtained above will be described. The production method of the laminate using the prepreg is not particularly limited, and is, for example, as follows.

One or more prepregs are stacked, and the metal foil is superposed on the outer side, the upper and lower sides, or the single side, and the bonding is performed under a high vacuum condition using a bonding device or a Beckler device, or the metal foil is directly superposed on the pre-preg. The outer side of the dip is double-sided or single-sided.

Then, a laminate is obtained by heating, pressurizing, or heating with a drier in which the prepreg is superimposed with a metal foil by a vacuum press.

The thickness of the metal foil is, for example, 1 μm or more and 35 μm or less. Better 2 μm or more and 25 μm or less. When the thickness of the metal foil is at least the above lower limit value, the mechanical strength at the time of producing the laminated plate can be sufficiently ensured. Further, when the thickness is equal to or less than the above upper limit value, it is possible to easily form 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, iron and iron alloys, Kehua alloy (trade name), 42 alloy, nickel-steel or ultra-nickel steel and other Fe-Ni alloys, W or Mo. Further, an electrolytic copper foil with a carrier or the like can also be used.

The method of the heat treatment is not particularly limited, and for example, it can be carried out using a hot air drying device, an infrared heating device, a heating roller device, a flat plate hot plate pressurizing device, or the like. In the case where a hot air drying device or an infrared heating device is used, it can be carried out substantially without applying pressure to the above-mentioned joining. Further, in the case of using a heating roll device or a flat hot plate pressurizing device, it is possible to apply a specific pressure to the above-mentioned joint.

The temperature at the time of heat treatment is not particularly limited, and it is preferably a temperature region in which the resin to be used is melted and the curing reaction of the resin does not proceed rapidly. The temperature at which the resin is melted is preferably 120 ° C or higher, more preferably 150 ° C or higher. Further, the temperature at which the curing reaction of the resin does not proceed rapidly is preferably 250 ° C or lower, more preferably 230 ° C or lower.

In addition, the time of the heat treatment differs depending on the type of the resin to be used and the like, and is not particularly limited. For example, it can be carried out by a treatment of 30 minutes or longer and 300 minutes or shorter.

Further, the pressure of the pressurization is not particularly limited, and is, for example, preferably 0.2 MPa or more and 6 MPa or less, more preferably 2 MPa or more and 5 MPa or less.

Further, a film may be laminated on at least one surface of the laminate in the present embodiment instead of the metal foil. Examples of the film include polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polyimine, and fluorine resin.

(semiconductor package)

Next, the semiconductor package 200 in the present embodiment will be described.

The obtained laminate can be used for the semiconductor package 200 as shown in FIG. As a method of manufacturing the semiconductor package 200, for example, there are methods as described below.

A through hole 215 for interlayer connection is formed in the laminate 213, and a wiring layer is formed by a subtractive method, a semi-additive method, or the like. Then, a build-up layer (not shown in FIG. 2) is laminated as needed, and the steps of interlayer connection and circuit formation by an additive method are repeated. Further, a solder resist layer 201 is laminated as needed, and a circuit is formed by the above method to obtain a circuit substrate. Here, some or all of the build-up and solder resist layer 201 may or may not contain a fibrous substrate.

Then, after the photoresist is applied to the entire surface of the solder resist layer 201, a part of the photoresist is removed to expose a portion of the solder resist layer 201. Further, a resist having a function as a photoresist can also be used for the solder resist layer 201. In this case, the step of applying the photoresist may be omitted. Then, the exposed solder resist layer is removed to form an opening portion 209.

Then, a reflow process is performed, whereby the semiconductor element 203 is fixed to the connection terminal 205 which is a part of the wiring pattern via the solder bump 207. Then, the semiconductor element 203, the solder bumps 207, and the like are sealed by the sealing member 211, whereby the semiconductor package 200 shown in FIG. 2 is obtained.

(semiconductor device)

Next, the semiconductor device 300 in the present embodiment will be described.

