TWI639371B - Manufacturing method of laminated board - Google Patents

Abstract

An object of the present invention is to efficiently produce a laminated board which can maintain mechanical strength and has excellent adhesive strength of a conductor layer.

The invention provides a method for manufacturing a laminated board, which comprises the following steps (A) and (B): Step (A) is prepared on an organic support to set a thickness of 1 μm to 10 μm, and the pencil is hardened with a hardness of 2B or more The step of adhering the sheet of the thermosetting resin composition layer. In step (B), one or more prepregs are disposed between the two adhering sheets in which the thermosetting resin composition layers are opposed to each other. The step of pressing, heating and pressing at a temperature above 200 ° C to form a unit.

Description

Manufacturing method of laminated board

This invention relates to the manufacturing method of a laminated board.

As a method for manufacturing a printed wiring board used in an electronic device, for example, a B-stage resin composition sheet including a resin composition layer attached to one side of a metal foil or a release film is known so that the resin composition layer faces the A manufacturing method of a method in which the material is arranged on the immersed side, and a step of integrally forming and forming a laminated board by a vacuum hot pressing step of heating and pressing under vacuum conditions and hardening (refer to Patent Document 1).

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2003-332734

According to the requirements of miniaturization of electronic equipment in recent years, The printed wiring boards used in electronic equipment, and further the laminated boards formed by laminating an insulating layer and a conductor layer (wiring layer) used in printed wiring boards, etc., are also required to be further thinner and finer wiring.

In these contexts, The resin composition used also requires a resin composition that can maintain the same mechanical strength as the conventional laminate even if the thickness of the laminate is thinner, and can prevent warping due to the difference in thermal expansion coefficient between the laminate and the conductor layer. .

For example, to maintain the mechanical strength of thinner laminates Considering a method of using a resin composition having a higher glass transition temperature (Tg) as the resin composition used for the prepreg used in the manufacture of the laminate. In order to reduce the thermal expansion coefficient of the resin composition, a method of blending inorganic fillers such as silicon dioxide is considered.

When using prepregs using this resin composition, The resin composition having a high glass transition temperature is thermally hardened, and the flowability of the resin composition is reduced due to the formulation of the inorganic filler, so a vacuum hot pressing step at a higher temperature and pressure is necessary.

However, when performing this vacuum hot pressing step, When the laminated board is roughened, it may be difficult to obtain a surface with suppressed roughness unevenness, and as a result, it may be difficult to form a conductive layer having excellent adhesion by plating.

When forming the conductor layer by plating, it is also considered that the ketone foil and the prepreg are integrally formed by joining the matting surface of the copper foil and the prepreg, and then the copper foil is removed, and the matting surface of the copper foil is used to make the prepreg. Surface roughening method. However, because this method excessively increases the roughness, it is not conducive to finer wiring. Refinement.

In order to solve the problem of forming a conductive layer by plating, a finer composition is formed. For the above problems at the time of wiring, it is considered to use a bonding sheet formed by adhering a thermosetting resin composition to one side of a support body. The surface of the prepreg can be provided by fine plating to form fine wiring. A thermosetting resin composition layer (undercoat layer).

However, according to the findings of the present inventors, Warm and high pressure vacuum hot-pressing step roughens the surface of the laminate obtained by integrally forming the prepreg and the subsequent sheet, which will cause uneven roughness, which will cause the adhesion of the conductor layer formed by plating to the laminate. And some problems occur in areas that are easily peeled off.

As a result of active review by the present inventors in view of the above-mentioned problems, it has been found that when a thermosetting resin composition layer and a prepreg are integrally formed under high temperature and high pressure conditions to form a laminate, a thermosetting resin having a hardness of a certain value or more is used. The flexible resin composition layer can suppress uneven unevenness of the surface of the hardened body that hardens the thermosetting resin composition layer, and can form a conductive layer having excellent adhesion strength. Thus, the present invention has been completed.

That is, the present invention provides the following [1] to [14].

[1] A method for manufacturing a laminated board, which includes the following steps (A) and (B). The step (A) is prepared on an organic support by setting a thickness of 1 μm to 10 μm and a pencil hardening with a hardness of 2B or more. Sex resin composition The step of layer-adhering sheet, step (B) is to arrange one or more prepregs between two pieces of the aforementioned adhesive sheet arranged such that the aforementioned thermosetting resin composition layers face each other, and under reduced pressure Step of heating and pressing above 200 ° C for integral molding.

[2] The method for producing a laminated board according to [1], wherein the thermosetting resin composition includes an inorganic filler, and when a nonvolatile component in the thermosetting resin composition is 100% by mass, The content of the inorganic filler is 15 mass% or more and 80 mass% or less.

[3] The method for producing a laminated board according to [2], wherein the content of the inorganic filler is 35% by mass or more and 60% by mass or less.

[4] The method for producing a laminate according to any one of [1] to [3], wherein the thermosetting resin composition contains an epoxy resin and a hardener.

[5] The method for producing a laminate according to any one of [1] to [4], wherein the thermosetting resin composition contains an organic filler, and the non-volatile matter in the thermosetting resin composition is non-volatile. When the component is 100% by mass, the content of the organic filler is 1% by mass or more and 10% by mass or less.

[6] The method for producing a laminate according to any one of [1] to [5], wherein the glass transition temperature of the organic support is 90 ° C or higher.

[7] The method for producing a laminated board according to any one of [1] to [6], wherein a thickness of the organic support is 5 μm to 50 μm.

[8] The method for manufacturing a laminated board according to any one of [1] to [7], wherein the step (B) uses two or more prepregs, and the prepregs are further arranged with an inner layer therebetween. The step of integrally forming the circuit substrate.

[9] The method for producing a laminate according to any one of [1] to [8], wherein the minimum melt viscosity of the thermosetting resin composition layer is 20,000 poise or more.

[10] The method for producing a laminated board according to any one of [1] to [9], further comprising a step (C) of removing the organic support.

[11] The method for manufacturing a laminated board according to any one of [1] to [10], further including a step (D) of forming a through hole.

