JP5029291B2 - Resin composition for multilayer printed wiring board, prepreg, laminate, multilayer printed wiring board, and semiconductor device - Google Patents

Description

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

In recent years, the multilayer printed wiring board is required to have various characteristics as electric and electronic devices become smaller and thinner.
For example, multilayer printed wiring boards used for applications such as semiconductor mounting packages are mainly based on black. As one of methods for making a multilayer printed wiring board black, a method of blending a black organic colorant or the like with a resin composition constituting the multilayer printed wiring board is known.
However, since these organic colorants generally have low solubility in organic solvents, there has been a problem that the resin composition constituting the multilayer printed wiring board cannot have a uniform color.
Therefore, the prepreg or the insulating resin sheet using the resin composition containing the organic colorant has a problem that aggregates and unevenness are generated in appearance.
In addition, with the recent reduction in size and thickness of electric and electronic devices, the prepreg or the insulating resin sheet becomes thinner, and thus aggregates and unevenness appear more noticeably in the appearance.
JP 2001-163969 A

  The present invention provides a uniform resin composition for a multilayer printed wiring board even if it contains a colorant or an inorganic filler having low solvent solubility, and uses the resin composition for a multilayer printed wiring board. The present invention provides a prepreg and a resin sheet that are free from aggregates and have no uneven appearance.

Such an object is achieved by the following [1] to [ 10 ].
[1] (A) A thermosetting resin having a softening point or melting point of 50 ° C. or less, (B) an organic colorant, and (A) heat- melt mixing at a temperature equal to or higher than the softening point of the thermosetting resin or the melting point A resin composition for a multilayer printed wiring board , wherein the molten mixture obtained is dispersed in a slurry obtained by mixing (C) an organic solvent and (D) an inorganic filler .
[2] The resin composition for a multilayer printed wiring board according to [1], wherein the organic colorant (B) has a weight loss by sublimation at 260 ° C. or decomposition of 10% or less.
[3] (B) the organic colorant, Ru anthraquinone compound der [1] or a multilayer printed wiring board resin composition according to [2].
[ 4 ] The inorganic filler (D) includes at least one selected from the group consisting of magnesium hydroxide, aluminum hydroxide, silica, talc, calcined talc, and alumina [1] to [3]. The resin composition for multilayer printed wiring boards according to any one of the above.
[ 5 ] An insulating resin sheet formed by forming an insulating resin layer made of the resin composition for multilayer printed wiring boards according to any one of [1] to [ 4 ] on a thermoplastic resin film or a metal foil.
[ 6 ] A prepreg obtained by impregnating a base material with the resin composition for a multilayer printed wiring board according to any one of [1] to [ 4 ].
[ 7 ] A laminate obtained by superposing one or more prepregs according to [ 6 ] and performing heat-press molding.
[ 8 ] A multilayer printed wiring board obtained by using the laminated board according to [ 7 ] as an inner circuit board.
[ 9 ] A multilayer printed wiring board comprising the insulating resin sheet according to [ 5 ] and / or the prepreg according to [ 6 ].
[ 10 ] A semiconductor device obtained by mounting a semiconductor element on the multilayer printed wiring board according to [ 9 ].

The resin composition for a multilayer printed wiring board of the present invention is a uniform resin composition for a multilayer printed wiring board, even if it contains a colorant and an inorganic filler with low solvent solubility, and has a uniform prepreg and appearance. An insulating resin sheet can be obtained.

Hereinafter, the resin composition for a multilayer printed wiring board, the prepreg, the laminated board, the multilayer printed wiring board, and the semiconductor device of the present invention will be described.

The resin composition for a multilayer printed wiring board of the present invention includes (A) a thermosetting resin having a softening point or a melting point of 50 ° C. or less (hereinafter referred to as (A) a thermosetting resin), and (B) an organic. Slurry formed by mixing (C) an organic solvent and (D) an inorganic filler with a molten mixture obtained by heating and mixing a colorant at a temperature equal to or higher than the softening point of the thermosetting resin (A) or the melting point. dispersed in, characterized by comprising.

(A) The temperature at which the (B) organic colorant is heated and melted and mixed with the thermosetting resin is preferably (A) the softening point or the melting point of the thermosetting resin and 120 ° C. or less. When the heating temperature is the softening point of the thermosetting resin (A) or below the melting point, the melt viscosity is not lowered sufficiently, resulting in poor dispersibility and the presence of aggregates in the resin composition for multilayer printed wiring boards. There is a case. If the temperature is higher than 120 ° C., depending on the type of (B) organic colorant, the curability of the resin composition for multilayer printed wiring boards may be affected, and the moldability may deteriorate.

Moreover, as stirring conditions, it is preferable to stir for 1 hour or more at a rotation speed of 300 rpm or more. When the rotation speed and the stirring time are less than the above, dispersibility may be deteriorated as described above, and aggregates may be present in the resin composition for multilayer printed wiring boards.

The (A) thermosetting resin used in the present invention is, for example, a product name EPICLON 840, a product name EPICLON 840-S, a product name EPICLON 850, a product name EPICLON 850-S manufactured by Dainippon Ink and Chemicals, Inc. as a bisphenol A type epoxy resin. Product name EPICLON850-CRP, Product name EPICLPN850-LC, Product name EPICLON860, Product name Epicoat 825, Product name Epicote 827, Product name Epicoat 828, Product name Epicoat 828EL, Product name Epicoat 828XA, Product name Epicoat 834 or the like. As the bisphenol F type epoxy resin, trade names manufactured by Japan Epoxy Resins Co., Ltd. such as trade names EPICLON 830, trade names EPICLON 830-S, trade names EPICLON 830-LVP, trade names EPICLPN 835, trade names EPICLPN 835-LV, etc. Epicoat 806, trade name Epicoat 806L, trade name Epicoat 807, and the like. Examples of the phenol novolac type epoxy resin include trade name EPICLON EXA-7240 manufactured by Dainippon Ink and Chemicals, product name Epicoat 152, product name Epicoat 154 and the like manufactured by Japan Epoxy Resin Co., Ltd. Product name EPICLON HP-4032D manufactured by Nippon Ink Chemical Co., Ltd., as hydrogenated epoxy resin, product name EPICLON EXA-7015 manufactured by Dainippon Ink Chemical Co., Ltd., product name YX-8000 manufactured by Japan Epoxy Resin Co., Ltd., product name YX -8034, trade name RXE21 and the like. As bismaleimide resin, trade name EPICLON EXA-7163 manufactured by Dainippon Ink Chemical Co., Ltd., as cyanate resin, trade name PRIMASET PT-30, trade name PRIMASET PT-15 manufactured by Lonza, etc., trade name B manufactured by Ciba Geigy -40S etc. are mentioned.
One of these can be used alone, two or more having different weight average molecular weights can be used together, or one or two or more can be used together.

Among these, the trade name PRIMASET PT-30, the trade name PRIMASET PT-15, and the trade name B-40S, manufactured by Ciba Geigy, are particularly preferable. Thereby, the thermal expansion coefficient of a prepreg can be made small. Furthermore, the electrical properties (low dielectric constant, low dielectric loss tangent), mechanical strength, etc. of the prepreg are also excellent.