The semiconductor package 200 can be used for the semiconductor device 300 as shown in FIG. The method of manufacturing the semiconductor device 300 is not particularly limited, and for example, there are methods as described below.

First, solder paste is supplied to the opening portion 209 of the solder resist layer 201 of the obtained semiconductor package 200, and a reflow process is performed to form solder bumps 301. Further, the solder bump 301 can also be formed by attaching a solder ball prepared in advance to the opening portion 209.

Then, the connection terminal 305 of the package substrate 303 and the solder bump 301 are bonded, whereby the semiconductor package 200 is mounted on the package substrate 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 board 213 having excellent insulation reliability can be provided. Further, the circuit board using the laminated board 213 is excellent in insulation reliability. Therefore, the laminated board 213 of the present embodiment can be preferably used for applications requiring higher insulation density, such as a printed wiring board having a higher density and a higher multilayer.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above may be employed. For example, in the present embodiment, the case where the prepreg is one layer is shown, but a laminate having one or more layers of the prepreg 100 may be used.

Further, it is also possible to adopt a configuration in which the buildup layer is laminated on the laminate on the present embodiment. Further, the prepreg 100 of the present embodiment can also be used for the prepreg used for the combination layer or the solder resist layer. In this case, insulation is available The semiconductor package 200 and the semiconductor device 300 are more excellent in reliability.

Example

Hereinafter, the present invention will be described by way of the present examples and comparative examples, but the present invention is not limited thereto. Further, in the examples, the parts represent parts by mass unless otherwise specified. Further, the respective thicknesses are expressed by an average film thickness.

In the examples and comparative examples, the following raw materials were used.

(1) Brominated bisphenol A type epoxy resin (5047 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of 560)

(2) Bisphenol A type epoxy resin (828 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of 190)

(3) bisphenol F type epoxy resin (830S manufactured by DIC Corporation, epoxy equivalent is 170)

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

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

(6) Phenol aralkyl resin (XLC-LL manufactured by Mitsui Chemicals Co., Ltd., hydroxyl equivalent: 175)

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

(8) 2-Phenylimidazole (manufactured by Shikoku Chemicals Co., Ltd.)

(9) Epoxy decane (KBM-403 manufactured by Shin-Etsu Silicones Co., Ltd.)

(10) molten cerium oxide (SO-E2 manufactured by Admatechs Co., Ltd., average particle diameter: 0.5 μm)

(11) Aluminium hydroxide (BE-033, manufactured by Nippon Light Metal Co., Ltd., with an average particle size of 3.0 μm)

(12) dicyanodiamine (manufactured by Degussa)

(13) 4,4'-Diaminodiphenylmethane (manufactured by Tokyo Chemical Industry Co., Ltd.)

(Example 1)

The laminate of the present invention was produced using the following procedure.

1. Preparation of varnish of resin composition

28.1 parts by mass of brominated bisphenol A type epoxy resin (5047 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 560), 20.0 parts by mass of bisphenol A type epoxy resin (828, epoxy manufactured by Mitsubishi Chemical Corporation) Ethylene phenol novolak resin (TD-2090, manufactured by DIC Corporation, hydroxyl equivalent: 105), 0.03 parts by mass of 2-phenylimidazole (manufactured by Shikoku Chemical Co., Ltd.), and 0.8 parts by mass of the equivalent of 190) and 16.3 parts by mass Oxy decane (KBM-403, manufactured by Shin-Etsu Silicone Co., Ltd.), 1.5 parts by mass of molten cerium oxide (SO-E2 manufactured by Admatechs Co., Ltd., average particle diameter: 0.5 μm), and 33.3 parts by mass of aluminum hydroxide (Japanese light metal) In the BE-033 manufactured by the company, the average particle diameter is 3.0 μm, 28.0 parts by mass of methyl ethyl ketone is added, and stirred by a high-speed stirring device to obtain a resin varnish having a resin composition of 78% by mass based on the solid content standard. . Further, the above theoretical nitrogen content was calculated. Further, in Example 1, the component containing a nitrogen atom in the chemical formula is 2-phenylimidazole.