[12] The method for manufacturing a laminated board according to [10], further comprising a step (E) of roughening the laminated board after the step (C).

[13] The method for manufacturing a laminated board according to [12], further comprising a step (F) of forming a conductor layer by plating after the aforementioned step (E).

[14] The method for manufacturing a laminated board according to [13], further comprising a step (G) of forming a wiring layer using the aforementioned conductor layer.

According to the method for manufacturing a laminated board of the present invention, it is possible to efficiently manufacture a laminated board that can maintain mechanical strength despite its thin thickness and is excellent in the adhesive strength of the conductor layer (wiring layer).

[Manufacturing method of laminated body]

Hereinafter, the manufacturing method of the laminated body of this invention is demonstrated in detail.

The method for producing a laminated body of the present invention includes steps (A) and Step (B): Step (A) is a step of setting a bonding sheet of a thermosetting resin composition layer having a thickness of 1 μm to 10 μm and a pencil hardness of 2B or more on an organic support. A step in which one or more prepregs are arranged between two of the aforementioned adhesive sheets arranged so that the thermosetting resin composition layers face each other, and are heated and pressurized at 200 ° C. or more under reduced pressure to be integrally molded.

<Step (A)>

First, a step (A) of preparing a bonding sheet for a thermosetting resin composition layer having a thickness of 1 to 10 μm and a pencil hardness of 2B or more on an organic support is performed.

The thermosetting resin composition layer included in the subsequent sheet can be applied to an organic support by any suitable coating method known in the past, such as a die applicator, and then applied by drying. Film to form a thermosetting resin composition layer.

The adhesive sheet in the other step (A) may be, for example, a previously prepared adhesive sheet stored under specific storage conditions.

(Organic support)

The organic supporting system used for the flakes is a plate-shaped body with two main surfaces facing each other or a structure formed of a thin film. As for organic supports, long Thin film-like structure.

Can be heated and pressurized above 200 ° C to include the organic support From the viewpoint of integrally forming a body structure, an organic support system uses an organic support having a glass transition temperature of 90 ° C or higher, preferably 100 ° C or higher. The organic support is specifically an organic support made of a material that can withstand the processing conditions in the vacuum hot pressing step described later, especially a material that is resistant to heating temperature.

The material of the organic support is, for example, polynaphthalene dicarboxylic acid. Polyesters such as ethylene glycol (PEN), acrylics such as polycarbonate (PC), polymethyl methacrylate (PMMA), cyclic polyolefins, triethyl cellulose (TAC), polyether sulfide (PES) ), Polyetherketone, polyetheretherketone (PEEK), polyphenylene sulfide (PPS), polyimide, and the like. Among these, polyethylene naphthalate and polyimide are preferred from the viewpoint of heat resistance.

Organic supports containing the aforementioned materials can also be cured against heat The surface to which the resin composition layer is bonded, that is, the surface coated with the thermosetting resin composition is subjected to a matting treatment or a corona treatment.

In addition, organic supports can also be used with thermosetting resins. An organic support with a release layer on the side where the composition layer is bonded, that is, the side on which the thermosetting resin composition is applied, has a release layer. The release agent used to form the release layer of the organic support with a release layer is selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, fluororesin, and silicone resin, for example. One or more release agents.

On the condition that the purpose of the present invention is not impaired, The thickness is not particularly limited, but is preferably 5 μm to 50 μm. Also, use attached In the case of the organic support of the mold layer, the thickness of the entire organic support with the release layer is preferably within the above range.

(Thermosetting resin composition layer)

The thickness of the thermosetting resin composition layer is preferably 1 μm to 10 μm. The thickness of the thermosetting resin composition layer is not particularly limited on the condition that a roughening step can be performed after the cured body is formed.

[Pencil hardness]

The pencil hardness of the thermosetting resin composition layer is 2B or more. Specifically, the pencil hardness is preferably 2B or more, that is, a hardness equal to or greater than 2B (for example, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H, 7H ).

The pencil hardness is a hardness measured in accordance with a measurement method standardized by JIS K5600-5-4.

Provided that the object of the present invention is not impaired, the upper limit of the pencil hardness in the thermosetting resin composition layer is not particularly limited, but when considering the time required for the drying treatment and the content of the inorganic filler, it is preferably 7H or less.

[Minimum melt viscosity]

Provided that the object of the present invention is not impaired, the minimum melt viscosity of the thermosetting resin composition layer is not particularly limited, but it is preferably 20,000 poise or more, more preferably 40,000 poise or more, and still more preferably 70,000 poise or more. Without compromising The purpose of the present invention is that the upper limit of the minimum melt viscosity of the thermosetting resin composition layer is not particularly limited.

Here, the "minimum of the so-called thermosetting resin composition layer" The "melt viscosity" refers to the lowest viscosity exhibited by the thermosetting resin composition layer when the resin (cured material) constituting the thermosetting resin composition layer is heated and melted. In detail, when the thermosetting resin composition layer is heated and melted at a constant temperature increase rate, the melt viscosity in the initial stage decreases to a minimum point as the temperature rises, and when the temperature exceeds a certain temperature, the melt viscosity rises as the temperature rises. The so-called "minimum melt viscosity" refers to the melt viscosity of the minimum point.

The minimum melt viscosity of the thermosetting resin composition layer can be obtained by Dynamic viscoelasticity. Specifically, the minimum melt viscosity of the thermosetting resin composition layer can be obtained by performing dynamic viscoelasticity measurement under conditions of a measurement start temperature of 60 ° C., a heating rate of 5 ° C./minute, a frequency of 1 Hz, and a skewness of 1 degree. The dynamic viscoelasticity measuring device is, for example, "Rheosol-G3000" manufactured by UBM Corporation.

This is used for the formation of a thermosetting resin composition layer The components of the thermosetting resin composition will be described. In addition, in the description in this specification, the content of each component is an amount when the total of the non-volatile components in the thermosetting resin composition is 100% by mass.

Next, as described above, the sheet system includes an organic support and a thermosetting resin composition layer provided so as to be bonded to the organic support.

The thermosetting resin composition used as the material of the thermosetting resin composition layer preferably contains an inorganic filler, and further preferably contains a ring. Oxygen resin and hardener.