(A) The thermosetting resin preferably has a lower melt viscosity, and preferably has a viscosity region of 0.1 Pa · s or less at 80 ° C to 150 ° C. This facilitates melting when heated and melted with (B) the organic colorant. The melt viscosity can be measured, for example, with a cone plate (ICI) high temperature viscometer.

The organic colorant (B) used in the present invention is not particularly limited, but an anthraquinone compound is preferable. Examples of the anthraquinone compound include Kayase Black A-N (manufactured by Nippon Kayaku Co., Ltd.), Kayase Black G (manufactured by Nippon Kayaku Co., Ltd.), Sudan Black 141 (manufactured by Chuo Synthetic Chemical Co., Ltd.), and the like. (B) One type of organic colorant may be used alone, or two or more types may be used in combination.

Among the colorants (B), those having a weight loss by sublimation at 260 ° C. or decomposition of 10% or less are preferable. Examples of the colorant whose weight loss due to sublimation or decomposition at 260 ° C. is 10% or less include Kayase Black A-N (manufactured by Nippon Kayaku Co., Ltd.) and Kayase Black G (manufactured by Nippon Kayaku Co., Ltd.). Thereby, the weight loss at the time of the high temperature of the laminated board manufactured using a resin composition can be decreased, and it becomes excellent in solder heat resistance. The weight decrease at 260 ° C. can be confirmed by measuring the weight decrease at 260 ° C. when the sample is heated at 10 ° C./min using a TGA (thermogravimetric measuring device).

The content of the organic colorant (B) used in the present invention is not particularly limited, but it is preferably 0.5 to 5 parts by weight, more preferably 1 with respect to (A) 100 parts by weight of the thermosetting resin. It is to contain ~ 4 parts by weight. If it is less than the above-mentioned parts by weight, the appearance of the resulting multilayer printed wiring board is uneven. If it is more than the above-mentioned parts by weight, the curability may be affected depending on the type of the colorant, and the moldability may deteriorate.

The melt mixture obtained by heating and mixing (B) the organic colorant with the (A) thermosetting resin is further dispersed in a slurry obtained by mixing (C) an organic solvent and (D) an inorganic filler. It is preferable that it is the resin composition for multilayer printed wiring boards which becomes.

The method for producing the slurry is not particularly limited. For example, the slurry is produced by mixing an inorganic filler and a solvent, and stirring and dispersing with a high-speed stirrer or a homomixer.

  The (C) organic solvent used for preparing the slurry is not particularly limited, and examples thereof include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, amide solvents such as dimethylacetamide and dimethylformamide, toluene, Examples include ethyl acetate, cyclohexane, heptane, cyclohexane, tetrahydrofuran, dimethyl sulfoxide, ethylene glycol, cellosolve, carbitol, and anisole. Of these, ketone solvents and amide solvents are particularly preferred because they have low reactivity with the (A) thermosetting resin. One of these can be used alone, or two or more can be used in combination.

The (D) inorganic filler is not particularly limited. For example, talc, calcined talc, calcined clay, uncalcined clay, mica, silicates such as glass, oxides such as titanium oxide, alumina, silica, and fused silica , Carbonates such as calcium carbonate, magnesium carbonate, hydrotalcite, hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, sulfates or sulfites such as barium sulfate, calcium sulfate, calcium sulfite, boric acid Borate salts such as zinc, barium metaborate, aluminum borate, calcium borate and sodium borate, nitrides such as aluminum nitride, boron nitride, silicon nitride and carbon nitride, titanic acid such as strontium titanate and barium titanate A salt etc. can be mentioned. One of these can be used alone, or two or more can be used in combination. Among these, magnesium hydroxide, aluminum hydroxide, silica, fused silica, talc, calcined talc, and alumina are preferable, and fused silica is particularly preferable in terms of excellent low thermal expansion. The shape is crushed and spherical, but in order to reduce the melt viscosity of the resin composition in order to ensure the impregnation of the fiber substrate, a method of use that suits the purpose, such as using spherical silica, is adopted. .

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

  Although content of the said (D) inorganic filler is not specifically limited, 50-300 weight part is preferable with respect to 100 weight part of (C) organic solvent, and 100-240 weight part is especially preferable. When the content is within the above range, particularly low thermal expansion and low water absorption can be achieved.

The average particle diameter of the (D) inorganic filler is not particularly limited, but is preferably 0.005 to 10 μm, particularly preferably 0.01 to 3 μm. When the particle size of the inorganic filler is less than the lower limit value, the viscosity of the multilayer printed wiring board resin composition increases, which may affect the workability at the time of preparing the prepreg. When the upper limit is exceeded, phenomena such as sedimentation of the inorganic filler may occur in the resin composition for multilayer printed wiring boards.
Further, spherical silica having an average particle diameter of 5.0 μm or less is preferable, and spherical fused silica having an average particle diameter of 0.01 to 3 μm is particularly preferable. Thereby, the filling property of an inorganic filler can be improved. The average particle diameter can be measured, for example, by a particle size distribution meter (manufactured by HORIBA, LA-500).

The resin composition for multilayer printed wiring boards of the present invention can be used in combination with other thermosetting resins (substantially free of halogen). Thermosetting resin compositions that can be used in combination include, for example, novolak epoxy resins such as phenol novolac epoxy resins and cresol novolac epoxy resins, biphenyl epoxy resins, biphenyl aralkyl epoxy resins, arylalkylene epoxy resins, and naphthalene. Epoxy resin, anthracene epoxy resin, phenoxy epoxy resin, dicyclopentadiene epoxy resin, norbornene epoxy resin, adamantane epoxy resin, epoxy resin such as fluorene epoxy resin, urea (urea) resin, melamine resin, etc. Resin having a triazine ring, unsaturated polyester resin, bismaleimide resin, polyurethane resin, diallyl phthalate resin, silicone resin, resin having a benzoxazine ring, cyanate resin Etc. The.
One of these can be used alone, or two or more having different weight average molecular weights can be used in combination, or one or two or more of these prepolymers can be used in combination. Among these, novolac type epoxy resins having a methylene bond such as biphenyl aralkyl type novolak epoxy resin and naphthalene aralkyl type novolak epoxy resin are excellent in heat resistance, flame retardancy and water absorption, and among them, biphenyl aralkyl type novolak. Epoxy resins are preferred. Thereby, moisture absorption solder heat resistance and a flame retardance can be improved.

In the resin composition for multilayer printed wiring boards of the present invention, in addition to (A) thermosetting resin and (B) colorant, a curing agent for (A) thermosetting resin may be used in combination. For example, if the thermosetting resin (A) is an epoxy resin or a cyanate resin, a curing accelerator for phenol resin, epoxy resin, or cyanate resin can be used. The phenol resin is not particularly limited. For example, a phenol novolak resin, a cresol novolak resin, a bisphenol A novolak resin, a novolak phenol resin such as an arylalkylene type novolak resin, an unmodified resole phenol resin, tung oil, linseed oil, walnut Examples include resol-type phenol resins such as oil-modified resol phenol resins modified with oil. One of these can be used alone, or two or more having different weight average molecular weights can be used in combination, or one or two or more of these prepolymers can be used in combination. Among these, arylalkylene type phenol resins are particularly preferable. Thereby, moisture absorption solder heat resistance can be improved further.