2. Manufacturing of prepreg

Using the above varnish, impregnated with resin in an amount of 208.0 parts by mass of glass woven fabric (thickness: 0.16 mm, basis weight: 208.0 g/m ² , air permeability of 5.1 cm ³ /cm ² /sec, manufactured by Nitto Denko Macao Co., Ltd.) The varnish of 192.0 parts by mass of the solid content of the composition was dried in a drying oven at 180 ° C for 5 minutes to prepare a prepreg having a resin composition content of 48.0% by mass.

The air permeability of the glass woven fabric was cut into 200 mm × 500 mm, and a Fraser measuring instrument (AP-360S manufactured by Daiei Scientific Co., Ltd.) was used as a pressure reduction of 1.27 cm per 1 cm in 1 sec. The amount of air in the cloth is determined by the amount of air in the cloth.

3. Manufacturing of laminates

Four sheets of the above prepreg were stacked, and an electrolytic copper foil (GTSMP manufactured by Furukawa Circuit Foil Co., Ltd.) having a thickness of 18 μm was placed on top of each other, and subjected to heat and pressure molding at a pressure of 4 MPa and a temperature of 200 ° C for 180 minutes to obtain a thickness of 0.8mm double-sided copper foil laminate.

4. Manufacturing of printed wiring boards

The double-sided copper foil laminate obtained above was subjected to through-hole processing using a 65 μm drill, and then immersed in a swelling liquid at 70 ° C (Swelling Dip Securigant P manufactured by Atotech Japan Co., Ltd.) for 5 minutes, and further immersed at 80 ° C. After 15 minutes of the potassium manganate aqueous solution (Concentrate Compact CP manufactured by Atotech Japan Co., Ltd.), neutralization was carried out and the desmear treatment in the through holes was performed. Then, the surface of the electrodeposited copper foil layer was etched by about 1 μm by rapid etching, and then electroless copper plating was formed to have a thickness of 0.5 μm, and the resist layer for electrolytic copper plating was formed to have a thickness of 18 μm, and copper plating was performed at a temperature. The post heat treatment was carried out by heating at 200 ° C for 60 minutes. Then, peeling plating The resist was quickly etched over the entire surface to form a pattern of L/S = 75/75 μm. Finally, a solder resist (PSR4000/AUS308 manufactured by Sun Ink Co., Ltd.) was formed to a thickness of 20 μm on the surface of the circuit to obtain a double-sided printed wiring board.

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

A resin varnish was prepared in the same manner as in Example 1 except that a resin varnish was prepared according to the blending tables described in Tables 1 and 2, and a prepreg, a laminate, and a printed wiring board were produced.

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

1. Evaluation of prepreg (1) Production of resin accumulation

The state of occurrence of the resin accumulation on the surface of the prepreg obtained in each of the examples and the comparative examples was evaluated by visual observation. When the resin accumulation was not confirmed as "no abnormality", it was confirmed that the resin accumulation was made "yes" on the surface of the prepreg due to the pile of the glass woven fabric.

(2) Determination of nitrogen content in prepreg

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

The nitrogen content was measured in the manner described below using an organic element analyzer (PerkinElmer 2400 IICHNS). A 20 mg prepreg was placed in a tin plate, and placed in a device, the burning tube was dropped, and burned in oxygen at 1000 ° C, and the generated nitrogen gas was detected by a thermal conductivity detector.

2. Evaluation of printed wiring boards (1) Solder heat resistance

The printed wiring board obtained in the above examples and comparative examples was cut into 50 mm × 50 mm by a grinding saw, and treated at 85 ° C and 85% for 96 hours, and then the sample was immersed in a solder bath at 260 ° C for 30 seconds, and then the appearance was investigated. Whether there is an abnormality.