Thermosetting resin composition in addition to organic fillers such as rubber particles The filler may further include a hardening accelerator, a thermoplastic resin, a flame retardant, and the like. Each of these is explained below.

-Inorganic filler-

The thermosetting resin composition used for the formation of the thermosetting resin composition layer suppresses cracks and circuit deformation caused by the difference in thermal expansion rate between the cured body and the prepreg when the thermal expansion rate decreases when it becomes a cured body From the viewpoint of abnormal occurrence and suppressing excessive reduction in melt viscosity, when the non-volatile content in the thermosetting resin composition is 100% by mass, the content of the inorganic filler is preferably 15% by mass or more and 80% by mass. It is contained in the following manner, and the content of the inorganic filler is more preferably 35% by mass or more and 60% by mass or less.

Thermosetting that functions as a so-called undercoating Although the resin composition layer may not use an inorganic filler, the thermal expansion coefficient can be made smaller by the content described above, and the reflow resistance can be further improved.

Examples of the inorganic filler include silicon dioxide, aluminum oxide, Glass, cordierite, silicon oxide, barium carbonate, barium sulfate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, carbonic acid Calcium, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, zirconia, zirconium phosphate, zirconium phosphate tungstate, strontium carbonate, barium titanate, strontium titanate, titanium Calcium acid, magnesium titanate, bismuth titanate, barium zirconate titanate, titanium oxide, barium zirconate, and calcium zirconate. Among them, amorphous silicon dioxide, fused silicon dioxide, crystalline silicon dioxide, synthetic silicon dioxide, hollow silicon dioxide and the like are the best. The silicon dioxide is preferably spherical silicon dioxide. The inorganic fillers may be used singly or in combination of two or more kinds. The commercially available spherical (fused) silicon dioxide is exemplified by "SOC1", "SOC2", "SOC4", "SOC5", and "SOC6" made by ADMATECHS.

The average particle size of the inorganic filler increases the thermosetting tree From the viewpoint of the fluidity of the fat composition, a range of 0.01 μm to 4 μm is preferred, a range of 0.05 μm to 2.5 μm is more preferred, a range of 0.1 μm to 1.5 μm is more preferred, and 0.3 μm is even more preferred. The range is ~ 1.0μm. The average particle diameter of the inorganic filler can be measured by the laser diffraction and scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction scattering particle size distribution measurement device, and the median diameter can be measured as the average particle diameter. In this case, a measurement sample in which an inorganic filler is dispersed in water by ultrasonic waves can be suitably used. As the laser diffraction scattering particle size distribution measuring device, "LA-500" manufactured by Horiba Ltd. can be used.

Inorganic filler from the viewpoint of improving moisture resistance and dispersibility In terms of the surface, one or more kinds of amine-based coupling agents, epoxy-based silane coupling agents, mercapto-silane-based coupling agents, silane-based coupling agents, organic silazane compounds, and titanate-based coupling agents are preferred. Treatment agent treatment. Commercially available products of this surface treatment agent are, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., and "KBM803" (3 manufactured by Shin-Etsu Chemical Industry Co., Ltd.) -Mercaptopropyltrimethoxysilane Alkane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM573" (N-phenyl-3-aminopropyl propyl) manufactured by Shin-Etsu Chemical Industry Co., Ltd. Trimethoxysilane), "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., and the like.

Inorganic fillers with a surface treatment agent After the cleaning treatment with a solvent (for example, methyl ethyl ketone (MEK)), the carbon content per unit surface area of the inorganic filler is measured. Specifically, a sufficient amount of MEK as a solvent was added to the inorganic filler treated with the surface treatment agent, and ultrasonic cleaning was performed at 25 ° C for 5 minutes. Next, after removing the upper liquid and drying the non-volatile components, the carbon content per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V", etc., manufactured by Morioka Co., Ltd. can be used.

From the viewpoint of improving the dispersibility of the inorganic filler, the carbon content per unit surface area of the inorganic filler is preferably 0.02 mg / m ² or more, more preferably 0.1 mg / m ² or more, and still more preferably 0.2 mg. / m ² or more. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the thermosetting resin composition layer, the carbon content per unit surface area of the inorganic filler is preferably 1 mg / m ² or less, more preferably 0.8 mg / m ² or less. , And more preferably 0.5 mg / m ² or less.

-Organic Filler-

The thermosetting resin composition preferably contains an organic filler from the viewpoint of suppressing unevenness in roughness when it becomes a cured body. When the organic filler has a non-volatile content of 100% by mass in the thermosetting resin composition, The content is preferably such that the content is 1% by mass or more and 10% by mass or less.

Examples of the organic filler are rubber particles. Organic filling The rubber particles of the material are, for example, rubber particles which are insoluble in an organic solvent to be described later, and which are not compatible with an epoxy resin, a hardener, and a thermoplastic resin to be described later. Such rubber particles are generally prepared by increasing the molecular weight of the rubber particle components to such an extent that they are insoluble in organic solvents or resins, and are made into particles.

Examples of rubber particles of organic fillers include core-shell rubber Rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, acrylic rubber particles, and the like. Core-shell type rubber particles are rubber particles with a core layer and a shell layer. For example, the outer shell layer is composed of a glass-like polymer, the inner core layer is composed of a two-layer structure composed of a rubber-like polymer, or the outer shell The layer is made of glass-like polymer, the middle layer is made of rubber-like polymer, and the core layer is made of glass-like polymer. The glassy polymer layer is composed of, for example, a methacrylate polymer or the like, and the rubbery polymer layer is composed of, for example, butyl acrylate polymer (butyl rubber) or the like. Examples of usable rubber particles are "STAFYROID AC3816N" manufactured by AICA Industrial Co., Ltd. The rubber particles may be used singly or in combination of two or more kinds.

