KR101574907B1 - Prepreg, laminated plate, semiconductor package and method for manufacturing laminated plate - Google Patents

Abstract

The prepreg 100 of the present invention is obtained by impregnating a fiber substrate 101 with a resin composition containing an epoxy resin and an epoxy resin curing agent. The nitrogen content in the prepreg 100 is 0.10 mass% or less, and the air permeability of the fibrous substrate 101 is 3.0 cm 3 / cm 2 / sec or more and 30.0 cm 3 / cm 2 / sec or less.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a prepreg, a laminate, a semiconductor package, and a manufacturing method of the laminate,

The present invention relates to a prepreg, a laminate, a semiconductor package, and a method of manufacturing a laminate.

BACKGROUND ART [0002] With the recent demand for high-performance and thin-shortening of electronic devices, miniaturization of semiconductor devices used in these electronic devices is rapidly proceeding.

On the other hand, when miniaturizing a semiconductor device, it is necessary to increase the density of the circuit board to be used. Therefore, the number of through holes that are pierced for connection between circuits increases and the hole density increases. As the hole density becomes higher, the distance between the walls of the through holes becomes close to each other, so that metal ions are shifted along the single fibers of the fiber base material, and ion migration which short circuits the circuit is likely to occur. If this ion migration occurs, the insulation reliability of the circuit board is lowered (see, for example, Patent Documents 1 and 2).

Patent Document 3 (Japanese Unexamined Patent Publication (Kokai) No. 2004-149577) discloses a method for producing a thermosetting resin composition, which has a degree of air permeability of 2 to 4 cm 3 / cm 2 / sec by subjecting a glass cloth to at least one of a flattening process and a carding process, A resin composition is impregnated, and the thermosetting resin composition is put into a B-stage state.

In the laminate using such a prepreg, the impregnation property of the thermosetting resin composition to the fiber substrate is improved, so that the strength of the laminate is made uniform. Therefore, it is described that the inner wall of the hole formed by the drilling process can be formed smoothly, and the occurrence of ion migration can be suppressed even if the hole density becomes high and the distance between the walls of the through hole becomes close to each other.

In addition, it is described that the glass fiber yarn is spatially expanded by the carding process to improve the impregnation property with respect to the glass fiber, thereby reducing voids, thereby suppressing the occurrence of migration.

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

However, when the above-mentioned flattening or carding is performed on a fiber base material such as a glass cloth, the fiber base material may cause fluff. When napping is generated on the fibrous substrate, the strength of the fibrous base material is lowered, or the resin protrusion is generated in the protruded portion of the napping, resulting in a rough surface of the prepreg.

Therefore, the technique of improving the insulation reliability of the laminated board by processing the fiber base material as in Patent Document 3 described above was effective in improving the insulation reliability, but there was still room for improvement in terms of the yield.

Therefore, it is an object of the present invention to provide a prepreg in which a laminated board excellent in insulation reliability can be obtained and a yield is good.

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

That is, according to the present invention,

A prepreg obtained by impregnating a fiber substrate with a resin composition containing an epoxy resin and an epoxy resin curing agent,

The nitrogen content in the prepreg is 0.10 mass% or less,

Wherein the fiber substrate has an air permeability of 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 mass% or less, it is possible to improve the ion migration resistance of the laminated sheet even if a fiber base material having the aforementioned air permeability is used. In addition, in the above-described fiber substrate having air permeability, generation of fluffs is suppressed, and the yield of the prepreg can be improved.

Further, according to the present invention,

There is provided a laminate including the cured product of the prepreg.

Further, 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,

A step of impregnating a fiber substrate with a resin varnish containing an epoxy resin, an epoxy resin curing agent and a solvent to obtain a prepreg;

A step of heating the prepreg to obtain a cured product of the prepreg,

And then,

A manufacturing method of a laminated board for performing a step of forming a via by a laser,

The resin varnish has a theoretical nitrogen content of 0.50 mass% or less,

Wherein 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, it is possible to obtain a laminated board having excellent insulation reliability, and to provide a prepreg having a good yield.

The foregoing and other objects, features and advantages of the present invention will become more apparent from the following description of a preferred embodiment thereof 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 the semiconductor package in this embodiment.
3 is a cross-sectional view showing an example of the configuration of the semiconductor device in the present embodiment.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, the same constituent elements are denoted by the same reference numerals, and a description thereof will be omitted. It should be noted that the drawings are schematic diagrams and do not necessarily correspond to the actual dimensional ratios.

(Prepreg)

First, the structure of the prepreg in this embodiment will be described. 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 substrate 101 with a resin composition P containing (A) an epoxy resin and (B) an epoxy resin curing agent.