The curing accelerator is not particularly limited. For example, organic metals such as zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, bisacetylacetonate cobalt (II), trisacetylacetonate cobalt (III), and the like. Salt, triethylamine, tributylamine, tertiary amines such as diazabicyclo [2,2,2] octane, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-ethylimidazole 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 2-phenyl-4-methyl -5 Imidazoles such as loxyimidazole, 2-phenyl-4,5-dihydroxyimidazole, 2,3-dihydro-1H-pyrrolo (1,2-a) benzimidazole, phenolic compounds such as phenol, bisphenol A, nonylphenol, acetic acid, benzoic acid Examples thereof include acids, organic acids such as salicylic acid and p-toluenesulfonic acid, and mixtures thereof. One of these can be used alone, including derivatives thereof, or two or more of these can be used in combination.

The resin composition for a multilayer printed wiring board of the present invention is not particularly limited, but preferably further contains a coupling agent.

The coupling agent improves the heat resistance, especially the solder heat resistance after moisture absorption, by uniformly fixing the resin and filler to the substrate by improving the wettability of the interface between the resin and the inorganic filler. To make it.

  Although the said coupling agent is not specifically limited, For example, an epoxy silane coupling agent, a cationic silane coupling agent, an aminosilane coupling agent, a titanate coupling agent, a silicone oil type coupling agent etc. are mentioned. Thereby, the wettability with the interface of an inorganic filler can be made high, and thereby heat resistance can be improved more.

Although the addition amount of the coupling agent is not particularly limited, it is preferably 0.05 to 3 parts by weight, particularly preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the inorganic filler. If the content is less than the lower limit, the inorganic filler cannot be sufficiently coated, and thus the effect of improving the heat resistance may be reduced. If the content exceeds the upper limit, the reaction is affected, and the bending strength is reduced. There is a case.

The resin composition for a multilayer printed wiring board of the present invention improves the adhesion between the insulating resin layer and the conductor layer when an insulating resin layer made of the resin composition for a multilayer printed wiring board is formed during the production of the multilayer printed board. Ingredients may be included. For example, a phenoxy resin, a polyvinyl alcohol resin, a coupling agent that improves the adhesion with the metal constituting the conductor layer, and the like. Among these, the adhesion is particularly excellent, and the influence on the curing reaction rate is small. Phenoxy resin is preferred. Examples of the phenoxy resin include a phenoxy resin having a bisphenol skeleton, a phenoxy resin having a novolak skeleton, a phenoxy resin having a naphthalene skeleton, and a phenoxy resin having a biphenyl skeleton. A phenoxy resin having a structure having a plurality of these skeletons can also be used.

Moreover, the resin composition for multilayer printed wiring boards of the present invention, if necessary, other than the above components such as an antifoaming agent, a leveling agent, an ultraviolet absorber, a foaming agent, an antioxidant, a flame retardant, and an ion scavenger. Additives may be added.

Next, the insulating resin sheet of the present invention will be described.

The insulating resin sheet of the present invention is formed by forming an insulating resin layer made of the resin composition for a multilayer printed wiring board on a thermoplastic resin film or a metal foil. Here, the method for forming the insulating resin layer on the substrate is not particularly limited. For example, the resin composition for a multilayer printed wiring board is coated on a thermoplastic resin film or a metal foil using various coater apparatuses. And a method of drying the resin composition for a multilayer printed wiring board after spraying it onto a substrate using a spray device, and the like. Among these, a method of drying the resin composition for a multilayer printed wiring board on a film or a metal foil using various coaters such as a comma coater and a die coater is preferable. Thereby, there can be efficiently produced an insulating resin sheet having no voids and having a uniform insulating resin layer thickness.

The thermoplastic resin film or metal foil used for the insulating resin sheet of the present invention is not particularly limited. For example, in the case of a thermoplastic resin film, a polyester resin such as polyethylene terephthalate or polybutylene terephthalate, a fluorine resin, or a polyimide resin. In the case of metal foil, copper and / or copper-based alloy, aluminum and / or aluminum-based alloy, iron and / or iron-based alloy, silver and / or Alternatively, silver alloy, gold and gold alloy, zinc and zinc alloy, nickel and nickel alloy, tin and tin alloy metal foil, and the like can be given.

Although it does not specifically limit as thickness of the said thermoplastic resin film or metal foil, When the thing of 10-100 micrometers is used, the handleability at the time of manufacturing an insulating resin sheet is favorable, and is preferable.
In manufacturing the insulating resin sheet of the present invention, it is preferable that the unevenness on the surface of the thermoplastic resin film or metal foil to be bonded to the insulating resin layer is as small as possible. Thereby, the effect | action of this invention can be expressed effectively.

Next, the prepreg will be described.

The prepreg of the present invention is obtained by impregnating a base material with a resin composition for multilayer printed wiring boards. Thereby, it is possible to obtain a prepreg suitable for manufacturing a printed wiring board excellent in various characteristics such as dielectric characteristics, mechanical and electrical connection reliability under high temperature and high humidity.

The base material is not particularly limited, but glass fiber base materials such as glass woven fabric and glass nonwoven fabric, polyamide resin fibers, aromatic polyamide resin fibers, polyamide resin fibers such as wholly aromatic polyamide resin fibers, polyester resin fibers, Synthetic fiber substrate, kraft paper, cotton linter composed of woven or non-woven fabric mainly composed of aromatic polyester resin fiber, polyester resin fiber such as wholly aromatic polyester resin fiber, polyimide resin fiber, fluororesin fiber, etc. Examples thereof include organic fiber base materials such as paper base materials mainly composed of paper, mixed paper of linter and kraft pulp, and the like. Among these, a glass fiber base material is preferable. Thereby, the intensity | strength of a prepreg and a water absorption rate can be improved. Moreover, the thermal expansion coefficient of the prepreg can be reduced.

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 a glass fiber base material can be achieved and a thermal expansion coefficient can also be made small.

Examples of the method for impregnating the base material with the resin composition for a multilayer printed wiring board of the present invention include a method of applying with various coaters and a method of spraying with a spray. Among these, the method of immersing a base material in the resin composition for multilayer printed wiring boards is preferable. Thereby, the impregnation property of the resin composition with respect to the fiber base material can be improved. In addition, when a fiber base material is immersed in the resin composition for multilayer printed wiring boards, a normal impregnation coating equipment can be used.

Next, a laminated board is demonstrated.

The laminated board of this invention can obtain a laminated board by laminating | stacking metal foil on the upper and lower both surfaces of the laminated body which laminated | stacked the said prepreg at least 1 sheet, or multiple sheets, and heating and pressurizing. The heating temperature is not particularly limited, but is preferably 120 to 230 ° C, particularly preferably 150 to 210 ° C. Moreover, the pressure to pressurize is not particularly limited, but is preferably 1 to 5 MPa, and particularly preferably 2 to 4 MPa. Thereby, the laminated board excellent in the dielectric property and the mechanical and electrical connection reliability in high temperature and high humidity can be obtained.
The metal foil is, for example, copper, copper alloy, aluminum, aluminum alloy, silver, silver alloy, gold, gold alloy, zinc, zinc alloy, nickel, nickel alloy, tin, tin alloy, iron And metal foils such as iron-based alloys.

Next, a multilayer printed wiring board will be described.