The average particle diameter of the rubber particles of the organic filler is preferably The range is from 0.005 μm to 1 μm, and more preferably from 0.2 μm to 0.6 μm. The average particle diameter of the rubber particles can be measured using a dynamic light scattering method. For example, ultrasonic particles can be used to uniformly disperse rubber particles in an appropriate organic solvent, and a thick particle size analyzer (for example, "FPAR- 1000 "), the particle size distribution of the rubber particles was prepared on a mass basis, and the median diameter was measured as the average particle diameter. The content of the rubber particles of the organic filler in the thermosetting resin composition is preferably in a range of 1% to 10% by mass, and more preferably in a range of 3% to 10% by mass.

Filling material content (inorganic filling material content and organic filling material content When the total content of the non-volatile components in the thermosetting resin composition is 100% by mass, the range is preferably from 16% to 90% by mass, and more preferably from 36% to 70% by mass.

-Epoxy resin-

The epoxy resin is exemplified by bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, and ginseng phenol. Epoxy resin, naphthol novolac epoxy resin, phenol novolac epoxy resin, third butyl-catechol epoxy resin, naphthalene epoxy resin, naphthol epoxy resin, anthracene epoxy Resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, cresol novolac epoxy resin, biphenyl epoxy resin, linear aliphatic epoxy resin, ring with butadiene structure Oxygen resin, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing spiro ring, cyclohexanedimethanol epoxy resin, naphthalene ether epoxy resin and trimethylol epoxy resin Wait. The epoxy resin may be used alone or in combination of two or more.

The epoxy resin preferably contains two or more rings in one molecule Epoxy resin. When the non-volatile content of the epoxy resin is 100% by mass, at least 50% by mass or more are two or more epoxy groups in one molecule Its epoxy. Among them, an epoxy resin having two or more epoxy groups in one molecule and being liquid at a temperature of 20 ° C. (hereinafter referred to as a “liquid epoxy resin”) and three or more molecules in one molecule are preferred. An epoxy group and a solid epoxy resin (hereinafter referred to as a "solid epoxy resin") at a temperature of 20 ° C. By using a liquid epoxy resin and a solid epoxy resin together as the epoxy resin, excellent flexibility can be imparted. In addition, the fracture strength of the hardened body (insulating layer) formed by the vacuum hot pressing step described later can be improved.

The liquid epoxy resin is preferably, for example, a bisphenol A epoxy resin. Grease, bisphenol F-type epoxy resin, phenol novolac-type epoxy resin, bifunctional aliphatic epoxy resin, or naphthalene-type epoxy resin, exemplified by bisphenol A-type epoxy resin, bisphenol F-type epoxy resin , Or naphthalene type epoxy resin. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene-type epoxy resin) made by DIC (stock), "jER828EL", "jER1007" (made by Mitsubishi Chemical Corporation) Bisphenol A epoxy resin), "jER807" (bisphenol F epoxy resin), "jER152" (phenol novolac epoxy resin), "ZX1059" (bisphenol manufactured by Nippon Steel Chemical Co., Ltd.) A type epoxy resin and a mixture of bisphenol F type epoxy resin), "YL7410" (bifunctional aliphatic epoxy resin), etc. These may be used individually by 1 type, or may use 2 or more types together.

Examples of the solid epoxy resin include a crystalline bifunctional ring Oxygen resin, 4-functional naphthalene epoxy resin, cresol novolac epoxy resin, dicyclopentadiene epoxy resin, ginseng phenol epoxy resin, naphthol novolac epoxy resin, biphenyl epoxy resin Naphthyl ether epoxy resin. Specific examples of the solid epoxy resin include "HP-4700" manufactured by DIC (stock), `` HP-4710 '' (4-functional naphthalene type epoxy resin), `` N-690 '' (cresol novolac Varnish-type epoxy resin), "N-695" (cresol novolac-type epoxy resin), "HP-7200" (dicyclopentadiene-type epoxy resin), "EXA7311", "EXA7311-G3", `` HP6000 '' (naphthyl ether epoxy resin), `` EPPN-502H '' (ginseng phenol epoxy resin), `` NC7000L '' (naphthol novolac epoxy resin), `` NC3000H '', "NC3000", "NC3000H", "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475" (naphthol novolac type epoxy resin) made by Nippon Steel Chemical Co., Ltd., and "ESN485" (Naphthol novolac epoxy resin), `` YX4000H '' made by Mitsubishi Chemical Corporation, `` YL6121 '' (biphenyl type epoxy resin), `` YX4000HK '' (dixylenol, crystalline bifunctional epoxy resin) Type epoxy resin) and so on.

Use liquid epoxy and solid epoxy as ring In the case of an oxygen resin, the amount ratio (liquid epoxy resin: solid epoxy resin) is preferably in a range of 1: 0.1 to 1: 4 in terms of mass ratio. By making the amount ratio of the liquid epoxy resin to the solid epoxy resin fall within this range, the following effects i) to iii) can be obtained: i) moderate adhesion when used in the form of an adhesive sheet, ii ) When used in the form of an adhesive sheet, sufficient flexibility is obtained and workability is improved. Iii) A hardened body having sufficient fracture strength can be obtained. From the viewpoint of the effects of i) to iii) above, the amount ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is more preferably 1 in terms of mass ratio. : 0.3 ~ 1: 3.5, more preferably 1: 0.6 ~ 1: 3, and most preferably 1: 0.8 ~ 1: 2.5.

Good content of epoxy resin in thermosetting resin composition 3 mass% to 50 mass%, more preferably 5 mass% to 45 mass%, still more preferably 5 mass% to 40 mass%, and most preferably 7 mass% to 35 mass%.

The weight average molecular weight of the epoxy resin is preferably 100 ~ 5000, more preferably 250 ~ 3000, and more preferably 400 ~ 1500. Here, the weight average molecular weight of an epoxy resin is the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography (GPC) method.

The epoxy equivalent of the epoxy resin is preferably in the range of 50 to 3000, more preferably in the range of 80 to 2000, and still more preferably in the range of 110 to 1,000. By setting it as this range, the hardened | cured material with sufficient crosslinking density can be obtained. The epoxy equivalent can be measured by a method standardized according to JIS K7236. The epoxy equivalent here is the mass of a resin containing 1 equivalent of epoxy groups.