The nitrogen content in the prepreg 100 is 0.10 mass% or less, preferably 0.08 mass% or less, and more preferably 0.05 mass% or less. When the nitrogen content in the prepreg 100 is not more than the upper limit value, the ion migration resistance of the laminated plate can be improved. Therefore, in order to improve the ion migration resistance, it is possible to suppress special processing such as flat processing and carding processing performed on the fibrous substrate. Therefore, occurrence of occurrence of napping of the fibrous substrate can be suppressed, and the yield of the prepreg can be improved.

The reason why the ion migration resistance of the laminated board is improved is not very clear, but it is presumed that the following. When the nitrogen content in the prepreg 100 is reduced, the moisture resistance of the prepreg 100 is improved. Therefore, moisture does not adhere well to the inside of the laminate obtained from the prepreg 100, particularly, the gap between the fiber substrate and the resin, so that ionization of the metal and migration of metal ions are not generated well. As a result, it is presumed that the occurrence of ion migration is suppressed.

The nitrogen content in the prepreg 100 can be measured by a generally known method. For example, the prepreg may be burned and decomposed using an organic element analyzer, the generated gas may be converted into N ₂ , As shown in FIG.

The air permeability of the fiber substrate 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 or more . Since the prepreg 100 in this embodiment is excellent in ion-migration resistance, a fiber base material having an air permeability higher than the lower limit value described above can be used. In other words, in order to improve the ion migration resistance, it is possible to suppress special processing such as flattening and carding, which is performed on the fiber base material. Therefore, since the generation of the fluff of the fibrous substrate 101 is suppressed, a resin pool, which is likely to be generated at the projected portion of the fluff, is not generated well. Therefore, the yield of the prepreg can be improved.

The air permeability of the fibrous substrate 101 is 30.0 cm3 / cm2 / sec or less, more preferably 20.0 cm3 / cm2 / sec or less, further preferably 15.0 cm3 / cm2 / sec or less, particularly preferably 12.0 cm3 / Cm2 / sec or less. If the air permeability of the fibrous substrate 101 is not more than the upper limit, the impregnation property of the resin composition to the fibrous substrate is improved, so that the strength of the laminate can be made uniform. Therefore, the inner wall of the hole formed by the drilling process can be formed smoothly, and the occurrence of ion migration can be suppressed even if the hole density becomes high and the distance between the walls of the through hole approaches.

Here, the air permeability of the fibrous substrate 101 can be adjusted by, for example, processing such as flattening or carding.

In addition, the air permeability can be measured in accordance with the JIS R 3420 method (fibrillation method).

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

The prepreg 100 in this embodiment is obtained by impregnating the fiber substrate 101 with a resin composition P containing (A) an epoxy resin and (B) an epoxy resin curing agent, A fiber substrate 101, and resin layers 103 and 104. The sheet- 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 conditions, and is suitable for producing a laminated board for a circuit board.

(Resin composition)

The resin composition P to be impregnated into the fiber substrate 101 is not particularly limited as long as it contains (A) an epoxy resin and (B) an epoxy resin curing agent. However, the resin composition P has a low linear expansion coefficient and a high elastic modulus, .

(A) The epoxy resin is a compound having at least one glycidyl group in the molecule, which forms a three-dimensional network structure by reacting with a glycidyl group by heating and is cured. It is preferable that the epoxy resin (A) contains at least two glycidyl groups in one molecule. This is because the compound having only one glycidyl group can not exhibit sufficient cured characteristics even when it is reacted.

Specific examples of the epoxy resin (A) include epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol E type epoxy resin, bisphenol M type epoxy resin, bisphenol P type epoxy resin, bisphenol Z Novolak type epoxy resins such as phenol novolak type epoxy resins and cresol novolak type epoxy resins, biphenyl type epoxy resins, biphenyl aralkyl type epoxy resins, and the like An epoxy resin such as an arylalkylene type epoxy resin, a naphthalene type epoxy resin, an anthracene type epoxy resin, a phenoxy type epoxy resin, a dicyclopentadiene type epoxy resin, a norbornene type epoxy resin, an adamantane type epoxy resin and a fluorene type epoxy resin And the like. One of these may be used alone, or two or more of them may be used in combination.

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 total amount of the resin composition P. [ More preferably 25 mass% or more and 60 mass% or less. A liquid epoxy resin such as a liquid bisphenol A type epoxy resin or a bisphenol F type epoxy resin is preferably used in combination because the impregnation property to the fiber base material 101 can be improved. The content of the liquid epoxy resin in the resin composition P is more preferably 3% by mass or more and 30% by mass or less. When a solid bisphenol A type epoxy resin or a bisphenol F type epoxy resin is used in combination, adhesion to a conductor can be improved.

