KR20140038519A - Laminated plate manufacturing method - Google Patents

Abstract

The preform 200 for buildup formed by the resin composition containing a thermosetting resin is laminated on the circuit formation surface 103 of the core layer 102 which has the circuit formation surface 103 on one side or both surfaces, and is laminated. The lamination process of obtaining a laminated body and the smoothing process of smoothing the surface of the laminated buildup prepreg 200 are performed continuously, and the hardening process which heats a laminated body further and advances hardening of a thermosetting resin is performed subsequently. As a manufacturing method of the laminated board 100, the measuring range 50-200 degreeC, the temperature increase rate of 3 degree-C / min, frequency 62.83rad / by the dynamic viscoelastic test of the buildup prepreg 200 in the stage which completed the lamination process When the minimum value of the complex dynamic viscosity in seconds is made into (eta) 1, (eta) 1 is 20 Pa * s or more and 300 Pa * s or less.

Description

Manufacturing method of laminated board {LAMINATED PLATE MANUFACTURING METHOD}

The present invention relates to a method for producing a laminate.

As a manufacturing method of the laminated board for multilayer printed wiring boards, the manufacturing method by the buildup system which alternately piles an insulating layer and a conductor layer on the circuit board which is a core layer is known. According to this method, the adhesive film in which the thermosetting resin layer was formed on the plastic film is mainly used for formation of an insulation layer. After laminating (laminating) this adhesive film to a core layer and peeling a plastic film, an insulating layer is formed by thermosetting a thermosetting resin.

On the other hand, due to the recent demand for miniaturization of electronic devices and electronic components, in multilayer printed wiring boards, there is a tendency to become even thinner, for example, thinning and omission of core layers are required. In this way, in order to maintain the mechanical strength of the multilayer printed wiring board while thinning of the multilayer printed wiring board is progressing, it is preferable to apply a prepreg provided with a sheet-like fibrous base material and a thermosetting resin instead of the above-described adhesive film as a material for forming the insulating layer. Valid.

For example, Patent Document 1 (Japanese Patent Laid-Open No. 2009-231240) discloses a cured prepreg layer obtained by compressing and thermosetting a prepreg impregnated with a thermosetting resin composition on a sheet-like fibrous substrate, and a thermosetting resin layer formed on both sides of the cured prepreg layer. It is described to use an insulating resin sheet having an adhesive for the production of a multilayer printed wiring board. It is shown that using such an insulating resin sheet can suppress exposure of the sheet-like fiber base material even when the surface of the formed insulating layer is roughened.

In addition, in Patent Document 2 (International Publication No. 2009/035014), after laminating an adhesive sheet on which a prepreg is formed on a support film to a circuit board, the prepreg is thermally cured without peeling the support film to form an insulating layer. It is described. When such an adhesive sheet is used, even when the thermosetting resin composition with fluidity enough to embed the circuit irregularities is used in the prepreg, the insulating layer is formed without the resin leaking out of the prepreg in the thermosetting step. What can be done is shown.

Japanese Patent Laid-Open No. 2009-231240 International Publication No. 2009/035014 Brochure

However, when the prepreg is used as the insulating layer as in Patent Documents 1 and 2, since the prepreg contains a fiber base material having a large elastic modulus such as glass cloth, the surface of the laminate can be smoothed sufficiently. There was no case. For this reason, the unevenness | corrugation derived from a fiber base material may remain on the laminated body surface after a smoothing process, and in that case, a gap will arise in the thickness of the laminated board obtained even through a smoothing process.

This invention is made | formed in view of the said situation, and provides the manufacturing method of the laminated board which can stably produce the laminated board which was excellent in surface smoothness.

According to the present invention,

A laminating step of laminating a prepreg for buildup formed of a resin composition containing a thermosetting resin on the circuit forming surface of the core layer having a circuit forming surface on one or both surfaces thereof to obtain a laminate;

Smoothing process for smoothing the surface of the laminated prepreg laminated

Then continuously,

As a manufacturing method of the laminated board which heats the said laminated body and performs the hardening process which advances hardening of the said thermosetting resin further,

The minimum value of the complex dynamic viscosity in the measurement range 50-200 degreeC, the temperature increase rate of 3 degree-C / min, and the frequency 62.83 rad / sec by the dynamic viscoelastic test of the said buildup prepreg in the step of completing the lamination process is made into (eta) 1. When you do,

There is provided a method for producing a laminated sheet having a η1 of 20 Pa · s or more and 300 Pa · s or less.

According to this invention, since the fluidity of the thermosetting resin in the prepreg is not excessively increased by setting the complex dynamic viscosity? 1 of the buildup prepreg at the completion of the lamination process to 20 Pa · s or more, the thermosetting resin permeates in the smoothing step Can be suppressed and the laminated body can be smoothed stably.

When the complex dynamic viscosity η1 of the buildup prepreg at the stage of completing the lamination process is 300 Pa · s or less, it is possible to ensure proper fluidity of the thermosetting resin in the prepreg so that the irregularities derived from the fiber- Since it does not remain, a laminated body can be smoothed stably.

Therefore, in this invention, the laminated board which was excellent in the surface smoothness in which the unevenness | corrugation derived from a fiber base material does not remain can be stably produced.

According to this invention, the manufacturing method of the laminated board which can stably produce the laminated board excellent in surface smoothness is provided.

The above-mentioned objects and other objects, features, and advantages will become more apparent from the preferred embodiments described below and the accompanying drawings attached thereto.
1 is a cross-sectional view showing a step of manufacturing a laminated plate in the present embodiment.
2 is a cross-sectional view showing the configuration of the prepreg for buildup in the present embodiment.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described using drawing. In addition, in all drawings, the same code | symbol is attached | subjected to the same component, and description is abbreviate | omitted suitably.

(Manufacturing Method of Laminated Plates)

The outline | summary of the manufacturing method of the laminated board in this embodiment is demonstrated. 1 is a cross-sectional view showing a step of manufacturing the laminated plate 100 in the present embodiment.

Initially, the thermosetting resin layer 201, the fiber base material 202, and the thermosetting resin layer 203 under heating pressurization to the circuit formation surface 103 of the core layer 102 in which the circuit 101 was formed in one or both surfaces. The buildup prepreg 200 provided with the laminate is laminated to obtain a laminate (lamination step). Subsequently, for example, the surface of the laminated prepreg 200 laminated is smoothed by a hot press through a pair of opposing metal members (smoothing step). Thereafter, the laminate is heated to further advance the curing of the thermosetting resin (curing step), whereby the laminate 100 in the present embodiment can be obtained.

Here, the build-up prepreg 200 at the stage of completing the lamination process is a minimum value of the complex dynamic viscosity in the measurement range 50-200 ° C., the temperature increase rate 3 ° C./min, and the frequency 62.83 rad / sec by a dynamic viscoelastic test. (eta) 1 is 20 Pa * s or more, Preferably it is 30 Pa * s or more, More preferably, it is 40 Pa * s or more. By setting complex dynamic viscosity (eta) 1 more than the said lower limit, since the fluidity | liquidity of the thermosetting resin in a prepreg does not become large too much, a thermosetting resin can be prevented from seeping out and it can stably smooth a laminated body.

In addition, the build-up prepreg 200 in the stage which completed the lamination process is the minimum value of the complex dynamic viscosity in the measurement range 50-200 degreeC, the temperature increase rate of 3 degree-C / min, and the frequency 62.83 rad / sec by a dynamic viscoelastic test. (eta) 1 is 300 Pa * s or less, Preferably it is 200 Pa * s or less, More preferably, it is 100 Pa * s or less. By making the complex dynamic viscosity (eta) 1 below the said upper limit, the fluidity | liquidity of the thermosetting resin in a prepreg can be ensured, and the unevenness | corrugation derived from the fiber base material 202 does not remain on the laminated body surface, and can laminate | stack smoothly a laminated body.

Moreover, even after completing a lamination process and before performing a smoothing process, reaction may advance with the heat which remain | survives in the laminated body by the prepreg 200 for buildup. Therefore, the step of completing the lamination step represents a state immediately before entering the smoothing step. Therefore, the buildup prepreg 200 does not need to satisfy said complex dynamic viscosity (eta) 1 immediately after a lamination process, and needs to satisfy said complex dynamic viscosity (eta) 1 until just before a smoothing process.