-hardener-

The hardener is not particularly limited as long as it has a function of hardening the epoxy resin, and examples thereof include a phenol-based hardener, a naphthol-based hardener, an active ester-based hardener, a benzoxazine-based hardener, and a cyanate-based hardener. Agent and carbodiimide hardener. The hardener may be used alone or in combination of two or more.

Examples of the phenol-based hardener and naphthol-based hardener include a phenol-based hardener having a novolac structure, a naphthol-based hardener having a novolac structure, a nitrogen-containing phenol-based hardener, and a cresol-based hardener containing a triazine skeleton. Agent, phenolic hardener containing a triazine skeleton.

Specific examples of the phenol-based hardener and the naphthol-based hardener are listed below. For example, `` MEH-7700 '', `` MEH-7810 '', `` MEH-7851 '' by Meiwa Kasei Co., Ltd., `` NHN '', `` CBN '', `` GPH '' by Tohoku Kasei Co., Ltd., and Toto Kasei Co., Ltd. ) System "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN375", "SN395", DIC (share) system "LA7052", "LA7054", " LA3081 "and so on.

There is no particular limitation on the active ester hardener, but it is generally better Phenol esters, thiophene esters, N-hydroxyamine esters, heterocyclic hydroxy compound esters, and the like are used as compounds having two or more highly reactive ester groups in one molecule. The active ester-based hardener is preferably a hardener obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. Especially from the viewpoint of improving heat resistance, an active ester-based hardener obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based hardener obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Agent. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methyl Bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxy Naphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, pyrogallol, pyroglycerol, dicyclopentadiene type diphenol compound, Phenolic novolac, etc.

Active ester hardeners are specifically listed as dicyclopentadiene-containing An active ester compound of a diphenol condensation structure, an active ester compound of a naphthalene structure, an active ester compound of an acetic acid compound containing a phenol novolac, and an active ester compound of a benzamidine compound containing a phenol novolac.

Commercially available active ester hardeners, for example as bicyclic Examples of active ester compounds with a pentadiene-type diphenol condensation structure are "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T" (manufactured by DIC (stock)), and examples of active ester compounds containing a naphthalene structure "EXB9416-70BK" (manufactured by DIC), listed as the active ester compound of acetic acid compound containing phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.), and benzamidine containing novolac Examples of the active ester compound of the compound include "YLH1026" (manufactured by Mitsubishi Chemical Corporation).

Specific examples of the benzoxazine-based hardener include, for example, Showa "HFB2006M" for polymer (stock) system, "P-d" and "F-a" for Shikoku Chemical Industry (stock) system.

Examples of the cyanate-based curing agent include bisphenol A dicyanate Ester, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis (2,6-dimethylphenyl cyanate) (Ester), 4,4'-ethylenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1- Bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1) -Bifunctional cyanate resins such as ((methylethylene)) benzene, bis (4-cyanatephenyl) sulfide, and bis (4-cyanatephenyl) ether; phenol novolac And cresol novolac and other polyfunctional cyanate resins, and these cyanate resins are partially triazinated Prepolymers, etc. Specific examples of the cyanate-based hardener include "PT30" and "PT60" (both phenol novolac-type polyfunctional cyanate resins) and "BA230" (bisphenol A dicyanate) made by Japan LONZA Co., Ltd. One or all of the esters are partially or completely triazinated into a prepolymer of a trimer).

Specific examples of the carbodiimide-based hardener include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd.

The ratio of epoxy resin to hardener is Basis count]: The ratio of [reaction base count of hardener] is preferably in the range of 1: 0.2 to 1: 2, more preferably in the range of 1: 0.3 to 1: 1.5, and more preferably 1: The range is from 0.4 to 1: 1. Here, the reactive group of the hardener is an active hydroxyl group, an active ester group, and the like, and it depends on the type of the hardener. In addition, the epoxy epoxy group total number is the value obtained by dividing the mass of each epoxy resin by the epoxy equivalent weight for all epoxy resins. The hardener is a value obtained by dividing the mass of the nonvolatile component of each hardener by the equivalent of the reactive group. By setting the amount ratio of the epoxy resin to the hardener within this range, the heat resistance at the time of becoming a hardened body is further improved.

About the content of hardener, total epoxy groups of epoxy resin The ratio of the number to the total number of reactive groups of the hardener is preferably in the range of 1: 0.2 to 1: 2, more preferably in the range of 1: 0.3 to 1: 1.5, and even more preferably in the range of 1: 0.4 to 1: 1. range.

The thermosetting resin composition preferably contains each as an epoxy resin. Mixture of liquid epoxy resin and solid epoxy resin (liquid epoxy resin: solid epoxy resin is better in the range of 1: 0.1 ~ 1: 4 Range, more preferably 1: 0.3 ~ 1: 3.5, still more preferably 1: 0.6 ~ 1: 3, most preferably 1: 0.8 ~ 1: 2.5), and phenol as a hardener Hardener, naphthol-based hardener, active ester-based hardener, and cyanate-based hardener selected from one or more (preferably including a phenol-based hardener and a naphthol-based hardener One or more selected from the group, more preferably one or more selected from the group consisting of a phenol novolac resin containing a triazine skeleton, and a naphthol-based hardener, and further preferably a hardening of the phenol novolac resin containing a triazine skeleton剂).

-Thermoplastic resin-

Examples of the thermoplastic resin include a phenoxy resin, an acrylic resin, a polyethylene acetal resin, a polyimide resin, a polyimide resin, a polyimide resin, and a polyimide resin. The thermoplastic resin may be used singly or in combination of two or more kinds.

Polystyrene equivalent weight average of thermoplastic resin The sub-quantity is preferably in the range of 8000 to 70,000, more preferably in the range of 10,000 to 60,000, and more preferably in the range of 20,000 to 60,000. The polystyrene-equivalent weight average molecular weight of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the weight-average molecular weight in terms of polystyrene of the thermoplastic resin can be measured using LC-9A / RID-6A manufactured by Shimadzu Corporation, and Shodex K-800P / K-804L / K- manufactured by Showa Denko Corporation. 804L was used as a column, and chloroform or the like was used as a mobile phase. The column temperature was measured at 40 ° C, and calculated using a calibration line of standard polystyrene.