Examples of the epoxy resin curing agent (B) include, but are not limited to, phenolic curing agents, aliphatic amines, aromatic amines, dicyandiamide, dihydrazide compounds and acid anhydrides. Among them, an organic compound containing no nitrogen atom in the formula is particularly preferable, and a phenolic curing agent and an acid anhydride which do not contain a nitrogen atom in the formula are particularly preferable. When a phenol-based curing agent or an acid anhydride is used, a prepreg having a nitrogen content of 0.10 mass% or less can be obtained more efficiently.

The phenolic curing agent (B) as the 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 can not be obtained, the properties of the cured product deteriorate and can not be used.

Examples of the phenol-based curing agent include known phenol novolac resins, alkylphenol novolak resins, bisphenol A novolac resins, dicyclopentadiene-type phenol resins, xylocophenol resins, terpene-modified phenol resins, Can be used singly or in combination of two or more kinds.

The blending amount of the phenol curing agent is preferably 0.1 to 1.0 in terms of the equivalent ratio (phenolic hydroxyl group equivalent / epoxy group equivalent) to the epoxy resin (A). As a result, the unreacted phenol curing agent is prevented from remaining and the moisture absorption and heat resistance is improved. When the resin composition P is used in combination with an epoxy resin and a cyanate resin, a range of 0.2 or more and 0.5 or less is particularly preferable. This is because the phenol resin acts not only as a curing agent but also accelerates curing of a cyanate group and an epoxy group.

Examples of the acid anhydride as the epoxy resin curing agent (B) include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecenylsuccinic anhydride, maleic anhydride And the like.

Examples of the dihydrazide compound (B) as the epoxy resin curing agent include carboxylic acid esters such as adipic acid dihydrazide, dodecanic acid dihydrazide, isophthalic acid dihydrazide and p-oxybenzoic acid dihydrazide, Dihydrazide and the like.

The resin composition P may also be used in combination with the following curing catalyst (C) to such an extent that the nitrogen content in the obtained prepreg 100 does not exceed 0.10 mass%. The (C) curing catalyst is a catalyst having a function of promoting the curing reaction between the epoxy resin (A) and the epoxy resin curing agent (B), and is distinguished from the epoxy resin curing agent (B).

For example, organic metal salts such as zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, cobalt (II) bisacetylacetonate and cobalt (III) trisacetylacetonate; organic metal salts such as triethylamine, tributylamine, 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazole, Imidazoles such as ethylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxyimidazole and 2-phenyl- , Phenol compounds such as phenol, bisphenol A and nonylphenol, organic acids such as acetic acid, benzoic acid, salicylic acid and para toluenesulfonic acid, and onium salt compounds, and the like, or mixtures thereof. As the (C) curing catalyst, one type of curing catalyst may be used alone, or two or more types of these curing catalysts may be used in combination.

The content of the curing catalyst (C) is not particularly limited as long as the nitrogen content in the obtained prepreg 100 does not exceed 0.10 mass%. For example, the total amount of the resin composition P is preferably 0.010% by mass or more, more preferably 0.10% by mass or more. If the content of the curing catalyst (C) is lower than the lower limit, the effect of promoting curing can be sufficiently obtained. The content of the curing catalyst (C) in the resin composition P is preferably 5.0 mass% or less, more preferably 2.0 mass% or less. When the content of the curing catalyst (C) is not more than the upper limit value, deterioration of the preservability of the prepreg (100) can be suppressed.

The resin composition P preferably further contains (D) an inorganic filler. Examples of the inorganic filler (D) include silicates such as talc, calcined clay, unbaked clay, mica and glass, oxides such as titanium oxide, alumina, silica and fused silica, calcium carbonate, magnesium carbonate, hydrotalcite, Hydroxides such as carbonates of aluminum hydroxide, magnesium hydroxide and calcium hydroxide; sulfates or sulfites of barium sulfate, calcium sulfate and calcium sulfite; borates such as zinc borate, barium metaborate, aluminum borate, calcium borate and sodium borate; Nitrides such as boron nitride, silicon nitride, and carbon nitride, and titanate salts such as strontium titanate and barium titanate. One of these may be used alone, or two or more of them may be used in combination.

Of these, silica is particularly preferable, and fused silica (particularly spherical fused silica) is preferable because of its excellent low-temperature expansion. When the melt viscosity of the resin composition P is lowered to secure the impregnation property with respect to the fiber substrate 101, a spherical silica is used, and a method suitable for the purpose is adopted.