In addition, complex dynamic viscosity (eta) 1 can cut out the resin composition containing a thermosetting resin (it does not contain a fiber base material) from the buildup layer 300 of the laminated body surface, and sets it as a measurement sample, and can measure it using a dynamic viscoelasticity measuring apparatus.

Then, each material which comprises the laminated board 100 in this embodiment is demonstrated.

(Core layer)

The core layer 102 has a circuit forming surface 103 on which one or both surfaces of a substrate, such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate, is patterned. A branch says a sheet-like thing. In addition, the core layer 102 further includes an inner circuit board of the intermediate product on which the buildup layer 300 and the circuit 101 should be formed.

Although the manufacturing method of the core layer 102 is not specifically limited, For example, it uses a core layer which has metal foil on both surfaces, opens a predetermined place with a drill, and achieves the electrical conduction of both surfaces of a core layer by electroless plating. Then, the circuit 101 is formed by etching the metal foil. In addition, the thing which performed roughening process, such as blackening process, can be used suitably for an inner-layer circuit part. In addition, the opening portion can be appropriately buried with a conductor paste or a resin paste.

(Prepreg for buildup)

2 is a cross-sectional view showing the configuration of the prepreg 200 for buildup in the present embodiment. The prepreg 200 includes a thermosetting resin layer 201 and a thermosetting resin layer 203 provided on both sides of the fiber substrate 202 and the fiber substrate 202. The prepreg 200 can be formed by impregnating the resin composition P in the fiber base material 202.

Hereinafter, although the resin composition P used for the prepreg 200 is demonstrated, the thermosetting resin layer 201 and the thermosetting resin layer 203 provided in both surfaces of the fiber base material 202 may be mutually same, and may differ, respectively. .

The resin composition P used for the prepreg 200 contains the (A) epoxy resin. As the (A) epoxy resin, for example, 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 type Novolak type epoxy resins such as phenol novolak type epoxy resin and cresol novolak type epoxy resin, aryl alkylene type epoxy resins such as biphenyl type epoxy resin and biphenyl aralkyl type epoxy resin, And epoxy resins such as naphthalene type epoxy resins, anthracene type epoxy resins, phenoxy type epoxy resins, dicyclopentadiene type epoxy resins, norbornene type epoxy resins, adamantane type epoxy resins, and fluorene type epoxy resins. One type of them may be used alone, or two or more types may be used in combination.

Although content of (A) epoxy resin is not specifically limited, It is preferable that they are 15 mass% or more and 80 mass% or less of the whole resin composition P. More preferably, they are 25 mass% or more and 50 mass% or less. Moreover, when using together liquid epoxy resins, such as a liquid bisphenol-A epoxy resin and a bisphenol F-type epoxy resin, since impregnation with respect to the fiber base material 202 can be improved, it is preferable. Content of liquid epoxy resin is more preferable in it being 2 mass% or more and 18 mass% or less of the whole resin composition P. 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.

Moreover, the resin composition P may contain thermosetting resins other than epoxy resins, such as a melamine resin, a urea resin, and a cyanate ester resin, and it is preferable to use a cyanate ester resin together. Examples of the cyanate resin include, but are not limited to, bisphenol cyanates such as novolac cyanate resin, bisphenol A cyanate resin, bisphenol E cyanate resin and tetramethyl bisphenol F cyanate resin Resins and the like. Among them, a phenol novolak type cyanate resin is preferable from the viewpoint of low heat expansion. Moreover, one type or two or more types may also be used together and another cyanate resin is not specifically limited. It is preferable that cyanate resin is 8 mass% or more and 20 mass% or less of the whole resin composition P.

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

Among these, silica is especially preferable, and fused silica (especially spherical fused silica) is preferable at the point which is excellent in low thermal expansion. Although the shape is crushed and spherical, in order to lower the melt viscosity of the resin composition P in order to ensure the impregnation with respect to a fiber base material, the usage method according to the objective is employ | adopted, such as using spherical silica.

Although the average particle diameter of (B) inorganic filler is not specifically limited, 0.01 micrometer or more and 3 micrometers or less are preferable, and 0.02 micrometer or more and 1 micrometer or less are especially preferable. By setting the particle size of the inorganic filler (B) to 0.01 µm or more, the resin substrate P can be satisfactorily impregnated with the varnish as a low viscosity. Moreover, sedimentation etc. of (B) inorganic filler can be suppressed in a varnish by setting it as 3 micrometers or less. This average particle diameter can be measured, for example by a particle size distribution meter (made by Shimadzu Corporation, product name: laser diffraction type particle size distribution analyzer SALD series).

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

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

Although content of (B) inorganic filler is not specifically limited, 2 mass% or more and 70 mass% or less of the whole resin composition P are preferable, and 5 mass% or more and 65 mass% or less are especially preferable. If content is in the said range, it can be made especially low thermal expansion and low absorption. In addition, in the thermosetting resin layer 201 and the thermosetting resin layer 203, the content of the inorganic filler (B) may be changed as necessary to achieve both close contact with the conductor and low thermal expansion.

Although the resin composition P used for the prepreg 200 is not specifically limited, It is preferable to use the (C) coupling agent. The coupling agent (C) improves the wettability of the interface between the (A) epoxy resin and the (B) inorganic filler, thereby uniformly fixing the (A) epoxy resin and the (B) inorganic filler to the fiber base material, thereby providing heat resistance, in particular moisture absorption. Post soldering heat resistance can be improved.

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

Since the addition amount of (C) coupling agent depends on the specific surface area of (B) inorganic filler, it does not specifically limit, but 0.05 mass% or more and 3 mass% or less are preferable with respect to 100 mass parts of (B) inorganic fillers, Especially 0.1 mass % Or more and 2 mass% or less are preferable. By making content into 0.05 mass% or more, (B) inorganic filler can fully be coat | covered and heat resistance can be improved. By setting it as 3 mass% or less, reaction advances favorably and the fall of flexural strength etc. can be prevented.

Resin composition P can further use (D) phenol type hardening | curing agent. Examples of the phenol-based curing agent include phenol novolac resins, alkylphenol novolak resins, bisphenol A novolak resins, dicyclopentadiene-type phenol resins, xylyl-type phenol resins, terpene-modified phenol resins and polyvinyl phenols, It can be used in combination of two or more kinds.

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

You may use (E) hardening catalyst for resin composition P as needed. A well-known thing can be used as (E) hardening catalyst. For example, organometallic salts, such as zinc naphthenate, cobalt naphthenate, tin octylic acid, cobalt octylate, bisacetylacetonate cobalt (II), and trisacetylacetonate cobalt (III), triethylamine, tributylamine, diadia Tertiary amines such as xabicyclo [2,2,2] octane, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 2-ethyl-4-ethylimidazole, 2 Imidazoles such as -phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxy imidazole, 2-phenyl-4,5-dihydroxy imidazole, phenol, bisphenol A, nonyl Phenol compounds such as phenol, organic acids such as acetic acid, benzoic acid, salicylic acid, paratoluenesulfonic acid, and the like, or mixtures thereof. One type may be used independently including derivatives in these as a curing catalyst, and two or more types may be used together including these derivatives.

Although content of (E) hardening catalyst is not specifically limited, 0.05 mass% or more of the whole resin composition P is preferable, and 0.08 mass% or more is especially preferable. By making content of a hardening catalyst more than the said lower limit, the buildup prepreg whose complex dynamic viscosity (eta) 1 by a dynamic-viscoelasticity test is 20 Pa * s or more can be obtained more efficiently. Moreover, hardening can fully be promoted.

Moreover, although content of a curing catalyst is not specifically limited, 5 mass% or less of the whole resin composition P is preferable, and 2 mass% or less is especially preferable. By using below the said upper limit, the buildup prepreg whose complex dynamic viscosity (eta) 1 by a dynamic-viscoelasticity test is 300 Pa * s or less can be obtained more efficiently. In addition, the deterioration of the preservation of the prepreg 200 can be prevented.