As the phenoxy resin, for example, bisphenol A Frame, bisphenol F frame, bisphenol S frame, bisphenol acetophenone frame, novolak frame, biphenyl frame, fluorene frame, dicyclopentadiene frame, norbornene frame, naphthalene frame, anthracene frame, adamantane One or more phenoxy resins selected from the group consisting of a skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. The phenoxy resin may be used singly or in combination of two or more kinds. Specific examples of the phenoxy resin include "1256" and "4250" (both phenoxy resin containing a bisphenol A skeleton) and "YX8100" (phenoxy resin containing a bisphenol S skeleton) made by Mitsubishi Chemical Corporation. And "YX6954" (phenoxy resin containing bisphenol acetophenone skeleton), and other examples are "FX280" and "FX293" made by Totsu Kasei Co., Ltd., and "YX7553" and "YL6794" "," YL7213 "," YL7290 ", and" YL7482 ".

As an acrylic resin, the thermal expansion rate and elastic modulus are further improved. From a low viewpoint, the functional group-containing acrylic resin is preferable, and the epoxy group-containing acrylic resin having a glass transition temperature of 25 ° C. or lower is more preferred.

The number average molecular weight (Mn) of the functional group-containing acrylic resin is preferably 10,000 to 1,000,000, more preferably 30,000 to 900,000.

The functional group equivalent of the functional group-containing acrylic resin is preferably 1,000 to 50,000, and more preferably 2500 to 30,000.

The epoxy group-containing acrylic resin having a glass transition temperature of 25 ° C. or lower is preferably an epoxy group-containing acrylate copolymer resin having a glass transition temperature of 25 ° C. or lower. Specific examples thereof include “made by Nagase Chemtex” SG-80H '' (epoxy-containing acrylate copolymer resin (number average Molecular weight Mn: 350,000 g / mol, epoxy value 0.07 eq / kg, Tg 11 ° C), "SG-P3" (epoxy-containing acrylate copolymer resin (number-average molecular weight Mn: 850000 g) manufactured by Nagase Chemtex / mol, epoxy value 0.21 eq / kg, glass transition temperature 12 ° C)).

Specific examples of polyethylene acetal resin are listed in electrochemistry Electrochemical butyraldehyde 4000-2, 5000-A, 6000-C, 6000-EP made by industrial (stock), SLEC BH series, BX series, KSI, KS series, BL series, BM made by Sekisui Chemical Industry (stock) Series, etc.

Specific examples of polyimide resins are listed as Nippon Physico Chemical Co., Ltd. "RIKACOAT SN20" and "RIKACOAT PN20". Specific examples of the polyimide resin are linear polyimide obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a quaternary acid anhydride (Polyimide described in Japanese Patent Application Laid-Open No. 2006-37083 Polyimide resins), polyimide containing a polysiloxane skeleton (polyimide resins described in JP 2002-12667 and JP 2000-319386, etc.) and other modified polymers醯 imine.

Specific examples of polyimide / imide resins are listed as Toyobo (Share) system "VYLOMAX HR11NN" and "VYLOMAX HR16NN". Specific examples of the polyamidoamine imine resin include modified polyamidoamine imines such as polyamidoamimine "KS9100" and "KS9300" containing a polysiloxane skeleton manufactured by Hitachi Chemical Industries, Ltd.

Specific examples of polyether resins are listed by Sumitomo Chemical Co., Ltd. "PES5003P", etc.

Specific examples of polyfluorene resins are Solvay Advanced Polymers (P1700), "P3500", etc.

Thermoplastic resin content in thermosetting resin composition It is preferably from 0.1% by mass to 20% by mass. By setting the content of the thermoplastic resin within this range, the viscosity of the thermosetting resin composition is made moderate, and a thermosetting resin composition layer having a uniform thickness or overall properties can be formed. The content of the thermoplastic resin in the thermosetting resin composition is more preferably 0.5% by mass to 10% by mass.

-Hardening accelerator-

Examples of the hardening accelerator include a phosphorus-based hardening accelerator, an amine-based hardening accelerator, an imidazole-based hardening accelerator, and a guanidine-based hardening accelerator.

Examples of the phosphorus-based hardening accelerator include triphenylphosphine and lutetium borate Compound, triphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate, tetrabenzene Sulfonium thiocyanate, butyltriphenylsulfonium thiocyanate, and the like.

Examples of the amine-based hardening accelerator include triethylamine and tributylamine. Isotrialkylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-p- (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5.4.0 ) -Undecene and the like.

Examples of the imidazole-based hardening accelerator include 2-methylimidazole, 2-undecylimidazole, 2-pentadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methyl Imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecane Imidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecyl Alkyl imidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-Ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1')]-ethyl-s-triazine, 2,4 -Diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'- Methyl imidazolyl- (1 ')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethyl Imidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydroxy-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2- Imidazole compounds such as methyl-3-benzimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and the addition of imidazole compounds to epoxy resins.

Examples of guanidine-based hardening accelerators include dicyandiamide, 1- Methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethyl Guanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] dec- 5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1- (o-tolyl) biguanide and the like.

Hardening accelerators can be used alone or in combination of 2 More than one kind of use. When the content of the hardening accelerator in the thermosetting resin composition is 100% by mass, the total amount of the nonvolatile components of the epoxy resin and the hardener is preferably used in the range of 0.05% by mass to 3% by mass.

-Flame retardant-

Examples of the flame retardant include an organic phosphorus-based flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a polysiloxane flame retardant, and a metal hydroxide. Examples of usable flame retardants are "HCA-HQ" manufactured by Mitsuko Corporation. The flame retardant can be used singly or in combination of two or more kinds. The content of the flame retardant in the thermosetting resin composition layer is not particularly limited, but is preferably in the range of 0.5% to 10% by mass, more preferably in the range of 1% to 9% by mass, and even more preferably 1.5% by mass. % To 8% by mass.