The average particle diameter of the inorganic filler (D) is not particularly limited, but is preferably 0.01 mu m or more and 3 mu m or less, particularly preferably 0.02 mu m or more and 1 mu m or less. By setting the particle size of the inorganic filler (D) to be at least 0.01 mu m, the resin composition P can be impregnated with the resin composition P well by setting the varnish at a low viscosity. Further, by setting the thickness to 3 m or less, (D) sedimentation of the inorganic filler can be suppressed in the varnish. The average particle size can be measured by, for example, a particle size distribution meter (manufactured by Shimadzu Corporation, product name: laser diffraction particle size distribution measurement apparatus SALD series).

The inorganic filler (D) is not particularly limited, but an inorganic filler whose average particle size is monodispersed may be used, or an inorganic filler whose average particle size is polydispersed may be used. One kind or two or more types of inorganic fillers having an average particle size of monodisperse and / or polydisperse may be used in combination.

Furthermore, spherical silica having an average particle size of 3 μm or less (particularly spherical fused silica) is preferable, and spherical fused silica having an average particle size of 0.02 μm or more and 1 μm or less is particularly preferable. As a result, the filling property of the inorganic filler (D) can be improved.

The content of the inorganic filler (D) is not particularly limited, but is preferably 2% by mass or more and 70% by mass or less, more preferably 5% by mass or more and 60% by mass or less, When the content is within the above range, particularly low thermal expansion and low absorption can be achieved.

The resin composition P is not particularly limited, but it is preferable that the resin composition P further contains a coupling agent (E). (E) The coupling agent improves the interfacial wettability between the epoxy resin (A) and the inorganic filler (D), thereby uniformly fixing the epoxy resin (A) and the inorganic filler (D) to the fiber substrate, The solder heat resistance after soldering can be improved.

As the coupling agent (E), any of conventionally used coupling agents may be used. Specifically, the coupling agent may be selected from an epoxy silane coupling agent, a cationic silane coupling agent, an aminosilane coupling agent, a titanate coupling agent and a silicone oil coupling agent It is preferable to use at least one kind of coupling agent. As a result, the wettability with the interface of the inorganic filler (D) can be increased, and the heat resistance can be further improved accordingly.

The amount of the (E) coupling agent to be added is not particularly limited because it depends on the specific surface area of the inorganic filler (D), and is preferably 0.05 mass% or more and 5 mass% or less with respect to 100 mass parts of the inorganic filler (D) % Or more and 3 mass% or less. When the content is 0.05% by mass or more, the inorganic filler (D) can be sufficiently coated to improve the heat resistance. When the content is 5% by mass or less, the reaction progresses well and the decrease in the bending strength and the like can be prevented.

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

Examples of the cyanate resin include, but are not limited to, bisphenol-type cyanates such as novolak type cyanate resin, bisphenol A type cyanate resin, bisphenol E type cyanate resin and tetramethyl bisphenol F type cyanate resin Resins and the like. Among them, a phenol novolak type cyanate resin is preferable because of its low thermal expansion. In addition, one or more other cyanate resins may be used in combination, and it is not particularly limited. The cyanate resin is preferably not less than 8% by mass and not more than 20% by mass of the entire resin composition P. [

Examples of the resin composition P include a thermoplastic resin 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, Butadiene copolymers and styrene-isoprene copolymers; thermoplastic elastomers such as polyolefin thermoplastic elastomers, polyamide elastomers and polyester elastomers; thermoplastic elastomers such as polybutadiene, epoxy-modified polybutadiene, acrylic modified polybutadiene, And a diene-based elastomer such as cryl-modified polybutadiene may be used in combination. 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 the heat resistance and the insulation of the fine wiring are excellent as the wiring board. Additives other than the above components such as pigments, dyes, antifoaming agents, leveling agents, ultraviolet absorbers, foaming agents, antioxidants, flame retardants and ion scavengers may be added to the resin composition P, if necessary.

The fiber substrate 101 impregnated with the resin composition P is not particularly limited, and examples thereof include glass fiber materials such as glass cloth, glass woven fabric and glass nonwoven fabric, carbon fiber materials such as carbon cloth and carbon fiber fabric, Polyamide resin fiber such as polyamide resin fiber, aromatic polyamide resin fiber and all aromatic polyamide resin fiber, polyester resin fiber, aromatic polyester resin fiber and all aromatic polyester resin fiber A synthetic fiber base material composed of a woven or nonwoven fabric composed mainly of an ester type resin fiber, a polyimide resin fiber and a fluororesin fiber, a paper base material mainly composed of a kraft paper, a korean paper cloth, Based organic fiber substrate and the like. Of these, glass fiber substrates are preferred. Thereby, a prepreg having low water absorption, high strength, and low thermal expansion can be obtained.