The resin composition P is 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, a styrene- Thermoplastic elastomers such as polystyrene-based thermoplastic elastomers such as copolymers and styrene-isoprene copolymers, polyolefin-based thermoplastic elastomers, polyamide-based elastomers, polyester-based elastomers, polybutadiene, epoxy-modified polybutadiene, acrylic-modified polybutadiene, and methacryl-modified polybutadiene You may use diene type elastomers, such as butadiene, together. 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, it is excellent in the thickness uniformity of a prepreg, and excellent in heat resistance and the insulation of a micro wiring as a wiring board.

Moreover, you may add additives other than the said component, such as a pigment, dye, an antifoamer, a leveling agent, a ultraviolet absorber, a foaming agent, antioxidant, a flame retardant, and an ion trapping agent, to this resin composition P as needed.

Although the fiber base material 202 which impregnates the resin composition P is not specifically limited, Glass fiber base materials (glass cloth), such as a glass woven fabric and a glass nonwoven fabric, polyamide resin fiber, aromatic polyamide resin fiber, wholly aromatic polyamide resin fiber, etc. Composed of polyester resin fibers such as polyamide resin fibers, polyester resin fibers, aromatic polyester resin fibers, wholly aromatic polyester resin fibers, polyimide resin fibers, fluorine resin fibers, etc. Organic fiber base materials, such as a paper base material whose main component is a synthetic fiber base material, kraft paper, cotton linter paper, a blender of a linter and a kraft pulp, etc. are mentioned.

Among these, a glass fiber base material (glass cloth) is preferable. Thereby, a low absorption, high strength, low thermal expansion prepreg can be obtained.

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

The method of impregnating the resin composition P into the fiber base material 202 is, for example, a method of preparing a resin varnish V using the resin composition P to immerse the fiber base material 202 in the resin varnish V, and a method of applying by various coaters. The method of spraying by spray, the resin varnish V is apply | coated and dried to a base material, the resin sheet is produced, the resin sheet is arrange | positioned so that a resin layer may contact the fiber woven fabric 202, and the method etc. are mentioned. Among these, the method of immersing the fiber base material 202 in resin varnish V is preferable. Thereby, the impregnation property of the resin composition P with respect to the fiber base material 202 can be improved. In addition, when the fiber base material 202 is immersed in resin varnish V, normal impregnation coating equipment can be used.

It is preferable that the solvent used for the resin varnish V shows favorable solubility with respect to the resin component in the resin composition P, but you may use a poor solvent in the range which does not adversely affect. The solvent showing good solubility is, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene glycol, cellosolve And carbitol systems.

Although solid content of resin varnish V is not specifically limited, 20 mass% or more and 80 mass% or less of solid content of resin composition P are preferable, and 50 mass% or more and 65 mass% or less are especially preferable. Thereby, the impregnation property of the resin varnish V with respect to the fiber base material 202 can be improved further. Although the predetermined temperature which impregnates the resin composition P in the fiber base material 202 is not specifically limited, For example, the prepreg 200 can be obtained by drying at 90 degreeC or more and 220 degrees C or less. It is preferable that the thickness of the prepreg 200 is 20 micrometers or more and 100 micrometers or less.

The prepreg 200 may be substantially the same as or different from the thickness of the thermosetting resin layer 201 and the thermosetting resin layer 203 around the fiber substrate 202. In other words, the prepreg 200 may shift the center of the thickness direction of a fiber base material, and the center of the thickness direction of a prepreg.

The prepreg 200 may be laminated in plural sheets through a metal foil or a film. Metallic foils are for example 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, and the like. Metal foils may be mentioned. Among these, copper foil is especially preferable.

After laminating | stacking multiple sheets through metal foil or a film, you may heat and pressurize. Although the temperature to heat is not specifically limited, 120 degreeC or more and 230 degrees C or less are preferable, and 150 degreeC or more and 210 degrees C or less are especially preferable. Moreover, although the pressure to pressurize is not specifically limited, 1 MPa or more and 5 MPa or less are preferable, and 2 MPa or more and 4 MPa or less are especially preferable. By using such a prepreg 200, the laminated board which is excellent in dielectric characteristics and mechanical and electrical connection reliability in high temperature and high humidity can be obtained.

The prepreg 200 may be laminated by roll shape. At this time, the support base material may be provided on one side or both surfaces, and may be wound and laminated | stacked in the state which this support base material interposed. As a method of winding-up the prepreg 200 in roll shape, the following are mentioned, for example.

After impregnating the resin composition P in the fiber base material 202, it is conveyed to a roll laminating apparatus with a support base material, and it laminates by continuously pressurizing and heating a support base material to the prepreg 200 with a metal roll or an elastic material roll. Thereafter, the prepreg 200 can be rolled up into a roll by winding in a roll.

Moreover, you may manufacture the prepreg 200 wound by roll shape by conveying the sheet-like fiber base material 202 wound in roll shape continuously with a roll, and impregnating and drying the resin varnish V. As shown in FIG.

Plastic films may be used as the supporting substrate, and examples thereof include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polycarbonate (PC), acrylic resin (PMMA), cyclic polyolefin, and triacetyl. Cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide and the like. Among these, PET film and PEN film are preferable and PET film is especially preferable. The supporting base material may be subjected to mat treatment or corona treatment on the laminated surfaces of the thermosetting resin layers 201 and 203. After thermosetting of the prepreg 200, you may have a release layer in the surface which contact | connects the prepreg 200 in order to peel a support base material.

Moreover, when providing a support base material on one side, you may provide a protective material on the other side. In this case, it conveys to a roll type laminating apparatus so that a support material may contact a 2nd surface S2, and a protective material may contact | connect a 1st surface S1, and it laminates by pressing and heating with a metal roll or an elastic roll from both surfaces of a support base material and a protective material. You can. As a protective material, polyolefins, such as polyethylene, a polypropylene, polyvinyl chloride, polyesters, such as PET and PEN, a plastic film, such as PC and a polyimide, can be used, for example. It is preferable that the thickness of a protective material is 5 micrometers or more and 30 micrometers or less.

Then, each process of the manufacturing method of a laminated board is demonstrated in detail, respectively.

(Lamination process)

First, it is preferable to prepare the prepreg 200 wound by roll shape, and to convey it to a laminator with the sheet-like core layer 102. FIG. The laminator includes, for example, a pair of opposing elastic members, and is preferably laminated by heating and pressing through the elastic member in a state where the core layer 102 and the prepreg 200 are sandwiched between the elastic members. Do.

At this time, it is preferable to press through an elastic member using the laminator further equipped with elastic members, such as a heat insulating rubber. Since the elastic member is flexible and follows the uneven shape of the circuit 101 formed on the core layer, the core layer 102 and the prepreg 200 can be brought into close contact with each other.

It is preferable to use a laminator (vacuum laminator) which heats and pressurizes under vacuum as a laminator. As the elastic member, for example, a plate or rolled rubber can be used.

Although heating temperature is not specifically limited, 80 degreeC or more is preferable and 90 degreeC or more is more preferable. By setting it as the said lower limit or more, the buildup prepreg whose minimum value (eta) 1 of the complex dynamic viscosity by a dynamic-viscoelasticity test is 20 Pa * s or more can be obtained more efficiently. Moreover, 150 degrees C or less is preferable, and 140 degrees C or less of a heating temperature is more preferable. By setting it as the said upper limit or less, the buildup prepreg whose minimum value (eta) 1 of the complex dynamic viscosity by a dynamic-viscoelasticity test is 300 Pa * s or less can be obtained more efficiently.

Although heating time is not specifically limited, 10 second or more is preferable and 30 second or more is more preferable. By carrying out more than the said lower limit, the buildup prepreg whose complex dynamic viscosity (eta) 1 by a dynamic-viscoelasticity test is 20 Pa * s or more can be obtained more efficiently. Moreover, heating time is not specifically limited, 500 second or less is preferable and 300 second or less is more preferable. By using below the said upper limit, the buildup prepreg whose complex dynamic viscosity (eta) 1 by a dynamic-viscoelasticity test is 300 Pa * s or less can be obtained more efficiently.