-Other additives-

The thermosetting resin composition used for the formation of the thermosetting resin composition layer may optionally contain other additives to adjust the properties of the thermosetting resin composition layer or the hardened body, for example. The other additives are exemplified by organic copper compounds, organic Organometallic compounds such as zinc compounds and organic cobalt compounds; and resin additives such as tackifiers, defoamers, leveling agents, adhesion-imparting agents, and coloring agents.

The organic solvents used in the preparation of resin paints include ketones such as acetone, methyl ethyl ketone and cyclohexanone, ethyl acetate, butyl acetate, lysin acetate, propylene glycol monomethyl ether acetate And acetates such as carbitol acetate, carbitols such as lysin and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide And amine-based solvents such as N-methylpyrrolidone. The organic solvents may be used singly or in combination of two or more kinds.

(Formation step of thermosetting resin composition layer)

The drying treatment of the coating film of the thermosetting resin composition for forming the thermosetting resin composition layer can be performed by any known and preferable drying method such as heating and blowing with hot air. The coating film becomes a thermosetting resin composition layer by this drying process.

The drying conditions of each drying process only need to consider the resin composition Or the boiling point of the organic solvent contained in the resin paint can be set to any preferable conditions. The stated pencil hardness and minimum melt viscosity can be adjusted according to the drying conditions, that is, the drying method, drying temperature, and drying processing time. Specifically, if the drying temperature is the same, the longer the drying time, the higher the pencil hardness and the minimum melt viscosity.

This drying process is not limited to being performed only once, and may be repeated Implemented multiple times. When the drying process is repeatedly performed several times, the drying conditions may be the same as or different from each other.

When the drying process is repeated several times, for example, at a lower temperature The first drying process is performed, and the second and subsequent drying processes are performed at a higher temperature than the first drying process. Accordingly, even when plural organic solvents having different boiling points are used, the organic solvent with a lower boiling point can be effectively volatilized by the first drying treatment, and the organic solvent with a higher boiling point can be effectively volatilized by the second and subsequent drying treatments Therefore, a high-quality thermosetting resin composition layer having a small amount of residual solvent can be formed.

Step (A) preferably uses a long support as an organic support The body is carried out in a roll-to-roll manner, but it can also be carried out in a batch manner.

The step (A) of the roll-to-roll method can be specifically performed as follows Row: Spread across at least 2 rolls including the take-up roll and take-up roll The long organic support is continuously conveyed, and the thermosetting resin composition is coated on one of the main surfaces of the support exposed between the take-up roll and the take-up roll, so that the continuous coating film is dried. Process to form a thermosetting resin composition layer.

In this way, it is possible to prepare a thermosetting tree on an organic support Adhesive sheet of lipid composition layer.

When the prepared adhesive sheet is temporarily stored, that is, temporarily When the manufacturing steps of the laminated sheet are discontinued, it is preferable to further set the exposed surface of the side of the thermosetting resin composition layer that is not joined to the organic support (that is, the side opposite to the organic support) when it is opened again after a period of time Surface) bonded protective film. This protective film helps to prevent dirt or the like from adhering to the thermosetting resin composition layer or to prevent scratches. As a protective film, a polypropylene film, a polyethylene film, etc. can be used, for example. A thin film made of the same material as that of the organic support can be used. The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. The thickness of the protective film is preferably thinner than the thickness of the organic support.

Bonding of a protective film to an adhesive sheet can be performed using the conventional laminator apparatus.

<Step (B)>

Next, two sheets of thermosetting resin composition layers are arranged to face each other, and then one or more prepregs are arranged between the sheets, and they are integrally molded by heating and pressing at 200 ° C or higher under reduced pressure. Step (B).

(Prepreg)

The prepreg is a sheet-like structure in which a resin composition is impregnated into a sheet-like fiber substrate. The prepreg that can be used in the manufacturing method of the laminated board of the present invention can use any preferred prepreg according to the use of the laminated board. As the prepreg, a commercially available prepreg can also be used. Commercially available prepregs are listed, for example, as "GEA-800G" by Hitachi Chemical Co., Ltd.

The sheet-like fibrous substrate constituting the prepreg is not particularly limited It can use glass cloth, aramide, non-woven fabric, liquid crystal polymer non-woven fabric and other prepregs. Depending on the purpose of the laminate, the thickness of the prepreg can be any preferred thickness, but when using a laminate in the formation of an insulating layer of a multilayer printed wiring board, it is preferred to use a thin sheet-like fiber substrate having a thickness of 50 μm or less, especially A sheet-like fibrous substrate having a thickness of 10 μm to 40 μm is preferable, a sheet-like fibrous substrate having a thickness of 10 μm to 30 μm, and a sheet-like fibrous substrate having a thickness of 10 μm to 20 μm is more preferable. When a laminate is used as the insulating substrate (core substrate), a sheet-like fibrous substrate having a thickness of 10 μm to 150 μm is preferably used, and a sheet-like fibrous substrate having a thickness of 10 μm to 100 μm is preferably used.

Specific examples of the glass cloth substrate that can be used as a sheet-like fiber substrate include, for example, "STYLE 1027MS" manufactured by ASAHI SCHWEBEL (strand density of 75 warps / 25mm, weft density of 75 / 25mm, and cloth weight of 20g). / m ² , thickness 19 μm), "STYLE 1037MS" by Asahi Schwebel (strand density 70 warps / 25 mm, weft density 73/25 mm, cloth weight 24 g / m ² , thickness 28 μm), Arisawa Manufacturing Co., Ltd. ( "1078" (warp density of 54 / 25mm, weft density of 54 / 25mm, cloth weight of 48g / m ² , thickness of 43μm), "1037NS" (warp density of 72) Article / 25mm, weft density of 69 / 25mm, fabric weight 23g / m ^2, a thickness of 21μm), Arisawa (shares) manufactured by the "1027NS" (warp density of 75 / 25mm, weft density of 75 / 25mm, Cloth weight 19.5g / m ² , thickness 16μm), "1015NS" manufactured by Ariza Seisakusho Co., Ltd. (warp yarn density 95 / 25mm, weft density 95 / 25mm, cloth weight 17.5g / m ² , thickness 15μm) , Arisawa (shares) manufactured by the "1000NS" (warp density of 85 / 25mm, the weft yarn density of 85 / 25mm, fabric weight 11g / m ^2, thickness 10 m) and the like. Specific examples of the liquid crystal polymer nonwoven fabric include, for example, "VECRUS" (unit area weight: 6 g / m ² to 15 g / m ² ) or "VECTRAN" of an aromatic polyester nonwoven fabric made by Kuraray (strand) by melt blow molding. "Wait.