Examples of the glass constituting the glass fiber base material include E glass, C glass, A glass, S glass, D glass, NE glass, T glass, H glass and the like. Of these, E glass or T glass is preferable. As a result, it is possible to achieve a high elasticity of the prepreg and to reduce the thermal expansion coefficient of the prepreg.

The fibrous substrate used in the present embodiment preferably has a basis weight (mass of fiber base material per 1 m 2) of 145 g / m 2 or more and 300 g / m 2 or less, more preferably 160 g / m 2 or more and 230 g / , More preferably not less than 190 g / m 2 and not more than 205 g / m 2.

When the basis weight is not more than the upper limit value, the impregnation property of the resin composition in the fiber substrate is improved, and deterioration of the strand canvas and insulation reliability can be suppressed. In addition, formation of through holes by laser such as carbon dioxide, UV, excimer or the like may be facilitated. When the basis weight is not less than the above lower limit value, strength of the glass cloth or prepreg is improved. As a result, the handling property may be improved, the prepreg may be easily manufactured, or the bending reduction effect of the substrate may be improved.

The thickness of the fiber substrate is not particularly limited, but is preferably 50 占 퐉 or more and 300 占 퐉 or less, more preferably 80 占 퐉 or more and 250 占 퐉 or less, further preferably 100 占 퐉 or more and 200 占 퐉 or less. By using the fibrous base material having such a thickness, the handling property at the time of preparing the prepreg is further improved, and the effect of reducing warpage is remarkable.

When the thickness of the fibrous substrate is not more than the upper limit, the impregnating property of the resin composition in the fibrous substrate is improved, and deterioration of the stranded structure and insulation reliability can be suppressed. In addition, formation of through holes by laser such as carbon dioxide, UV, excimer or the like may be facilitated. When the basis weight is not less than the above lower limit value, strength of the glass cloth or prepreg is improved. As a result, the handling property may be improved, the prepreg may be easily manufactured, or the bending reduction effect of the substrate may be improved.

The number of fibers used is not limited to one, and a plurality of thin fiber substrates may be stacked. When a plurality of fiber substrates are stacked and used, the total thickness may satisfy the above range.

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

The prepreg 100 in this embodiment is obtained by impregnating the fiber substrate 101 with a resin composition P containing (A) an epoxy resin and (B) an epoxy resin curing agent, and then semi-curing .

The resin composition P may be impregnated into the fiber substrate 101 by, for example, preparing a resin varnish V by using the resin composition P, immersing the fiber substrate 101 in the resin varnish V, A method of applying the varnish V, a method of spraying the resin varnish V by spraying, a method of laminating the resin layer with the supporting substrate to the fiber substrate, and the like. Among them, a method of immersing the fiber substrate 101 in the resin varnish V, and a method of laminating the resin base layer with the supporting substrate to the fiber substrate are preferable. The method of immersing the fiber substrate 101 in the resin varnish V can improve the impregnability of the resin composition P with respect to the fiber substrate 101. [ Further, when the fiber substrate 101 is immersed in the resin varnish V, a conventional impregnation coating equipment can be used.

Particularly, when the thickness of the fibrous substrate 101 is 0.1 mm or less, a method of laminating the resin base layer with the supporting substrate to the fibrous substrate is preferable. Thus, the impregnation amount of the resin composition P with respect to the fiber substrate 101 can be freely adjusted, and the moldability of the prepreg can be further improved. In the case of laminating a resin layer on a film, it is more preferable to use a vacuum laminator or the like.

The solvent used in the resin varnish V preferably shows good solubility with respect to the resin component in the resin composition P, but a poor solvent may be used within a range not adversely affecting. Examples of the solvent having good solubility include alcohols such as methanol and ethanol, alcohols such as toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, tetrahydrofuran, dimethylformamide, dimethylacetamide , Dimethyl sulfoxide, ethylene glycol, cellosolve, carbitol and the like.

Among them, an organic compound containing no nitrogen atom in the formula is particularly preferable as a solvent, and alcohols, methyl ethyl ketone, and toluene are particularly preferable. When an organic compound containing no nitrogen atom in the 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, but is preferably 20% by mass or more and 90% by mass or less, more preferably 50% by mass or more and 80% by mass or less, As a result, the impregnation property of the resin varnish V with respect to the fiber base material 101 can be further improved. The predetermined temperature for impregnating the fiber substrate 101 with the resin composition P is not particularly limited, but the prepreg 100 can be obtained, for example, by drying at 90 ° C or higher and 220 ° C or lower. The thickness of the prepreg 100 is preferably 20 占 퐉 or more and 100 占 퐉 or less.