It is preferable to perform a pressure in the range of 0.4 Mpa or more and 1.5 Mpa or less.

The laminator process can be performed using a vacuum laminator that is commercially available. For example, the vacuum pressurized laminator with which Nippon-Morton Co., Ltd. CPV300 is equipped, or the equivalent can be used.

(Smoothing process)

After the laminator process, the thermosetting resin layer 201 and the thermosetting resin layer 203 forming the prepreg 200 soften and follow the circuit 101 formed on the core layer 102 to deform into irregularities. Thus, the laminated laminate is smoothed by hot pressing through a pair of metal members facing the laminated buildup layer 300 and the core layer 102.

The smoothing process is carried out by heating and pressing the laminate through a metal member under atmospheric pressure.

Here, the build-up prepreg 200 at the stage where the smoothing process is completed has the minimum value of the complex dynamic viscosity in the measurement range 50-200 degreeC, the temperature increase rate of 3 degree-C / min, and the frequency 62.83 rad / sec by a dynamic viscoelastic test. It is preferable that η2 (hereinafter sometimes simply referred to as complex dynamic viscosity η2) satisfies η2 ≧ η1 × 1.1. By satisfying the above relationship, it is difficult to cause expansion or the like of the laminate in a subsequent curing step, and a laminate having more excellent surface smoothness can be obtained. Moreover, a hardening process can be performed more efficiently by satisfying the said relationship.

Moreover, it is preferable that the minimum value (eta) 2 of the complex dynamic viscosity by a dynamic viscoelasticity test is 350 Pa * s or more, and, as for the buildup prepreg 200 in the stage which completed the smoothing process, it is more preferable that it is 400Pa * s or more, 500Pa * s It is especially preferable that it is above. By carrying out complex dynamic viscosity (eta) 2 more than the said lower limit, expansion | lamination of a laminated body hardly arises in a subsequent hardening process, and the laminated board which was more excellent in surface smoothness can be obtained. Moreover, a hardening process can be performed more efficiently by satisfying the said relationship.

Moreover, it is preferable that minimum value (eta) 2 of the complex dynamic viscosity by a dynamic viscoelasticity test is 50,000 Pa * s or less, and, as for the buildup prepreg 200 in the stage which completed the smoothing process, it is more preferable that it is 10,000 Pa * s or less. By carrying out complex dynamic viscosity (eta) 2 below the said upper limit, since the hardening process is performed in the state with little stress distortion, the laminated board which is hard to produce expansion can be obtained.

In addition, complex dynamic viscosity (eta) 2 can cut out the resin composition containing a thermosetting resin (not including a fiber base material) from the buildup layer 300 of the laminated body surface, and makes it a measurement sample, and can measure it using a dynamic viscoelasticity measuring apparatus.

Although such a smoothing process can be performed using a commercially available hot press apparatus, the hot press apparatus which Nippon-Morton Co., Ltd. CPV300 makes, or the equivalent can be used, for example.

Although heating temperature is not specifically limited, 80 degreeC or more is preferable and 90 degreeC or more is more preferable. By setting it as the said lower limit or more, the buildup prepreg whose complex dynamic viscosity (eta) 2 by the dynamic viscoelasticity test in the step which completed the smoothing process is 350 Pa * s or more can be obtained more efficiently. Moreover, 180 degrees C or less is preferable, and 170 degrees C or less of heating temperature is more preferable. By using below the said upper limit, the buildup prepreg whose complex dynamic viscosity (eta) 2 by a dynamic-viscoelasticity test is 50,000 Pa * s or less can be obtained more efficiently.

Although heating time is not specifically limited, 10 second or more is preferable and 30 second or more is more preferable. By setting it as the said lower limit or more, the buildup prepreg whose complex dynamic viscosity (eta) 2 by the dynamic viscoelasticity test in the step which completed the smoothing process is 350 Pa * s or more can be obtained more efficiently. Moreover, heating time is not specifically limited, 500 second or less is preferable and 300 second or less is more preferable. By using below the said upper limit, the buildup prepreg whose complex dynamic viscosity (eta) 2 by the dynamic-viscoelasticity test in the stage which completed the smoothing process is 50,000 Pa * s or less can be obtained more efficiently.

It is preferable to perform a pressure in the range of 0.4 Mpa or more and 1.5 Mpa or less.

Moreover, it is preferable that the time of the lamination process and the time of the smoothing process which matched vacuum pumping and pressurization time are the same. By doing in this way, since the line speed which conveys a laminated body can be made constant, a lamination process and a smoothing process can be performed continuously and efficiently.

(Second smoothing process)

In the manufacturing method of the laminated board in this embodiment, the 2nd smoothing process is further performed between the said smoothing process (henceforth a 1st smoothing process) and the said hardening process, and further builds a prep for buildup, advancing reaction of a thermosetting resin further. The surface of the leg 200 may be further smoothed. Thereby, reaction of a thermosetting resin can further advance and the expansion of the surface of the laminated board 100 by volatilization etc. of an unreacted component in a process can be suppressed after that.

Moreover, it is not necessary to make heating temperature and a pressure into strict conditions by which hardening of a thermosetting resin arises by dividing and performing a smoothing process. For this reason, the surface of a laminated body can be smoothed, suppressing generation | occurrence | production of the residual stress of a laminated body on moderate conditions. Thereby, the generation amount of residual stress is suppressed and the deterioration of heat resistance and moisture resistance reliability is also suppressed.

In addition, depending on the amount of residual stress generated, warpage may occur in the laminate, and this warpage may occur remarkably after the laser via forming step is performed. When warpage arises in a laminated board, the curvature of a semiconductor package will become large and mounting yield will fall. Moreover, since the residual stress which arises in a laminated board can be further suppressed by carrying out the smoothing process separately, curvature can be suppressed and the laminated board which is more excellent in reliability can be obtained.

Although the collection | recovery of a 2nd smoothing process is not specifically limited, You may implement twice or more according to the surface state of a laminated body. By carrying out two or more times, the laminated board which is further excellent by surface smoothness can be obtained.

The second smoothing step may be carried out by changing conditions such as pressure and temperature while maintaining the pressure applied to the laminate during the first smoothing process, and after releasing the pressure applied to the laminate after the first smoothing process. You may carry out. In particular, it is preferable to perform a 2nd smoothing process after releasing the pressure applied to a laminated body after a 1st smoothing process.

Although a 2nd smoothing process is not specifically limited, You may carry out by the method similar to a 1st smoothing process, or you may implement by another method. As another method, the method using the belt conveyor shown below is mentioned, for example.

Initially, the laminated body after a 1st smoothing process is mounted on a belt conveyor. Next, a weight such as a metal member is placed on the laminate to place the laminate in a pressurized state. Subsequently, heating is performed while pressurizing the laminate by operating the belt conveyor and passing it through the drying furnace.

The metal member to be placed on the laminate is not particularly limited as long as it has a mass capable of pressing the laminate, but a plate made of stainless steel or the like is preferable because of corrosion resistance and availability.

Although the mass per unit area of the metal member mounted on a laminated body is not specifically limited, It is preferable that they are 0.01 kg / cm <2> or more and 15 kg / cm <2> or less. If it is the mass of the said range, the laminated body which was more excellent in surface smoothness can be obtained.

The mass per unit area may be adjusted depending on the thickness and the number of sheets of the metal member, or may be adjusted by placing a weight on the metal member.

Although the heating temperature in a 2nd smoothing process is not specifically limited, It is preferable that temperature is higher in the range of 10 degreeC or more and 100 degrees C or less than a 1st smoothing process. By setting higher than the temperature of a 1st smoothing process, the surface of the buildup prepreg 200 can be smoothed more efficiently, further advancing reaction of a thermosetting resin.

Such a second smoothing step can be performed using a commercially available apparatus, but for example, a thermoforming press manufactured by Kitagawa Precision Machinery Co., Ltd., a hot press apparatus manufactured by Meiki Corporation, a heater press apparatus manufactured by Mikado Technos, Held's belt press device, Sandpik's belt press device, or the like can be used.