A multilayer printed wiring board can be manufactured using the said laminated board. Although a manufacturing method is not specifically limited, For example, the laminated board which has copper foil on the both surfaces is used, an opening part is provided in a predetermined position with a drill machine, and conduction | electrical_connection of both surfaces of an inner-layer circuit board is aimed at by electroless plating. Then, an inner layer circuit is formed by etching the copper foil.
The inner layer circuit portion can be suitably used after roughening treatment such as blackening treatment. The opening can be appropriately filled with a conductor paste or a resin paste.

Next, using the prepreg of the present invention or an insulating resin sheet in which an insulating resin layer is formed on a thermoplastic resin film, lamination is performed so as to cover the inner layer circuit to form an insulating resin layer. The lamination method is not particularly limited, but a lamination method using a vacuum press, an atmospheric laminator, and a laminator that is heated and pressurized under vacuum is preferable, and a method using a laminator that is heated and pressurized under vacuum is more preferable. It is. Thereafter, the insulating resin layer is cured by heating. Although the temperature to harden | cure is not specifically limited, For example, it can be made to harden | cure in the range of 100 to 250 degreeC. Preferably it is made to harden | cure at 150 to 200 degreeC.

Next, the thermoplastic resin film of the laminated insulating resin sheet is peeled off, and the insulating resin layer is irradiated with a laser to form an opening. Resin residues after the laser irradiation are permanganate, dichromate, etc. It is preferable to remove with an oxidizing agent such as. Further, the surface of the smooth insulating resin layer can be simultaneously roughened, and the adhesion of the outer layer circuit formed by subsequent metal plating can be improved. The insulating resin layer formed from the resin composition for a multilayer printed wiring board according to the present invention can be uniformly provided with fine irregularities in the roughening step. In addition, since the surface of the insulating resin layer is highly smooth, a fine outer layer circuit can be formed with high accuracy. In the case of an insulating resin sheet on the metal foil, the metal foil may be used as an outer layer circuit by etching, or the outer layer circuit may be formed by front etching and the same method as in the case of the thermoplastic resin film. good.

Next, an opening was provided in the insulating resin layer by using a carbonic acid laser device, and an outer layer circuit was formed on the surface of the insulating resin layer by electrolytic copper plating to achieve conduction between the outer layer circuit and the inner layer circuit. The outer layer circuit is provided with a connection electrode portion for mounting a semiconductor element.

After that, a solder resist is formed on the outermost layer, the connection electrode part is exposed so that a semiconductor element can be mounted by exposure / development, nickel gold plating treatment is performed, and it is cut into a predetermined size to obtain a multilayer printed wiring board. Can do.

  Next, a semiconductor device will be described.

A semiconductor element having a solder bump is mounted on the multilayer printed wiring board obtained above, and the multilayer printed wiring board and the semiconductor element are connected via the solder bump. A liquid sealing resin is filled between the multilayer printed wiring board and the semiconductor element to manufacture a semiconductor device. The solder bump is preferably made of an alloy made of tin, lead, silver, copper, bismuth or the like. The semiconductor element and the multilayer printed wiring board are connected by aligning the connection electrode portion on the multilayer printed wiring board with the solder bump of the semiconductor element using a flip chip bonder or the like, The solder bumps are heated to the melting point or higher by using a board or other heating device, and the multilayer printed wiring board and the solder bumps are connected by fusion bonding. In order to improve connection reliability, a metal layer having a relatively low melting point such as a solder paste may be formed in advance on the connection electrode portion on the multilayer printed wiring board. Prior to this joining step, the connection reliability can be improved by applying flux to the surface layers of the solder bumps and / or the connection electrode portions on the multilayer printed wiring board.

Hereinafter, the contents of the present invention will be described in detail by way of examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

The organic colorant (B) used in the present invention is as follows.
B1: Perinone and anthraquinone dyes (trade name Kayase Black A-N (manufactured by Nippon Kayaku Co., Ltd.))
Weight reduction rate at 260 ° C 1.5%
B2: Methine and anthraquinone dye (trade name Kayase Black G (manufactured by Nippon Kayaku Co., Ltd.))
Weight reduction rate at 260 ° C 1.5%
B3: Organic colorant (trade name Sudan Black 141 (manufactured by Chuo Synthetic Chemical))
Weight reduction rate at 260 ° C 4.4%

The weight reduction rate at 260 ° C. of the (B) organic colorant was determined by the following method.

Measurement of weight loss rate of colorant The weight loss rate was measured by increasing the temperature of the used colorant from 30 ° C. to 450 ° C. at 10 ° C./min by TG-DTA (differential thermogravimetric simultaneous measurement). The change in weight was traced, and a value obtained by ((30 ° C. sample weight) − (260 ° C. sample weight)) / (30 ° C. sample weight) × 100 was obtained.

Fabrication of resin composition for multilayer printed wiring boards

Example 1
[Step A] ((A) Heat-melt mixing step of (A) thermosetting resin and (B) organic colorant)
(A) As a thermosetting resin, 24.6 parts by weight of novolak-type cyanate resin (Lonza Japan Co., Ltd. Primaset PT-30; melting point 13 ° C., 0.3 to 0.75 Pa · s at 80 ° C.) at 80 ° C. (B) B1: Perinone and anthraquinone dye (Nippon Kayaku Co., Ltd., Kayase Black A-N) 0.6 parts by weight as an organic colorant were added, and the mixture was heated and melted and mixed at 100 ° C. for 1 hour, 50 Cooled to ° C. In addition, the stirring rotation speed at the time of heat-melt mixing was 500 rpm.

[Step B] ((C) (D) Step of dispersing inorganic filler in organic solvent)
(C) Methyl ethyl ketone (MEK) is used as the organic solvent, and (D) 49.8 parts by weight of spherical fused silica (manufactured by Admatechs, SO25R, average particle size 0.5 μm) is dispersed in methyl ethyl ketone (MEK) as the inorganic filler. To obtain a slurry having a concentration of 60% by weight. The slurry was obtained by stirring at room temperature at a rotation speed of 500 rpm for 1 hour.

[Step C]
(The step of dispersing the molten mixture obtained in [Step A] and the slurry obtained in [Step B] and other components)
The molten mixture obtained in Step A was added to the slurry obtained in [Step B] and stirred for 30 minutes at 50 ° C. and a rotation speed of 500 rpm.
Next, 14.0 parts by weight of a biphenyl aralkyl type novolak epoxy resin (manufactured by Nippon Kayaku Co., Ltd., NC-3000; 0.07 Pa · s at a softening point of 58 ° C. and 150 ° C.) as an epoxy resin, and a biphenyl dimethylene type as a curing agent 10.8 parts by weight of a phenol resin (Maywa Kasei Co., Ltd., MEH-7851HHH) and 0.2 parts by weight of a coupling agent (GE Toshiba Silicone Co., Ltd., A187) were added and stirred at room temperature for 1 hour at a rotation speed of 1000 rpm. A resin composition for a multilayer printed wiring board having a solid content of 70% by weight was produced.

2. Preparation of prepreg A glass woven fabric (thickness 94 μm, manufactured by Nitto Boseki Co., Ltd., WEA-2116) is impregnated with the above resin composition for a multilayer printed wiring board, dried in a heating furnace at 150 ° C. for 2 minutes, and multilayered in the prepreg. A prepreg having a resin composition solid content for a printed wiring board of about 50% by weight was obtained.