Evaluation criteria: no abnormalities

: There is expansion (the whole part of the expansion)

(2) migration resistance

50 V was applied to the through-hole portions of the printed wiring board obtained in the above Examples and Comparative Examples under the conditions of 85% at 85 ° C, and the insulation resistance after the treatment for 300 hours was measured. Furthermore, the distance between the through hole and the wall of the through hole was 0.35 μm. Here, if the insulation resistance is reduced to 10 ^-8 Ω or less, it is set to "insulation reduction".

3. Evaluation results

As is clear from Table 1, in Examples 1 to 9, no resin was accumulated, and the printed wiring board was excellent in solder heat resistance and migration resistance.

Since the glass woven fabric of Comparative Example 1 has a small air permeability, resin accumulation occurs.

Since Comparative Examples 2 and 3 used nitrogen containing a solvent, solder heat resistance and migration resistance were deteriorated.

Since Comparative Examples 4, 6, and 7 used nitrogen containing a hardener, migration resistance deteriorated.

Since the glass woven fabric of Comparative Example 5 had a small air permeability, the use of nitrogen contained in the curing agent did not cause migration. However, since the glass woven fabric has a small air permeability, resin accumulation occurs.

Since the air permeability of the glass woven fabric of Comparative Example 8 was more than 30 cm ³ /cm ² /sec, the migration resistance was deteriorated.

The priority of the Japanese Patent Application No. 2011-142630, filed on Jun. 28, 2011, is hereby incorporated by reference.

100‧‧‧Prepreg

101‧‧‧Fiber substrate

103, 104‧‧‧ resin layer

200‧‧‧Semiconductor package

201‧‧‧Solder layer

203‧‧‧Semiconductor components

205, 305‧‧‧ connection terminal

207, 301‧‧‧ solder bumps

209‧‧‧ openings

211‧‧‧ Sealing material

213‧‧‧Laminated boards

215‧‧‧through hole

300‧‧‧Semiconductor device

303‧‧‧Package substrate

Fig. 1 is a cross-sectional view showing an example of a configuration of a prepreg in the embodiment.

Fig. 2 is a cross-sectional view showing an example of a structure of a semiconductor package in the embodiment.

Fig. 3 is a cross-sectional view showing an example of the configuration of a semiconductor device in the embodiment.

100‧‧‧Prepreg

101‧‧‧Fiber substrate

103, 104‧‧‧ resin layer

Claims (11)

A prepreg obtained by impregnating a fiber substrate containing a resin composition containing an epoxy resin and an epoxy resin hardener; the nitrogen content in the prepreg is 0.10% by mass or less; The air permeability is 3.0 cm ³ /cm ² /sec or more and 30 cm ³ /cm ² /sec or less. The prepreg according to claim 1, wherein the resin composition further contains a hardening catalyst. The prepreg of claim 2, wherein the hardening catalyst contains an imidazole compound. The scope of the patent prepreg, Paragraph 1, wherein the basis weight of the fibrous base material is ² or less 145g / m ² or more, 300g / m. The prepreg according to claim 1, wherein the fibrous base material has a thickness of 50 μm or more and 300 μm or less. The prepreg of claim 1, wherein the fibrous substrate is a glass fiber substrate. A laminate comprising the hardened body of the prepreg according to any one of claims 1 to 6. A semiconductor package in which a semiconductor element is mounted on a circuit board obtained by circuit-processing a laminated board of claim 7 of the patent application. A method for manufacturing a laminated board, which comprises the steps of: impregnating a fiber base material with a resin varnish containing an epoxy resin, an epoxy resin hardener and a solvent to obtain a prepreg; and heating the prepreg to obtain a prepreg a hardened body; then a channel is formed by laser; the theoretical nitrogen content in the resin varnish is 0.50% by mass or less; and the air permeability of the fibrous substrate is 3.0 cm ³ /cm ² /sec or more, 30 cm ³ / Cm ² /sec or less. The method for producing a laminate according to the ninth aspect of the invention, wherein the epoxy resin hardener is an organic compound containing no nitrogen atom in the chemical formula. The method for producing a laminate according to claim 9 or 10, wherein the solvent is an organic compound containing no nitrogen atom in the chemical formula.