(Curing Process)

After the smoothing step, the thermosetting resin layer 201 and the thermosetting resin layer 203 forming the prepreg 200 for build-up are further cured by heating. Although the temperature to harden | cure is not specifically limited, For example, it can harden | cure in the range of 100 degreeC or more and 250 degrees C or less, Preferably it can harden at 150 degreeC or more and 200 degrees C or less. Preferably hardening time can be about 30 to 75 minutes.

A hardening process is normally performed by heating a laminated body under atmospheric pressure.

In the hardening process in this embodiment, it is preferable to gradually raise the temperature of a laminated body from initial temperature to maximum achieved temperature. By doing in this way, the thermosetting resin layer 201 and the thermosetting resin layer 203 which form the prepreg 200 for buildup can be hardened, suppressing the expansion which generate | occur | produces on the laminated body surface, and the generation of the residual stress of a laminated body. By suppressing the expansion occurring on the surface of the laminate, a laminate having more excellent surface smoothness can be obtained.

In addition, depending on the amount of residual stress generated, warpage may occur in the laminate, and particularly, after the laser via forming step is performed, this warpage may occur remarkably. When warpage arises in a laminated board, the curvature of a semiconductor package will become large and mounting yield will fall. In the hardening process, since the residual stress which arises in a laminated board can be suppressed by gradually raising the temperature of a laminated body from initial temperature to the highest achieved temperature, curvature can be suppressed and the laminated board which is more reliable can be obtained.

The initial temperature is not particularly limited as long as it is a temperature at which a rapid curing reaction does not occur. When a hardening process is performed after cooling the temperature of a laminated body to room temperature vicinity after a smoothing process, the initial temperature is preferably near room temperature. For example, they are 0 degreeC or more and 40 degrees C or less.

After the smoothing step, when the curing step is subsequently performed, the curing step may not be performed after the temperature of the laminate is cooled to around room temperature. In that case, 40 degreeC or more is preferable and 60 degreeC or more is more preferable. By setting it more than the said lower limit, hardening of a thermosetting resin layer can be advanced more efficiently, suppressing the expansion which arises on the surface of a laminated body, and generation | occurrence | production of the residual stress of a laminated body.

Moreover, although initial stage temperature is not specifically limited, 90 degrees C or less is preferable, and 80 degrees C or less is more preferable. By setting it below the said upper limit, rapid temperature rise of a laminated body hardly arises, hardening of a thermosetting resin layer can be advanced, further suppressing the expansion which generate | occur | produces on the surface of a laminated body, and generation | occurrence | production of the residual stress of a laminated body further.

Although the maximum achieved temperature is not specifically limited, 90 degreeC or more is preferable and 120 degreeC or more is more preferable. By carrying out more than the said lower limit, hardening can be fully promoted.

Moreover, although the maximum achieved temperature is not specifically limited, 230 degrees C or less is preferable, and 200 degrees C or less is more preferable. By setting it as the said upper limit or less, hardening of a thermosetting resin layer can be advanced more efficiently, suppressing the expansion which arises on the surface of a laminated body, and generation | occurrence | production of the residual stress of a laminated body.

The average temperature increase rate from the initial temperature to the highest achieved temperature is not particularly limited as long as the rapid curing reaction does not occur, but is preferably at least 1 ° C / minute, more preferably at least 3 ° C / minute. By carrying out more than the said lower limit, hardening reaction can be advanced more efficiently.

Moreover, although the average temperature increase rate from an initial temperature to a maximum achieved temperature is not specifically limited, 15 degrees C / min or less is preferable, and 12 degrees C / min or less is more preferable. By setting it as the said upper limit or less, hardening of a thermosetting resin layer can be advanced more efficiently, suppressing the expansion which arises on the surface of a laminated body, and generation | occurrence | production of the residual stress of a laminated body.

In addition, the average temperature increase rate from the initial temperature to the highest achieved temperature can be calculated from the time until the surface temperature of the laminate reaches the highest achieved temperature and the difference between the highest achieved temperature and the initial temperature. Here, the surface temperature of a laminated body can be measured by embedding a thermocouple in a laminated body, for example.

In addition, the temperature increase rate from an initial temperature to a maximum achieved temperature may be constant, and you may change at least 2 or more steps. In order to proceed the curing process more efficiently while suppressing the expansion occurring on the surface of the laminate and the occurrence of residual stress of the laminate, the initial temperature increase rate of the curing process is set to be slow, and the temperature increase rate gradually increases as the curing proceeds. It is preferable to set so that it is.

Although the heating apparatus of the laminated body in a hardening process is not specifically limited, A well-known heating method is used. For example, a heat drying apparatus such as hot air drying, far-infrared heating, high frequency induction heating or the like can be used.

Although the heating method of a laminated body is not specifically limited, You may pass a laminated body in a transverse conveyance type heat drying apparatus, and may heat continuously, You may leave a laminated body in a heat drying apparatus, and may heat in a batch type.

Although the method of gradually raising the temperature of a laminated body from initial temperature to maximum achieved temperature is not specifically limited, The following methods are mentioned. For example, when a laminated body is continuously heated through the horizontal conveyance type heat drying apparatus, it can implement using the heat drying apparatus which has two or more units. The temperature at which the laminate is heated is raised in steps by raising the temperature from the first unit through which the laminate passes. For this reason, the temperature of a laminated body can be changed in steps from an initial temperature to a maximum achieved temperature.

Moreover, when a laminated body is left still in a heat-drying apparatus and it heats batch-wise, the temperature of a laminated body can be gradually raised from initial temperature to maximum achieved temperature, for example by setting the temperature rising profile of a heat-drying apparatus. Moreover, even if the laminated body of an initial temperature state is arrange | positioned so that the whole laminated body may be heated uniformly in the heat drying apparatus previously set to the highest achieved temperature, the temperature of a laminated body can be raised gradually from initial temperature to maximum achieved temperature.

Although hardening time is not specifically limited, 30 minutes or more are preferable and 45 minutes or more are more preferable. By carrying out more than the said lower limit, hardening can be fully promoted.

Moreover, although hardening time is not specifically limited, 75 minutes or less are preferable and 60 minutes or less are more preferable. By setting it as the said upper limit or less, hardening of a thermosetting resin layer can be advanced more efficiently, suppressing the expansion which arises on the surface of a laminated body, and generation | occurrence | production of the residual stress of a laminated body.

Moreover, also in the process of reducing the temperature of a laminated body, it is preferable to gradually lower the temperature of a laminated body from the highest achieved temperature. By doing in this way, the temperature of a laminated body can be returned to room temperature, suppressing generation | occurrence | production of the residual stress of a laminated body.

(Laser via forming process)

Next, a via hole is formed by irradiating the hardened build-up layer 300 with a laser such as a carbon dioxide laser or a YAG laser. The resin residue after laser irradiation is preferably removed by an oxidizing agent such as a permanganate or a dichromate. Moreover, the surface of the smooth buildup layer 300 can be matched simultaneously, and the adhesiveness of the circuit 101 formed by metal plating which follows can be improved. The buildup layer 300 can uniformly perform fine concavo-convex shapes in the roughening process. In addition, since the smoothness of the surface of the buildup layer 300 is high, the fine wiring circuit 101 can be formed with high accuracy. After that, a solder resist is formed on the outermost layer, the electrode portion for connection is exposed, nickel-gold plating treatment is carried out so that the semiconductor element can be mounted by exposure and development, and the laminate can be cut to a predetermined size.

When the manufacturing method of the laminated board in this embodiment is used, since the residual stress which arises in a laminated board is suppressed, even if it performs a laser via formation process, curvature hardly arises in the laminated board obtained. For this reason, the laminated board with curvature suppressed can be obtained.

(Semiconductor package)

Next, the semiconductor package will be described.

This semiconductor package can be manufactured by mounting a semiconductor element on said laminated board. The mounting method and the sealing method of a semiconductor element are not specifically limited. For example, it can manufacture by the following method.