3. Fabrication of Laminate Laminate having a copper foil with a thickness of 0.1 mm on both sides by stacking 18 μm copper foil on both sides of the above prepreg and heating and pressing at a pressure of 4 MPa and a temperature of 200 ° C. for 2 hours. Got.

4). Preparation of Insulating Resin Sheet The resin composition for a multilayer printed wiring board obtained above was dried on a single side of a 25 μm thick PET (polyethylene terephthalate) film using a comma coater device, and the thickness of the insulating film was 60 μm. Then, this was dried with a drying apparatus at 160 ° C. for 10 minutes to produce an insulating resin sheet.

5. Fabrication of multilayer printed wiring board After opening the laminated board having copper foil on both sides with a drilling machine, conducting conduction between upper and lower copper foils by electroless plating, etching the copper foil on both sides, Formed. (L / S = 120 / 180μm, clearance holes 1mmφ, 3mmφ, slit 2mm)
Next, the chemical | medical solution (Asahi Denka Kogyo Co., Ltd. TEC SO-G) which has a hydrogen peroxide solution and a sulfuric acid as a main component was sprayed on the inner layer circuit by the spray, and the unevenness | corrugation formation by the roughening process was performed. Thereafter, the insulating resin sheet obtained above was laminated on the inner layer circuit using a vacuum laminator, the PET film was peeled off, and heated at 170 ° C. for 60 minutes to semi-cure the insulating resin layer. The conditions for laminating the insulating resin sheets were a temperature of 100 ° C., a pressure of 1 MPa, and a time of 30 seconds. Next, a φ60 μm opening (blind via hole) is formed using a carbonic acid laser device, immersed in a swelling liquid at 70 ° C. (Swelling Dip Securigant P, manufactured by Atotech Japan) for 10 minutes, and further at 80 ° C. After immersion for 20 minutes in an aqueous potassium permanganate solution (manufactured by Atotech Japan Co., Ltd., Concentrate Compact CP), it was neutralized and roughened. Next, after passing through degreasing, catalyst application, and activation steps, an electroless copper plating film was formed with a power supply layer of about 0.5 μm. Next, a 25 μm-thick UV photosensitive dry film (AQ-2558 manufactured by Asahi Kasei Co., Ltd.) is bonded to the surface of the power feeding layer by a hot roll laminator, and a chromium having a pattern with a minimum line width / line spacing of 20/20 μm is drawn. Using a vapor deposition mask (manufactured by Towa Process Co., Ltd.), the position was adjusted, exposure was performed with an exposure apparatus (UX-1100SM-AJN01 manufactured by USHIO INC.), And development was performed with a sodium carbonate aqueous solution to form a plating resist.
Next, electrolytic copper plating (81-HL, manufactured by Okuno Pharmaceutical Co., Ltd.) was performed at 3 A / dm ² for 30 minutes using the power feeding layer as an electrode to form a copper wiring having a thickness of about 25 μm. Here, the plating resist was peeled off using a two-stage peeling machine. Each chemical solution is mainly composed of monoethanolamine solution (R-100 manufactured by Mitsubishi Gas Chemical Co., Ltd.) in the first stage alkaline aqueous solution layer, and potassium permanganate and sodium hydroxide as the main ingredients in the second stage oxidizing resin etchant. An aqueous solution of acidic amine (Mc. Dicer 9279, manufactured by Nihon McDermid Co., Ltd.) was used for neutralization.
Next, the power feeding layer was immersed in an aqueous ammonium persulfate solution (AD-485 manufactured by Meltex Co., Ltd.) to remove it by etching and ensure insulation between the wirings. Next, the insulating resin layer is finally cured at a temperature of 200 ° C. for 60 minutes, and finally a solder resist (PSR4000 / AUS308 manufactured by Taiyo Ink Co., Ltd.) is formed on the circuit surface, which corresponds to the solder bump arrangement of the semiconductor element by exposure and development. A connecting electrode portion subjected to nickel gold plating treatment was provided, nickel gold plating treatment was performed, and cut into a size of 50 mm × 50 mm to obtain a multilayer printed wiring board.

6). Fabrication of Semiconductor Device A semiconductor element (TEG chip, size 15 mm × 15 mm, thickness 0.8 mm) used for the semiconductor device was used having a solder bump formed of a eutectic of Sn / Pb composition.
Moreover, the circuit protection film of the semiconductor element used what was formed with positive photosensitive resin (Sumitomo Bakelite Co., Ltd. CRC-8300). To assemble the semiconductor device, first apply a flux material uniformly to the solder bumps of the semiconductor element by a transfer method, and then mount it on the multilayer printed wiring board obtained above by thermocompression bonding using a flip chip bonder device. Then, after melt-bonding the solder bumps in an IR reflow furnace, a liquid sealing resin (manufactured by Sumitomo Bakelite Co., Ltd., CRP-4152S) was filled and the liquid sealing resin was cured to obtain a semiconductor device. The curing condition of the liquid sealing resin was a temperature of 150 ° C. and 120 minutes.

(Example 2)
A prepreg, a laminate, an insulating resin sheet, a multilayer printed wiring board, and a semiconductor device were produced in the same manner as in Example 1 except that the resin composition for a multilayer printed wiring board was produced as follows.

[Step A]
(A) 49.2 parts by weight of novolak-type cyanate resin (Lonza Japan Co., Ltd., Primaset PT-30; melting point 13 ° C., 0.3 to 0.75 Pa · s at 80 ° C.) as thermosetting resin at 80 ° C. (B) As an organic coloring agent, B1: Perinone and anthraquinone dye (Nippon Kayaku Co., Ltd., Kayase Black A-N) 1.2 parts by weight were added, and the mixture was heated and melted at 80 ° C. for 1 hour. Cooled to 50 ° C. In addition, the stirring rotation speed at the time of heat-melt mixing was 500 rpm.

[Step D] ((C) Step of dispersing the molten mixture obtained in [Step A] and other components in an organic solvent)
(C) Using methyl ethyl ketone (MEK) as an organic solvent, methyl isobutyl ketone was added to the mixture obtained in Step A, and the mixture was stirred at 50 ° C. and 500 rpm for 30 minutes. Then, 28.0 parts by weight of biphenyl aralkyl type novolak epoxy resin (manufactured by Nippon Kayaku Co., Ltd., NC-3000; 0.07 Pa · s at a softening point of 58 ° C. and 150 ° C.) as an epoxy resin, and biphenyldimethylene type phenol as a curing agent 21.6 parts by weight of resin (Maywa Kasei Co., Ltd., MEH-7851HHH; softening point 103 ° C., 3.0 to 5.0 Pa · s at 150 ° C.) was added and stirred at 50 ° C. for 1 hour at 1000 rpm. Thus, a resin composition for a multilayer printed wiring board having a solid content of 70% by weight was produced.

(Example 3)
A prepreg, a laminate, an insulating resin sheet, a multilayer printed wiring board, and a semiconductor device were produced in the same manner as in Example 1 except that the resin composition for a multilayer printed wiring board was produced as follows.