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 not more than the upper limit, a prepreg having a nitrogen content of 0.10 mass% or less can be obtained more efficiently.

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

The thickness of the resin layer 103 and the resin layer 104 may be substantially the same or different from each other with the fiber base 101 as the center. In other words, the center of the prepreg 100 in the thickness direction of the fiber base material and the center of the prepreg in the thickness direction may be shifted.

(Laminates)

Next, the structure of the laminated board in this embodiment will be described. The laminated board in this embodiment includes a cured product of a prepreg obtained by curing the prepreg 100 described above.

(Production method of laminate)

Next, a method for producing a laminated plate using the prepreg 100 obtained as described above will be described. The method of producing the laminate using the prepreg is not particularly limited, but examples thereof are as follows.

One or more prepregs may be superimposed on each other and the metal foil may be superimposed on the upper and lower sides or one side of the outer side of the prepregs to bond them under a high vacuum condition using a laminator or a beaker apparatus, Overlap.

Next, the laminated plate obtained by superimposing the metal foil on the prepreg is heated, pressurized, or heated by a vacuum press.

The thickness of the metal foil is, for example, 1 mu m or more and 35 mu m or less. More preferably not less than 2 占 퐉 and not more than 25 占 퐉. When the thickness of the metal foil is not less than the above lower limit value, the mechanical strength at the time of producing the laminated board can be sufficiently secured. When the thickness is not more than the upper limit value, it is easy to 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, Cobal (trade name), Fe-Ni alloys such as 42 alloy, Invar or Super Invar, W or Mo and the like. An electrolytic copper foil with a carrier can also be used.

The method of performing the heat treatment is not particularly limited, and can be carried out by using, for example, a hot air drying apparatus, an infrared heating apparatus, a heating roll apparatus, a flat plate thermal press apparatus, or the like. When a hot-air drying apparatus or an infrared heating apparatus is used, the bonding can be carried out without substantially applying pressure. In the case of using a heating roll apparatus or a flat plate type hot press apparatus, it is possible to perform the above-mentioned bonding by applying a predetermined pressure.

The temperature at the time of the heat treatment is not particularly limited, but it is preferable that the temperature is in a range where the resin used is melted and the curing reaction of the resin does not progress rapidly. The temperature at which the resin is melted is preferably 120 占 폚 or higher, and more preferably 150 占 폚 or higher. The temperature at which the curing reaction of the resin does not proceed rapidly is preferably 250 DEG C or lower, more preferably 230 DEG C or lower.

The heating treatment time is not particularly limited because it varies depending on the kind of the resin to be used. For example, the heating treatment can be performed for 30 minutes or longer and 300 minutes or shorter.

The pressure for pressurizing is not particularly limited, but is preferably 0.2 to 6 MPa, more preferably 2 to 5 MPa.

Instead of the metal foil, a film may be laminated on at least one surface of the laminate according to the present embodiment. Examples of the film include polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polyimide, and fluorine-based resins.

(Semiconductor package)

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

The obtained laminated plate can be used for the semiconductor package 200 shown in Fig. As a manufacturing method of the semiconductor package 200, for example, the following method is available.

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. Thereafter, a buildup layer (not shown in Fig. 2) is stacked as necessary, and the steps of interlayer connection and circuit formation by the additive process are repeated. Then, a solder resist layer 201 is laminated as required, and a circuit is formed by a method similar to that 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 include a fiber substrate.

Next, 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 part of the solder resist layer 201. A resist having a photoresist function may also be used for the solder resist layer 201. [ In this case, the step of coating the photoresist can be omitted. Next, the exposed solder resist layer is removed to form openings 209. [

Subsequently, reflow processing is performed to fix the semiconductor element 203 on the connection terminal 205, which is a part of the wiring pattern, with the solder bumps 207 interposed therebetween. Thereafter, the semiconductor element 203, the solder bumps 207, and the like are sealed with the sealing material 211 to obtain the semiconductor package 200 shown in Fig.

(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 shown in Fig. The manufacturing method of the semiconductor device 300 is not particularly limited, and for example, the following method is available.