First, the soldering bump of the semiconductor element and the connection electrode part on a laminated wiring board are aligned using a flip chip bonder etc. Next, a solder bump is heated above melting | fusing point using an IR reflow apparatus, a hotplate, and other heating apparatuses, and it connects by melt-bonding a multilayer printed wiring board and a solder bump. Finally, a semiconductor package can be obtained by filling and hardening liquid sealing resin between a laminated wiring board and a semiconductor element.

As mentioned above, although embodiment of this invention was described with reference to drawings, these are illustrations of this invention, Various structures of that excepting the above are also employable.

For example, in FIG. 1, when the buildup layer is one layer, the structure which laminated | stacked two or more layers on one side or both sides of a core layer may be employ | adopted. In addition, although the case where one layer of sheet-like fiber base material is included in the prepreg for buildup was shown in FIG. 1 and FIG. 2, you may employ | adopt the structure in which two or more layers of fiber base material are contained in a prepreg. In addition, although the case where the thickness of the thermosetting resin layer 201 and the thermosetting resin layer 203 was the same in FIG. 1 and FIG. 2 was shown, the structure which differs in the thickness of the thermosetting resin layer 201 and the thermosetting resin layer 203 is employ | adopted. You may also

Example

Hereinafter, although an Example and a comparative example demonstrate this invention, this invention is not limited to these.

The raw material used by the Example and the comparative example is as follows.

Inorganic filler: Spherical silica (SO-25R made from admatex company, average particle diameter 0.5 micrometer)

Epoxy resin: Biphenyl aralkyl type novolak epoxy resin (NC-3000 made by Nippon Kayaku Co., Ltd.)

Epoxy resin: Dicyclopentadiene type novolak epoxy resin (product made in DIC Corporation, HP-7200)

Epoxy resin: Bisphenol A type liquid epoxy resin (made by Mitsubishi Chemical Corporation, jER-828)

Epoxy resin: Bisphenol F type liquid epoxy resin (made by Mitsubishi Chemical Corporation, jER-807)

Cyanate resin: Novolac-type cyanate resin (Prinmaset PT-30 made by LONZA company)

Phenolic hardener: Novolak-type phenol resin (made by DIC Corporation, TD-2090-60M, 60% (w / v) methyl ethyl ketone solution)

Phenoxy resin: (Mitsubishi Chemical Corporation, YX6954BH30, 30% (w / v) methyl ethyl ketone / anon solution)

Polyvinyl acetal resin: (Sekisui Chemicals, KS-10 (25 mol% of hydroxyl groups))

Curing catalyst: 2-ethyl-4-methylimidazole (made by Shikoku Chemical Co., Ltd., 2E4MZ)

Coupling agent: N-phenyl-3-aminopropyltrimethoxysilane (made by Shin-Etsu Chemical Co., Ltd., KBM-573)

( Example  One)

(1) Preparation of Resin Varnish A

Phenol novolak-type cyanate as 30 mass parts of dicyclopentadiene type epoxy resins (made by DIC Corporation, HP-7200), bisphenol F-type liquid epoxy resin (made by Mitsubishi Chemical Corporation, jER807) and cyanate resin 14 parts by mass of resin (manufactured by LONZA, Primaset PT-30), 3 parts by mass of YX6954BH30 manufactured by Mitsubishi Chemical Corporation as a phenoxy resin, and 0.2 parts by mass of imidazole (manufactured by Shikoku Chemical Co., Ltd., 2E4MZ) as a curing catalyst. It stirred for 60 minutes and mixed in the mixed solvent of cyclohexanone. In addition, 0.1 mass part of N-phenyl-3-aminopropyl trimethoxysilane (KBM-573 by Shin-Etsu Chemical Co., Ltd.) as a coupling agent, and spherical silica (SO25R by Admatex company, average particle diameter: 0.5 micrometer) as an inorganic filler 49.7 A mass part was added, and it stirred for 10 minutes with the high speed stirring apparatus, and produced the resin varnish of 65% of solid content.

(2) Preparation of Resin Sheet A

The obtained resin varnish was coated on one side of a 36-micrometer-thick PET (polyethylene terephthalate) film using a comma coater apparatus. This was dried for 3 minutes by the 160 degreeC drying apparatus, and the resin sheet A with a base material whose resin thickness is 17.5 micrometers was produced.

(3) Preparation of Prepreg A

The prepreg was manufactured by the vacuum lamination apparatus and the hot air drying apparatus using the glass woven fabric (cloth type | mold # 1017, width 530mm, thickness 15micrometer, basis weight 12g / m <2>) as a fiber base material.

Specifically, two sheets of resin sheet A were prepared (A1 and A2), and each sheet of resin sheet A1 and resin sheet A2 was placed on the both sides of the glass woven fabric so as to be positioned at the center of the width direction of the glass woven fabric, one by one, and then 0.1 MPa ( It bonded together using the lamination roll of 80 degreeC under reduced pressure conditions of 750 Torr).

Here, in the inner region of the width direction of the glass woven fabric, the resin layers of the resin sheet A1 and the resin sheet A2 are bonded to both sides of the fiber cloth, respectively, and in the outer region of the width direction of the glass fabric, the resin sheet A1 and the resin sheet. The resin layers of A2 were bonded together.

Subsequently, the above bonded was passed through a transverse conveying hot air drying apparatus set at 120 ° C. for 2 minutes to heat the product without applying a pressure to obtain a prepreg having a thickness of 40 μm.

(4) laminate process

The laminated body was manufactured from the prepreg with PET base material using the 2-stage buildup laminator CVP300 by Nichigo-Morton Corporation. Specifically, ELC-4785GS-B (manufactured by Sumitomo Bakelite Co., Ltd., copper foil 12 μm) having a thickness of 200 μm is used, opening a predetermined place with a drill to achieve conduction by electroless plating, and etching the copper foil. The core layer which has a circuit formation surface was produced. Moreover, the said prepreg was cut into the sheet | leaf, it was set to the said CVP300, was temporarily attached to the said core layer, and vacuum lamination was performed for 120 degreeC, 0.7 MPa, and 60 second in a vacuum laminator.

(5) smoothing process

Thereafter, hot pressing was performed at 120 ° C., 0.6 MPa for 60 seconds using a hot press device of CPV300 manufactured by Nichigo Morton, and smoothed.

(6) curing process

Then, it heat-processed at 170 degreeC for 60 minutes, hardened the thermosetting resin in the prepreg for buildup, and obtained the laminated board.

Examples 2-8 and Comparative Examples 1-3 produced the laminated board by the method similar to Example 1 except having changed the conditions of the composition of a resin varnish, the lamination process, and the smoothing process to the value shown in Table 1.

[evaluation]

(1) Measurement of complex dynamic viscosity η 1 by dynamic viscoelastic test

After completion of the laminating process, the resin composition (not including the fiber base material) containing the thermosetting resin was cut out from the prepreg for buildup on the laminate surface to be a measurement sample, and a dynamic viscoelasticity measuring device (manufactured by Anton Paar, device name Physica MCR) -301), the complex dynamic viscosity (eta) 1 was measured on condition of the following.

Frequency: 62.83rad / s

Measuring range 50 ~ 200 ℃

Temperature rise rate 3 degrees Celsius / minute

Geometry ： Parallel Plate

Plate diameter: 10mm

Plate spacing: 0.1mm

Load (normal force): 0N (constant)

Strain: 0.3%

Measurement atmosphere: Nitrogen

(2) Measurement of complex dynamic viscosity η 2 by dynamic viscoelastic test

After completion of the smoothing process, the resin composition containing the thermosetting resin (not including the fiber base material) is cut out of the prepreg for buildup on the surface of the laminate to obtain a measurement sample, and the complex dynamic viscosity under the same conditions as the complex dynamic viscosity η1 described above. (eta) 2 was measured.

(3) thickness gap

The cross section of the laminated board was observed with a scanning electron microscope (SEM), and the thickness difference between the part with and without the adjacent copper wiring was measured.

Thickness difference was measured by n = 10, the thing less than 0.8 micrometer in average was made into (circle), and also the thing of average 0.8 micrometer or more and less than 1.2 micrometer was made into (circle) as pass, and the thing of average 1.2 micrometers or more was made into x as rejection. The results are shown in Table 1.