[Step A]
(A) As a thermosetting resin, 24.6 parts by weight of bisphenol A type liquid epoxy resin (Dainippon Ink Chemical Co., Ltd., 850S; liquid at room temperature, 1100 Pa · s to 1500 Pa · s at 25 ° C.) is heated to 50 ° C. (B) B1: Perinone as an organic colorant and 0.6 part by weight of anthraquinone dye (manufactured by Nippon Kayaku Co., Ltd., Kayase Black A-N) were added, and melt mixed at 80 ° C. and a rotation speed of 500 rpm for 1 hour. Cooled to ° C. In addition, the stirring rotation speed at the time of heat-melt mixing was 500 rpm.

[Step B]
(C) Methyl ethyl ketone (MEK) is used as an organic solvent, and (D) 49.8 parts by weight of spherical fused silica (manufactured by Admatechs, SO25R, average particle size 0.5 μm) is dispersed in methyl isobutyl ketone as an inorganic filler. A slurry with a concentration of 60% by weight was obtained. The slurry was obtained by stirring for 30 minutes at a rotation speed of 500 rpm at room temperature.

[Step C]
[Step A] The molten mixture obtained in [Step A] and the slurry obtained in [Step B] were mixed and stirred, and then biphenylaralkyl type novolak epoxy resin (Nippon Kayaku Co., Ltd., NC-3000) 14 as an epoxy resin. 0.0 part by weight, 10.8 parts by weight of biphenyl dimethylene type phenol resin (Maywa Kasei Co., Ltd., MEH-7851HHH) as a curing agent, and 0.2 part by weight of coupling agent (GE Toshiba Silicone Co., Ltd., A187) were added. Then, the mixture was stirred for 1 hour at room temperature and a rotational speed of 1000 rpm using a high-speed stirrer, and dispersed to prepare a resin composition for a multilayer printed wiring board having a solid content of 70% by weight.

Example 4
A prepreg, a laminate, an insulating resin sheet, a multilayer printed wiring board, and a semiconductor device were produced in the same manner as in Example 1 except that the resin composition for a multilayer printed wiring board was produced as follows.

[Step A]
(A) As a thermosetting resin, 24.6 parts by weight of novolak type cyanate resin (Lonza Japan KK, Primaset PT-30; melting point 13 ° C., 0.3 to 0.75 Pa · s at 80 ° C.) 80 ° C. (B) 0.62 parts by weight of B2: methine and anthraquinone dye (manufactured by Nippon Kayaku Co., Ltd., Kayase Black G) were added as an organic colorant, and heated and melted and mixed at 80 ° C. for 1 hour. In addition, the stirring rotation speed at the time of heat-melt mixing was 500 rpm.

[Step B]
(C) Methyl ethyl ketone (MEK) is used as the organic solvent, and (D) 49.8 parts by weight of spherical fused silica (manufactured by Admatechs, SO25R, average particle size 0.5 μm) is dispersed in methyl ethyl ketone (MEK) as the inorganic filler. To obtain a slurry having a concentration of 60% by weight. The slurry was obtained by stirring for 1 hour at a rotation speed of 500 rpm at room temperature.

[Step C]
The molten mixture obtained in [Step A] and the slurry obtained in [Step B] were stirred at 50 ° C. and a rotation speed of 500 rpm for 30 minutes.
Next, 14.0 parts by weight of a biphenyl aralkyl type novolak epoxy resin (manufactured by Nippon Kayaku Co., Ltd., NC-3000; 0.07 Pa · s at a softening point of 58 ° C. and 150 ° C.) as an epoxy resin, and a biphenyl dimethylene type as a curing agent 10.8 parts by weight of a phenol resin (Maywa Kasei Co., Ltd., MEH-7851HHH) and 0.2 parts by weight of a coupling agent (GE Toshiba Silicone Co., Ltd., A187) were added and stirred at room temperature for 1 hour at a rotation speed of 1000 rpm. A resin composition for a multilayer printed wiring board having a solid content of 70% by weight was produced.

(Example 5)
A prepreg, a laminate, an insulating resin sheet, a multilayer printed wiring board, and a semiconductor device were produced in the same manner as in Example 1 except that the resin composition for a multilayer printed wiring board was produced as follows.
[Step A]
(A) As a thermosetting resin, 24.6 parts by weight of novolak type cyanate resin (Lonza Japan KK, Primaset PT-30; melting point 13 ° C., 0.3 to 0.75 Pa · s at 80 ° C.) 80 ° C. (B) B3: After adding 0.6 parts by weight of an organic colorant (Chuo Synthetic Chemical Co., Ltd., Sudan Black 141), the mixture was stirred at 80 ° C. for 1 hour at 500 rpm and dispersed. And cooled to 50 ° C.

[Step B]
(C) Methyl ethyl ketone (MEK) is used as the organic solvent, and (D) 49.8 parts by weight of spherical fused silica (manufactured by Admatechs, SO25R, average particle size 0.5 μm) is dispersed in methyl ethyl ketone (MEK) as the inorganic filler. To obtain a slurry having a concentration of 60% by weight. The slurry was obtained by stirring for 1 hour at a rotation speed of 500 rpm at room temperature.

[Step C]
The molten mixture obtained in [Step A] was added to the slurry obtained in [Step B] and stirred at 50 ° C. and a rotation speed of 500 rpm for 30 minutes.
Next, 24.8 parts by weight of a biphenyl aralkyl type novolak epoxy resin (Nippon Kayaku Co., Ltd., NC-3000) and 0.2 part by weight of a coupling agent (GE Toshiba Silicone Co., Ltd., A187) were added as an epoxy resin. The resin composition for multilayer printed wiring boards having a solid content of 70% by weight was prepared by stirring at room temperature and rotating at 1000 rpm for 1 hour.

(Example 6)
A prepreg, a laminate, an insulating resin sheet, a multilayer printed wiring board, and a semiconductor device were produced in the same manner as in Example 1 except that the resin composition for a multilayer printed wiring board was produced as follows.

[Step A]
(A) As a thermosetting resin, 24.6 parts by weight of novolak type cyanate resin (Lonza Japan KK, Primaset PT-30; melting point 13 ° C., 0.3 to 0.75 Pa · s at 80 ° C.) 80 ° C. (B) As an organic colorant, B1: Perinone and anthraquinone dye (Nippon Kayaku Co., Ltd., Kayase Black A-N) 0.6 parts by weight were added, and the mixture was heated, melted and mixed at 80 ° C. for 1 hour, 50 Cooled to ° C. In addition, the stirring rotation speed at the time of heat-melt mixing was 500 rpm.

[Step B]
(C) Dimethylacetamide (DMAc) is used as an organic solvent, (D) 49.8 parts by weight of spherical fused silica (manufactured by Admatechs, SO25R, average particle size 0.5 μm) is dispersed in dimethylacetamide as an inorganic filler. A slurry with a concentration of 60% by weight was obtained. The slurry was obtained by stirring for 1 hour at a rotation speed of 500 rpm at room temperature.

[Step C]
The molten mixture obtained in [Step A] was added to the slurry obtained in [Step B] and stirred at 50 ° C. and a rotation speed of 500 rpm for 30 minutes.
Next, 14.0 parts by weight of a biphenylaralkyl type novolak epoxy resin (Nippon Kayaku Co., Ltd., NC-3000) as an epoxy resin, and biphenyldimethylene type phenolic resin (MEH-7851HHH, manufactured by Meiwa Kasei Co., Ltd.) as a curing agent 8 parts by weight and 0.2 part by weight of a coupling agent (GE Toshiba Silicone Co., Ltd., A187) are added, and the mixture is stirred at room temperature for 1 hour at a rotation speed of 1000 rpm. A composition was prepared.