First, solder paste is supplied to the openings 209 of the solder resist layer 201 of the obtained semiconductor package 200, and reflow processing is performed to form the solder bumps 301. The solder bumps 301 can also be formed by mounting solder balls previously prepared in the openings 209. [

Next, the semiconductor package 200 is mounted on the mounting board 303 by bonding the connection terminals 305 of the mounting board 303 and the solder bumps 301 to obtain the semiconductor device 300 shown in Fig. 3 .

As described above, according to the present embodiment, it is possible to provide the prepreg 100 for the laminated plate 213 excellent in insulation reliability. The circuit board using the laminated plate 213 is excellent in insulation reliability. Therefore, the laminate plate 213 in the present embodiment can be preferably used for applications requiring higher insulation reliability such as printed wiring boards requiring high density and high multilayer structure.

As described above, the embodiments of the present invention have been described. However, the present invention may be applied to various configurations other than the above. For example, although the case where the prepreg is one layer is shown in the present embodiment, a laminated board may be produced using a laminate of one or more prepregs 100.

It is also possible to adopt a configuration in which a buildup layer is further laminated on the laminated board in the present embodiment. The prepreg 100 according to the present embodiment may also be used for a prepreg used for a buildup layer or a solder 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, the present invention will be described with reference to examples and comparative examples, but the present invention is not limited thereto. In the following Examples, "parts" means "parts by weight" unless otherwise specified. Each thickness is indicated by an average film thickness.

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

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

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

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

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

(5) Phenol novolak resin (TD-2090, manufactured by DIC, hydroxyl equivalent 105)

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

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

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

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

(10) Fused silica (SO-E2, manufactured by Admatechs Co., average particle diameter 0.5 mu m)

(11) Aluminum hydroxide (BE-033, average particle diameter 3.0 mu m, manufactured by Nippon Kayaku Co., Ltd.)

(12) Dicyandiamide (manufactured by Degussa)

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

(Example 1)

The following procedure was used to produce a laminate according to the present invention.

1. Varnish preparation of resin composition

28.1 parts by mass of a brominated bisphenol A type epoxy resin (Mitsubishi Chemical Corporation, 5047, epoxy equivalent: 560), 20.0 parts by mass of bisphenol A type epoxy resin (Mitsubishi Chemical Corporation, 828, epoxy equivalent 190) 16.3 parts by mass of TD-2090, hydroxyl equivalent 105), 0.03 parts by mass of 2-phenylimidazole (manufactured by Shikoku Chemicals), 0.8 parts by mass of epoxy silane (KBM-403, 1.5 parts by mass of silica (SO-E2 manufactured by Admatech Co., Ltd., average particle diameter 0.5 占 퐉), 33.3 parts by mass of aluminum hydroxide (BE-033, average particle size 3.0 占 퐉, manufactured by Nippon Light Metal Co., Ltd.), 28.0 mass parts of methyl ethyl ketone And the mixture was stirred using a high-speed stirring apparatus to obtain a resin varnish having a resin composition of 78 mass% based on the solid content. The above-described theoretical nitrogen content was calculated. Further, in Example 1, the component containing a nitrogen atom in the chemical formula is 2-phenylimidazole.

2. Preparation of prepreg

Using the varnish described above, varnish was added to 192.0 parts by mass of the resin composition as a solid component of a glass woven fabric (thickness 0.16 mm, basis weight 208.0 g / m 2, air permeability 5.1 cm 3 / cm 2 / sec, Nittobo Macao Co., Impregnated and dried in a drying oven at 180 캜 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 measured by cutting a sample to 200 mm x 500 mm and measuring the pressure drop per square centimeter when the pressure drop of water was 1.27 cm by using a pre-measuring machine (AP-360S manufactured by Taisei Scientific Co., Ltd.) The amount of air passing through the cloth was obtained.

3. Manufacture of laminates

Four sheets of the above prepregs were superimposed, and an electrolytic copper foil (GTSMP, manufactured by Kohaku Foil Co., Ltd.) having a thickness of 18 탆 was stacked on top and bottom and heated and pressed at a pressure of 4 MPa and a temperature of 200 캜 for 180 minutes. To obtain a copper clad laminate.