( Example  9)

The laminated board was manufactured by the method similar to Example 1 except having performed the hardening process as follows.

The laminated body obtained was put into the hot air drying apparatus which set the temperature profile to the initial temperature of 25 degreeC, the maximum achieved temperature of 160 degreeC, the temperature increase rate of 3 degree-C / min, and hardening time for 60 minutes, and hardened reaction of the thermosetting resin of the prepreg for buildups. .

In addition, hardening time here means the time from taking out a laminated body in the hot-air drying apparatus set to initial temperature, and taking out. After the apparatus reached | attained the highest achieved temperature, hardening reaction was performed for the remaining time, maintaining it at the highest reached temperature. Moreover, the temperature of the laminated body was measured by embedding a thermocouple in the laminated body, and confirmed that the temperature increase rate of the laminated body and the temperature increase rate of the hot air drying apparatus were substantially the same.

(7) making the circuit board

Next, via holes were formed in the obtained laminated plate by a carbonate laser. The via and the surface of the resin layer were immersed in a swelling liquid at 60 ° C. (manufactured by Atotech Japan Co., Ltd., swelling deep security P) for 5 minutes, and further aqueous solution of potassium permanganate at 80 ° C. (manufactured by Atotech Japan Co., Ltd. After immersion in compact CP) for 10 minutes, neutralization was performed.

After this process of degreasing, catalyzing and activating, an electroless copper plating film is formed to about 0.5 micrometer, a plating resist is formed, and an electroless copper plating film is used as a feed layer, and 10 micrometers of pattern electroplating copper are formed, The fine circuit processing of L / S = 50/50 micrometers was performed. Next, after performing annealing treatment at 200 degreeC for 60 minutes in the hot-air drying apparatus, the power supply layer was removed by flash etching.

Next, the solder resist layer was formed on the laminated board obtained above, and the blind via hole (non-through hole) was formed with the carbonate laser so that a semiconductor element mounting pad etc. might be exposed.

Finally, on the circuit layer exposed from the solder resist layer, a plating layer consisting of 3 µm of electroless nickel plating layer and 0.1 µm of electroless gold plating layer was further formed thereon, and the obtained substrate was cut into a size of 50 mm x 50 mm. The circuit board for semiconductor packages was obtained.

(8) Fabrication of Semiconductor Packages

On the circuit board for semiconductor packages, the semiconductor element (TEG chip, size 20mm * 20mm, thickness 725micrometer) which has a solder bump was mounted by heat-compression bonding by the flip chip bonder apparatus. Next, after the solder bumps were melt-bonded in an IR reflow furnace, a liquid sealing resin (CRP-X4800B manufactured by Sumitomo Bakelite Co., Ltd.) was filled and the semiconductor sealing package was obtained by curing the liquid sealing resin. In addition, the liquid sealing resin was hardened on the conditions of the temperature of 150 degreeC, and 120 minutes. Moreover, the solder bump of the semiconductor element used what was formed by the lead-free solder of Sn / Ag / Cu composition.

( Example  10)

A laminate, a circuit board, and a semiconductor package were manufactured in the same manner as in Example 9 except that the temperature increase rate was 10 ° C / min.

( Example  11)

In the curing step, the temperature of the hot air drying device is set to 100 ° C. in advance, and then the laminate is placed on a hot air drying device support so that the entire laminate is heated evenly, and the curing step is performed, and the curing time is 30 minutes. A laminate, a circuit board, and a semiconductor package were manufactured in the same manner as in Example 9 except for the above. In addition, the surface temperature of the laminated body was measured by embedding a thermocouple in the laminated body, and calculated the average temperature increase rate from the time until the laminated body reached the maximum temperature within the range of 5 degrees Celsius before and after 100 degrees Celsius which is set temperature. The temperature increase rate was 11 degree-C / min.

( Example  12)

The laminated board, the circuit board, and the semiconductor package were produced by the method similar to Example 9 except having set the compounding quantity of each component in the resin varnish as having shown in Table 2, and making temperature rising rate 5 degree-C / min.

( Example  13)

In the curing step, after setting the temperature of the hot air drying device to 160 ° C. in advance, the laminate is placed in the hot air drying device to perform a curing step, and the laminate is subjected to the same method as in Example 12 except that the curing time is 30 minutes. A circuit board and a semiconductor package were manufactured. The average temperature increase rate calculated by the method similar to Example 11 was 32 degreeC / min.

( Example  14)

A laminated plate, a circuit board, and a semiconductor package were manufactured in the same manner as in Example 13, except that the compounding amounts of the components in the resin varnish were as described in Table 2. The average temperature increase rate calculated by the method similar to Example 11 was 30 degreeC / min.

( Example  15)

A laminated sheet, a circuit board, and a semiconductor package were manufactured in the same manner as in Example 9, except that the temperature increase rate was 20 ° C / min, and the curing time was 30 minutes.

[evaluation]

(4) moisture resistance

The circuit board after electroplating and annealing is cut out into 50 mm squares, and processed three times in an IR reflow furnace (peak temperature 260 ° C.) after 168 hours under 85 ° C. and 85% moisture absorption conditions (MSL level). 1 equivalent treatment) confirmed the presence or absence of expansion.

○: There is no expansion

×: With expansion

( Example  16)

Between the smoothing process and the hardening process, the laminated board was manufactured by the method similar to Example 1 except having performed twice the same operation as the 1st smoothing process as a 2nd smoothing process. In addition, a circuit board and a semiconductor package were manufactured in the same manner as in Example 9.

( Example  17)

A laminated board, a circuit board, and a semiconductor package were manufactured in the same manner as in Example 16, except that the second smoothing step was changed to one-time smoothing at 140 ° C, 0.6 MPa, and 60 seconds of hot press.

( Example  18)

The 2nd smoothing process was changed into the method of smoothing by performing 60 minutes at a temperature increase rate of 3 degree-C / min, an initial temperature of 25 degreeC, the highest achieved temperature of 120 degreeC, and 0.6 MPa using a multistage heat press, and also does not perform a hardening process. A laminate, a circuit board, and a semiconductor package were manufactured in the same manner as in Example 16 except for the above. After reaching the highest achieved temperature, smoothing was performed for the remaining time while maintaining the highest achieved temperature.

( Example  19)

A laminated board, a circuit board, and a semiconductor package were manufactured in the same manner as in Example 18, except that the compounding amounts of the components in the resin varnish were described in Table 3.

( Example  20)

A laminated plate, a circuit board, and a semiconductor package were manufactured in the same manner as in Example 16 except that the second smoothing step was changed to the following method and the curing step was not performed.

Initially, the laminated body after a 1st smoothing process is mounted on a belt conveyor. Next, 10 sheets of stainless steel elastic bodies having a mass per unit area of 0.01 kg / cm 2 are stacked on the laminate, and the laminate is brought into a pressurized state. Subsequently, the belt conveyor was operated, the inside of a drying furnace with a temperature of 120 ° C. was operated at a speed of 0.05 m / min, and the laminate was heated and pressed to smooth.

( Example  21)

A laminate, a circuit board, and a semiconductor package were manufactured in the same manner as in Example 16 except that the second smoothing step was not performed.

The present invention can also take the following aspects.

[One]

A laminating step of laminating a prepreg for buildup formed of a resin composition containing a thermosetting resin on the circuit forming surface of the core layer having a circuit forming surface on one or both surfaces thereof to obtain a laminate;

The smoothing process of smoothing the surface of the laminated prepreg laminated was continuously performed, and after that,

As a manufacturing method of the laminated board which heats the said laminated body and performs the hardening process which advances hardening of the said thermosetting resin further,

The minimum value of the complex dynamic viscosity in the measurement range 50-200 degreeC, the temperature increase rate of 3 degree-C / min, and the frequency 62.83 rad / sec by the dynamic viscoelastic test of the said buildup prepreg in the step of completing the lamination process is made into (eta) 1. When you do,

The manufacturing method of the laminated board whose (eta) 1 is 20 Pa * s or more and 300 Pa * s or less.