(Example 7)
[Step A] ((A) Heat-melt mixing step of (A) thermosetting resin and (B) organic colorant)
(A) As a thermosetting resin, 24.6 parts by weight of novolak-type cyanate resin (Lonza Japan Co., Ltd. Primaset PT-30; melting point 13 ° C., 0.3 to 0.75 Pa · s at 80 ° C.) at 80 ° C. (B) B1: Perinone and anthraquinone dye (Nippon Kayaku Co., Ltd., Kayase Black A-N) 0.6 parts by weight as an organic colorant were added, and the mixture was heated and melted and mixed at 100 ° C. for 1 hour, 50 Cooled to ° C. In addition, the stirring rotation speed at the time of heat-melt mixing was 500 rpm.

[Step B] ((C) (D) Step of dispersing inorganic filler in organic solvent)
(C) Methyl ethyl ketone (MEK) is used as the organic solvent, (D) 49.8 parts by weight of aluminum hydroxide (Showa Denko, H-42M, average particle size 1.1 μm) as the inorganic filler is methyl ethyl ketone (MEK) To obtain a slurry having a concentration of 60% by weight. The slurry was obtained by stirring at room temperature at a rotation speed of 500 rpm for 1 hour.

[Step C]
(The step of dispersing the molten mixture obtained in [Step A] and the slurry obtained in [Step B] and other components)
The molten mixture obtained in Step A was added to the slurry obtained in [Step B] and stirred for 30 minutes at 50 ° C. and a rotation speed of 500 rpm.
Next, 14.0 parts by weight of a biphenyl aralkyl type novolak epoxy resin (manufactured by Nippon Kayaku Co., Ltd., NC-3000; 0.07 Pa · s at a softening point of 58 ° C. and 150 ° C.) as an epoxy resin, and a biphenyl dimethylene type as a curing agent 10.8 parts by weight of a phenol resin (Maywa Kasei Co., Ltd., MEH-7851HHH) and 0.2 parts by weight of a coupling agent (GE Toshiba Silicone Co., Ltd., A187) were added and stirred at room temperature for 1 hour at a rotation speed of 1000 rpm. A resin composition for a multilayer printed wiring board having a solid content of 70% by weight was produced.

(Comparative Example 1)
A prepreg, a laminate, an insulating resin sheet, a multilayer printed wiring board, and a semiconductor device were produced in the same manner as in Example 1 except that the method for producing the resin composition for a multilayer printed wiring board was as follows.

[Step E] ((C) Step of dispersing resin component in organic solvent at room temperature)
(C) Methyl ethyl ketone (MEK) is used as the organic solvent, and a biphenylaralkyl type novolac epoxy resin (Nippon Kayaku Co., Ltd., NC-3000; softening point 58 ° C., 150 ° C. is used as the epoxy resin in the methyl ethyl ketone (MEK) solvent. 07 Pa · s) 14.0 parts by weight, biphenyldimethylene type phenolic resin (manufactured by Nippon Kayaku Co., Ltd., MEH-7851HHH) as a curing agent, 10.8 parts by weight, novolac type cyanate resin (manufactured by Lonza Japan Co., Ltd., Primaset) 2-30 parts by weight of PT-30) was added, and the mixture was stirred at room temperature for 1 hour at 1000 rpm.

[Step F] (Step of adding other components to the mixture obtained in [Step E] and dispersing at room temperature)
In the mixture obtained in [Step E], (C) 49.8 parts by weight of spherical fused silica (manufactured by Admatechs Co., Ltd., “SO-25R”, average particle size 0.5 μm) as an inorganic filler and a coupling agent (Nihon Unicar Co., Ltd., A187) 0.2 parts by weight, (B) as a colorant, B1: perinone and anthraquinone dye (Nippon Kayaku Co., Ltd., Kayase Black A-N) 0.6 parts by weight, The resin composition for multilayer printed wiring boards having a solid content of 50% by weight was prepared by stirring at room temperature at a rotation speed of 1000 rpm for 10 minutes.

(Comparative Example 2)
A prepreg, a laminate, an insulating resin sheet, a multilayer printed wiring board, and a semiconductor device were produced in the same manner as in Example 1 except that the resin composition for a multilayer printed wiring board was produced as follows.
[Step G]
(Step of heating and mixing (B) colorant into thermosetting resin having softening point or melting point of 50 ° C. or higher)
Biphenyl aralkyl type novolak epoxy resin (Nippon Kayaku Co., Ltd., NC-3000; softening point: 58 ° C., 0.07 Pa · s at 150 ° C.) 14.0 wt. : 0.6 part by weight of perinone and anthraquinone dye (Nippon Kayaku Co., Ltd., Kayase Black A-N) was added, and the mixture was melted by heating at 80 ° C. for 1 hour. In addition, it was 500 rpm of stirring rotation in the case of superheated melt mixing.

[Step B]
(C) Methyl ethyl ketone (MEK) is used as the organic solvent, (D) 49.8 parts by weight of spherical fused silica (manufactured by Admatechs, SO25R, average particle size 0.5 μm) is dispersed as the inorganic filler, and 60% by weight A slurry of concentration was obtained. The slurry was obtained by stirring for 1 hour at a rotation speed of 500 rpm at room temperature.

[Step C]
Next, the mixture obtained in [Step G] was added to the slurry obtained in [Step B] and stirred at 50 ° C. and a rotation speed of 500 rpm for 30 minutes.
Thereafter, 24.6 parts by weight of a novolak cyanate resin (Lonza Japan Co., Ltd., Primaset PT-30) as the cyanate resin, and biphenyldimethylene type phenolic resin (Maywa Kasei Co., Ltd., MEH-7851HHH) 10.8 as the curing agent. Part by weight, 0.2 parts by weight of a coupling agent (GE 187 manufactured by Toshiba Silicone Co., Ltd.), stirred at room temperature for 1 hour at a rotational speed of 1000 rpm, and a resin composition for a multilayer printed wiring board having a solid content of 70% by weight A product was made.

(Comparative Example 3)
A prepreg, a laminate, an insulating resin sheet, a multilayer printed wiring board, and a semiconductor device were produced in the same manner as in Example 1 except that the resin composition for a multilayer printed wiring board was produced as follows.

[Step A]
(A) As a thermosetting resin, 24.6 parts by weight of novolak type cyanate resin (Lonza Japan KK, Primaset PT-30; melting point 13 ° C., 0.3 to 0.75 Pa · s at 80 ° C.) 80 ° C. (B) As a colorant as an organic colorant, B1: Perinone and anthraquinone dye (Nippon Kayaku Co., Ltd., Kayase Black A-N) 0.6 parts by weight are added, and heated and melted at 80 ° C. for 1 hour. Mix and cool to 50 ° C. In addition, the stirring rotation speed at the time of heat-melt mixing was 500 rpm.