4. Manufacture of printed wiring board

The double-sided copper clad laminate thus obtained was subjected to through-hole processing using a drill bit having a diameter of 65 mu m and then immersed in a swelling solution (Swelling Deep Sycregent P manufactured by Atotech Japan Co., Ltd.) at 70 DEG C for 5 minutes, And further immersed in an aqueous potassium permanganate solution (Concentrate Compact CP, manufactured by Atotech Japan) at 80 ° C for 15 minutes, neutralized and subjected to desmear treatment in a through hole. Next, the surface of the electrolytic copper foil layer was etched by about 1 탆 by flash etching, electroless copper plating was formed to a thickness of 0.5 탆, a resist layer for electrolytic copper plating was formed to a thickness of 18 탆, pattern copper plating was performed, And heated for a minute to post-cure. Subsequently, the plating resist was peeled off and the entire surface was subjected to flash etching to form a pattern of L / S = 75/75 μm. Finally, a solder resist (PSR4000 / AUS308, manufactured by TAIYO INK Co., Ltd.) was formed on the circuit surface to a thickness of 20 mu m 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 in accordance with the formulation tables shown in Tables 1 and 2 to prepare a prepreg, a laminate, and a printed wiring board.

The following evaluations were carried out on the prepreg and the printed wiring board obtained in each of the examples and the comparative examples. The evaluation results are shown in Table 1.

1. Evaluation of prepreg

(1) Outbreak situation

The occurrence of resin gaps on the surface of the prepreg obtained in each of the Examples and Comparative Examples was visually evaluated. A sample in which the resin adherence was not confirmed was defined as " no abnormality ", and a sample in which the resin adherence was confirmed on the prepreg surface by the fluff of the glass woven fabric was determined as "

(2) Measurement of nitrogen content in prepreg

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

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

2. Evaluation of printed wiring board

(1) Solder heat resistance

The printed wiring boards obtained in the above-mentioned Examples and Comparative Examples were cut into a grinder with a size of 50 mm x 50 mm, treated at 85 캜 and 85% for 96 hours, immersed in a solder bath at 260 캜 for 30 seconds, Were investigated.

Evaluation Criteria: No abnormality

          : Swelling (there is a swelling point as a whole)

(2) My migration ability

50 V was applied to the through-hole portions of the printed wiring boards obtained in the above Examples and Comparative Examples under the condition of 85 캜 and 85%, and the insulation resistance after the treatment for 300 hours was measured. The distance between the through-holes and the through-holes is 0.35 mu m. Here, insulation deterioration of not more than 10 < ^-8 >

3. Evaluation results

As apparent from Table 1, in Examples 1 to 9, there were no resin gaps and the solder heat resistance and migration resistance of the printed wiring board were excellent.

In Comparative Example 1, since the glass woven fabric having a low air permeability was used, a resin sticking occurred.

In Comparative Examples 2 and 3, since solder containing nitrogen was used, solder heat resistance and migration resistance deteriorated.

In Comparative Examples 4, 6, and 7, since the curing agent containing nitrogen was used, migration resistance deteriorated.

In Comparative Example 5, a glass woven fabric having a low air permeability was used, so that a material containing nitrogen as a curing agent was used, but migration did not occur. However, since the glass woven fabric having a low air permeability was used, a resin stain occurred.

In Comparative Example 8, the glass woven fabric having an air permeability exceeding 30 cm < 3 > / cm < 2 > / sec.

This application claims priority based on Japanese Patent Application No. 2011-142630 filed on June 28, 2011, and hereby accepts all of its disclosures.

Claims (11)

A prepreg obtained by impregnating a fiber substrate with a resin composition containing an epoxy resin and an epoxy resin curing agent,
The nitrogen content in the prepreg is 0.0024 mass% or less,
Wherein 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. The method according to claim 1,
Wherein the resin composition further comprises a curing catalyst. 3. The method of claim 2,
Wherein the curing catalyst contains an imidazole compound. The method according to claim 1,
Wherein a basis weight of the fibrous substrate is not less than 145 g / m < 2 > and not more than 300 g / m < 2 >. The method according to claim 1,
Wherein the thickness of the fiber substrate is not less than 50 占 퐉 and not more than 300 占 퐉. The method according to claim 1,
Wherein the fiber substrate is a glass fiber substrate. A laminate comprising the cured product of the prepreg according to any one of claims 1 to 6. A semiconductor package comprising a circuit board obtained by subjecting the laminate according to claim 7 to circuit processing and mounting a semiconductor element thereon. A step of impregnating a fiber substrate with a resin varnish containing an epoxy resin, an epoxy resin curing agent and a solvent to obtain a prepreg;
A step of heating the prepreg to obtain a cured product of the prepreg,
And then,
A manufacturing method of a laminated board for performing a step of forming a via by a laser,
The resin varnish has a theoretical nitrogen content of 0.005 mass% or less,
Wherein 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. 10. The method of claim 9,
Wherein the epoxy resin curing agent is an organic compound containing no nitrogen atom in the formula. 11. The method according to claim 9 or 10,
Wherein the solvent is an organic compound containing no nitrogen atom in the chemical formula.

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