[2]

The minimum value of the complex dynamic viscosity in the measurement range of 50-200 degreeC, the temperature increase rate of 3 degree-C / min, and the frequency of 62.83 rad / sec by the dynamic viscoelastic test of the said buildup prepreg in the step which completed the said smoothing process to (eta) 2 When you do,

The manufacturing method of the laminated board as described in said [1] which satisfy | fills (eta) 2≥ (eta) 1 * 1.1.

[3]

The said (2) manufacturing method of the laminated board as described in said [2] whose said (eta) 2 is 350 Pa * s or more.

[4]

The said prepreg for buildup is a manufacturing method of the laminated board in any one of said [1]-[3] formed by impregnating the said resin composition in a fiber base material.

[5]

The manufacturing method of the laminated board as described in said [4] whose said fiber base material is a glass fiber base material.

[6]

The said hardening process WHEREIN: The manufacturing method of the laminated board in any one of said [1]-[5] which raises the temperature of the said laminated body gradually from an initial temperature to a maximum achieved temperature.

[7]

The said hardening process WHEREIN: The manufacturing method of the laminated board as described in said [6] whose temperature increase rate from the said initial temperature to the said highest achieved temperature is constant.

[8]

The said hardening process WHEREIN: The manufacturing method of the laminated board as described in said [6] which makes the temperature increase rate from the said initial temperature to the said highest achieved temperature at least 2 steps or more.

[9]

In the said hardening process, the manufacturing method of the laminated board in any one of said [6]-[8] whose average temperature rising rate from the said initial temperature to the said highest achieved temperature is 1 degreeC / min or more and 15 degrees C / min or less.

[10]

The said hardening process WHEREIN: The manufacturing method of the laminated board in any one of said [6]-[9] whose said highest achieved temperature is 90 degreeC or more and 230 degrees C or less.

[11]

The manufacturing method of the laminated board in any one of said [1]-[10] which further performs the 2nd smoothing process which further smoothens the surface of the said prepreg for buildups between the said smoothing process and the said hardening process.

[12]

The manufacturing method of the laminated board as described in said [11] which performs the said 2nd smoothing process after releasing the pressure applied to the said laminated body after the said smoothing process.

[13]

The manufacturing method of the laminated board as described in said [11] or [12] which raises heating temperature rather than the said smoothing process and implements a said 2nd smoothing process.

[14]

The manufacturing method of the laminated board as described in said [13] whose difference of the heating temperature of the said smoothing process and the said 2nd smoothing process is 10 degreeC or more and 100 degrees C or less.

[15]

The said 2nd smoothing process WHEREIN: The manufacturing method of the laminated board in any one of said [11]-[14] which heats and pressurizes, carrying and conveying the said laminated body on a belt conveyor.

[16]

The manufacturing method of the laminated board as described in said [15] in which said pressurization is carried out by loading a metal member on the said laminated body.

[17]

The manufacturing method of the laminated board as described in said [16] whose mass per unit area of the said metal member is 0.01 kg / cm <2> or more and 1 kg / cm <2> or less.

[18]

The manufacturing method of the laminated board as described in said [16] or [17] which the said metal member consists of stainless steel.

[19]

The manufacturing method of the laminated sheet in any one of said [11]-[18] which performs a said 2nd smoothing process twice or more.

[20]

In the said lamination process, the manufacturing method of the laminated board in any one of said [1]-[19] which heats and pressurizes in the state which sandwiched the said core layer and the said buildup prepreg with a pair of opposing elastic members. .

[21]

The prepreg for buildup is wound and laminated in roll shape,

Production of the laminated board as described in any one of said [1] to [20] which conveys the said prepreg for winding up laminated | stacked, conveys the said sheet-like core layer, and performs the said lamination process and the said smoothing process continuously. Way.

[22]

In the said smoothing process, the manufacturing method of the laminated board as described in any one of said [1]-[21] which heats and pressurizes in the state which sandwiched the said core layer and the said buildup prepreg with a pair of metal member which opposes. .

[23]

The manufacturing method of the laminated sheet in any one of said [1]-[22] which performs a laser via formation process further after the said hardening process.

[24]

The manufacturing method of the laminated sheet in any one of said [1]-[23] which the time of the said lamination process and the time of the said smoothing process which matched vacuum pumping and pressurization time are the same.

This application claims the priority based on Japanese Patent Application No. 2011-137593 for which it applied on June 21, 2011, and includes all those disclosed here.

Claims (17)

On the circuit formation surface of the core layer which has a circuit formation surface on one side or both surfaces,
A lamination step of laminating a prepreg for buildup formed of a resin composition containing a thermosetting resin under heating and pressing to obtain a laminate;
Smoothing process for smoothing the surface of the laminated prepreg laminated
Then continuously,
As a manufacturing method of the laminated board which heats the said laminated body and performs the hardening process which advances hardening of the said thermosetting resin further,
The minimum value of the complex dynamic viscosity in the measurement range 50-200 degreeC, the temperature increase rate of 3 degree-C / min, and the frequency 62.83 rad / sec by the dynamic viscoelastic test of the said buildup prepreg in the step of completing the lamination process is made into (eta) 1. When you do,
The manufacturing method of the laminated board whose (eta) 1 is 20 Pa * s or more and 300 Pa * s or less. The method according to claim 1,
The minimum value of the complex dynamic viscosity in the measurement range 50-200 degreeC, the temperature increase rate of 3 degree-C / min, and the frequency of 62.83 rad / sec by the dynamic viscoelastic test of the said buildup prepreg at the stage which completed the said smoothing process to (eta) 2 When you do,
The manufacturing method of the laminated board which satisfy | fills (eta) 2≥ (eta) 1 * 1.1. The method of claim 2,
The said (eta) 2 is 350Pa * s or more manufacturing method of the laminated board. The method according to any one of claims 1 to 3,
The said prepreg for buildup is a manufacturing method of the laminated board formed by impregnating the said resin composition in a fiber base material. The method of claim 4,
The said fiber base material is a manufacturing method of the laminated board which is a glass fiber base material. The method according to any one of claims 1 to 5,
The said hardening process WHEREIN: The manufacturing method of the laminated board which raises a temperature of the said laminated body gradually from an initial temperature to a maximum achieved temperature. The method of claim 6,
The said hardening process WHEREIN: The manufacturing method of the laminated board which makes the temperature increase rate from the said initial temperature to the said highest achieved temperature at least 2 steps or more. The method according to any one of claims 1 to 7,
The manufacturing method of the laminated board which further performs the 2nd smoothing process which further smoothens the surface of the said buildup prepreg between the said smoothing process and the said hardening process. The method of claim 8,
The manufacturing method of the laminated board which performs the said 2nd smoothing process after releasing the pressure applied to the said laminated body after the said smoothing process. The method according to claim 8 or 9,
The manufacturing method of the laminated board which raises heating temperature rather than the said smoothing process and performs a said 2nd smoothing process. The method of claim 10,
The manufacturing method of the laminated board whose difference of the heating temperature of the said smoothing process and the said 2nd smoothing process is 10 degreeC or more and 100 degrees C or less. The method according to any one of claims 8 to 11,
The manufacturing method of the laminated board which performs the said 2nd smoothing process twice or more. The method according to any one of claims 1 to 12,
The said laminated process WHEREIN: The manufacturing method of the laminated board which heats and pressurizes in the state which sandwiched the said core layer and the said buildup prepreg with a pair of opposing elastic members. The method according to any one of claims 1 to 13,
The prepreg for buildup is wound and laminated in roll shape,
The rolled-up prepreg laminated | stacked is conveyed, the sheet-like core layer is conveyed, and the lamination process and the smoothing process are performed continuously. The method according to any one of claims 1 to 14,
In the said smoothing process, the manufacturing method of the laminated board which heats and pressurizes in a state which sandwiched the said core layer and the said buildup prepreg with a pair of metal member which opposes. The method according to any one of claims 1 to 15,
The manufacturing method of the laminated sheet which performs a laser via formation process further after the said hardening process. The method according to any one of claims 1 to 16,
A method for producing a laminated sheet, in which the time of the lamination process and the time of the smoothing process are matched with vacuum pumping and pressurization time.

Images