[Step H] (Step of dispersing (D) inorganic filler in distilled water)
(D) As an inorganic filler, 49.8 parts by weight of spherical fused silica (manufactured by Admatechs, SO25R, average particle size 0.5 μm) was dispersed in distilled water to obtain a slurry having a concentration of 60% by weight. The slurry was obtained by stirring for 1 hour at a rotation speed of 500 rpm at room temperature.

[Step I] (Step of dispersing the molten mixture obtained in [Step A] and the slurry obtained in [Step H] and other components)
The mixture obtained in [Step A] was added to the slurry obtained in [Step H] and stirred at 50 ° C. and a rotation speed of 500 rpm for 30 minutes.
Next, 14.0 parts by weight of a biphenylaralkyl type novolak epoxy resin (Nippon Kayaku Co., Ltd., NC-3000) as an epoxy resin, and biphenyldimethylene type phenolic resin (MEH-7851HHH, manufactured by Meiwa Kasei Co., Ltd.) as a curing agent 8 parts by weight and 0.2 parts by weight of a coupling agent (GE 187 manufactured by Toshiba Silicone Co., Ltd.) were added, and the mixture was stirred for 1 hour at a rotation speed of 1000 rpm at room temperature using a high-speed stirrer. A resin composition for a multilayer printed wiring board was produced.

The characteristics of the resin compositions for multilayer printed wiring boards, prepregs, laminates, multilayer printed wiring boards, and semiconductor devices obtained in the examples and comparative examples were evaluated. The results are shown in Table 1.

The evaluation method is as follows.

1. Filtration residue of resin composition for multilayer printed wiring board The produced resin composition for multilayer printed wiring board was filtered through 400 mesh, and the presence or absence of residues of inorganic filler, colorant, and other resin components was visually confirmed.

2. Measurement of Particle Size Distribution of Resin Composition for Multilayer Printed Wiring Board Using a particle size distribution meter (SALD-7000-WJA1 manufactured by Shimadzu Corporation), measurement of the particle size distribution of the prepared resin composition for multilayer printed wiring board is performed with a refractive index of 1. The test was performed under the condition of 60-0.10i. The average particle size and 90% particle size were measured in terms of volume.

3. Viscosity Measurement of Multilayer Printed Wiring Board Resin Composition Using an E-type viscometer, the viscosity of the multilayer printed wiring board resin composition was measured at 25 ° C. under the condition of a rotation speed of 100 rpm.

4). Appearance of prepreg In the prepared prepreg, the presence or absence of appearance unevenness due to aggregation of inorganic fillers and organic compounds was visually confirmed.

5. Appearance of Insulating Resin Sheet In the insulating resin sheet prepared, the presence or absence of appearance unevenness due to aggregation of inorganic fillers and organic compounds was visually confirmed.

6). The appearance of the insulating resin sheet after the roughening treatment was laminated on the inner layer substrate, and the appearance when the roughening treatment was performed was observed with a metallurgical microscope to observe whether there were any appearance defects such as roughening unevenness or cracks. .

7). Thermal expansion coefficient of laminated board The thermal expansion coefficient of the obtained laminated board was measured by raising the temperature at 10 ° C./min using a TMA apparatus (TA Instruments). Measurements were made in the MD direction.

8). Dispersibility of insulating resin layer in cross section of multilayer printed wiring board The central portion of the above multilayer printed wiring board was cut out, and the cross section was observed with a metal microscope. It was confirmed whether a uniform resin layer was formed on the insulating resin layer.

9. Moisture resistance reliability The humidity resistance reliability is determined by leaving the semiconductor device obtained above for 100 hours in an atmosphere of 85 ° C. and 85% humidity, then performing 3 times of 260 ° C. reflow, The backside peeling and solder bump defects were valued.
Each code is as follows.
○: practically no problem Only minute peeling around the underfill, no bump defect ×: practically unusable 10% or more peeling and bump defect

10. Thermal shock test (temperature cycle (TC) test)
After confirming the continuity of the semiconductor device, a temperature cycle (TC) test was performed in which one cycle was -50 ° C for 10 minutes and 125 ° C for 10 minutes. The presence or absence of disconnection failure after 1000 cycles of the TC test was evaluated.

  Examples 1 to 7 are uniform multilayer printed wiring board resin compositions having no aggregates, and no aggregation occurred in the multilayer printed wiring board resin composition, resulting in good results with low viscosity. It was. Moreover, the prepreg produced using the resin composition for multilayer printed wiring boards and the insulating resin sheet had a good appearance. In Example 2, no inorganic filler was added and no solvent-insoluble component was present, so no peak appeared in the particle size distribution.

On the other hand, Comparative Example 1 is an example in which (B) the organic colorant was added and stirred at room temperature without being melt-mixed. However, when a prepreg or an insulating resin sheet was produced, the inorganic filler or the colorant was aggregated. Appearance unevenness occurred. Moreover, also about the particle size distribution, the average particle diameter became high compared with Example 1, and as a result, the viscosity of the resin composition for multilayer printed wiring boards was thickened compared with Example 1. Moreover, roughening unevenness during roughening occurred.
Comparative Example 2 is an example using a thermosetting resin having a softening point exceeding 50 ° C., but a prepreg or an insulating resin sheet is produced in the same manner as Comparative Example 1 because the viscosity does not decrease sufficiently during heat-melt mixing. As a result, agglomerates were observed, resulting in roughening unevenness in the roughening treatment.
Comparative Example 3 is an example in which distilled water was used as a solvent without using an organic solvent. However, as in Comparative Examples 1 and 2, uneven appearance and roughening due to aggregation of inorganic fillers and colorants were caused. It was.

The multilayer printed wiring board resin composition of the present invention is uniform and free of agglomerates in spite of containing an organic colorant, so that it is possible to obtain a prepreg or a resin sheet that has good appearance and can exhibit high functionality. it can.

Claims (10)

(A) A softening point or a melting point of a thermosetting resin having a melting point of 50 ° C. or less, and (B) an organic colorant is heated and melted and mixed at a temperature equal to or higher than the softening point of the (A) thermosetting resin. A resin composition for a multilayer printed wiring board , wherein a molten mixture is dispersed in a slurry obtained by mixing (C) an organic solvent and (D) an inorganic filler . 2. The resin composition for a multilayer printed wiring board according to claim 1, wherein the (B) organic colorant has a weight loss by sublimation at 260 ° C. or decomposition of 10% or less. The resin composition for a multilayer printed wiring board according to claim 1, wherein the organic colorant (B) is an anthraquinone compound. The inorganic filler (D) is magnesium hydroxide, aluminum hydroxide, silica, talc, calcined talc, and according to any one of claims 1 to 3 selected from the group consisting of alumina are those containing at least one or more Resin composition for multilayer printed wiring boards. An insulating resin sheet formed by forming an insulating resin layer comprising the resin composition for a multilayer printed wiring board according to any one of claims 1 to 4 on a thermoplastic resin film or a metal foil. A prepreg obtained by impregnating a base material with the resin composition for a multilayer printed wiring board according to any one of claims 1 to 4 . A laminated board obtained by superposing one or more prepregs according to claim 6 and heating and pressing. A multilayer printed wiring board using the laminated board according to claim 7 . A multilayer printed wiring board comprising the insulating resin sheet according to claim 5 and / or the prepreg according to claim 6 . A semiconductor device comprising a semiconductor element mounted on the multilayer printed wiring board according to claim 9 .