The thermosetting resin composition that can be used for prepreg formation is only The cured product is not particularly limited as long as it has sufficient hardness and insulating properties. For example, a thermosetting resin composition having the same composition as the thermosetting resin composition used to form the aforementioned adhesive sheet may be used.

The prepreg can use conventional methods such as hot melt method and solvent method. Manufacturing. The hot-melt method is to temporarily apply a thermosetting resin composition to a release paper having good peelability without dissolving the thermosetting resin composition in an organic solvent, and laminating the thermosetting resin composition on a sheet-like fibrous substrate. Or, it can be directly coated on a sheet-like fibrous substrate by die coating, etc., to produce a prepreg. In addition, the solvent method is based on immersing the sheet-like fibrous substrate in a paint made by dissolving a thermosetting resin composition in an organic solvent, thereby impregnating the sheet-like fibrous substrate with the thermosetting resin composition. Then dried to make Dipping. Furthermore, the prepreg can be produced continuously by laminating a fibrous substrate with two resin sheets made of a thermosetting resin composition on both sides of the sheet, and heating and pressing.

(Vacuum hot pressing step)

Next, an example of a specific manufacturing process of a laminate using a vacuum hot pressing step will be described.

First, a laminated structure in which two sheets of thermosetting resin composition layers are arranged so as to face each other, and one or more prepregs are arranged between the sheets is fixed to a vacuum hot pressing device.

The laminated structure is preferably fixed to a vacuum hot pressing device through a metal plate such as a buffer paper, a stainless steel plate (SUS plate), and a release film. The laminated structure is laminated and fixed in the order of, for example, buffer paper / metal plate / release film / laminated structure (for example, adhesive sheet / prepreg / adhesive sheet) / release film / SUS board / buffer paper On a vacuum hot press.

Here, the symbol "/" means that it is arrange | positioned so that it may mutually connect via the component shown by this symbol (it is the same also in the description of a laminated structure etc. below).

Next, the layers were heated while being heated under reduced pressure. The structure is pressurized (pressed) to perform the vacuum hot pressing step.

The vacuum hot pressing step can use a heated SUS plate, etc. The conventionally known vacuum hot pressing device is used for pressing a metal plate from both sides as a target laminated structure. Commercially available vacuum hot-pressing apparatuses that can be used in the method for manufacturing the laminated board of the present invention are, for example, "MNPC- "V-750-5-200", "VH1-1603" manufactured by Kitagawa Seiki Co., Ltd., etc.

The vacuum hot pressing step can be performed only once, but it can also The laminated structure of the processing target is processed by repeating the vacuum hot pressing step more than 2 times.

The pressure (pressing) condition in the vacuum hot pressing step is preferably set to about 50 kgf / cm ² . The pressure is preferably 5 kgf / cm ² to 30 kgf / cm ² (0.5 N / m ² to 30 N / m ² ).

The vacuum conditions in the vacuum hot-pressing step, that is, the pressure at the time of decompression in the laminated structure storage object to be processed are set to about 1 × 10 ^-2 MPa. The pressure is usually 5 × 10 ^-3 MPa or less, and preferably 3 × 10 ^-2 MPa or less.

The heating conditions in the vacuum hot pressing step, that is, the heating temperature The composition varies with the composition of the thermosetting resin composition used for the adhesive sheet and the prepreg and the heat resistance of the organic support used, but it is set to 200 ° C or higher. The upper limit of the heating temperature is not particularly limited, but is generally 240 ° C or higher. The heating temperature is preferably 210 ° C or higher, and more preferably 220 ° C or higher.

In addition, it is suppressed from being formed integrally by the vacuum hot pressing step. From the viewpoint of generation of wrinkles on the surface of the cured hardened body, it is preferred to perform the vacuum hot pressing step while gradually increasing the temperature stepwise or continuously and / or decreasing the temperature stepwise or continuously.

The vacuum hot-pressing step can specifically specify a heating rate (for example, (E.g., 5 ° C / minute) is heated from normal temperature to a specific heating temperature (for example, 205 ° C), and after the specific heating temperature is maintained for a specific time, the heating is performed at a specific cooling rate (for example, 5 ° C / minute) to normal temperature.

The processing time in the vacuum hot pressing step can be The range of the purpose is set to any preferable processing time, but it is usually about 15 minutes to 90 minutes.

Step (B) can also use more than two pieces of prepreg. The step of further arranging the inner-layer circuit substrate between the immersion materials and forming them integrally.

The inner-layer circuit substrates usable in step (B) can be enumerated as including For example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate are used as the substrate. A conventionally known plate-like or sheet-like structure of a conductor layer (wiring layer) (forming a circuit).

When two or more prepregs are used, one or more of the composition of the thermosetting resin composition, the material of the sheet-like fiber substrate, and the thickness may be different from each other.

In step (B), for example, to When a protective film bonded to the thermosetting resin composition layer is placed, the protective film is peeled off, or step (B) is performed while peeling.

With the above vacuum hot pressing step, the adhesive film is hardened. The chemical resin composition layer and the prepreg (thermosetting resin composition contained in the prepreg) are hardened and integrally molded to produce a laminate.

〈Other steps〉

The manufacturing method of the laminated board of the present invention may further include step (C) of the step of peeling the organic support, step (D) of the step of forming a through hole, and roughening Step (E) of the logical step, step (F) of the step of forming a conductor layer by plating, and step (G) of the step of forming a wiring layer by patterning the conductor layer. Provided that the purpose of the present invention is not impaired, these steps (C) to (G) may be any preferred steps known to those skilled in the art.

(Step (C))

Step (C) is a step of peeling off the organic support. In this step (C), the surface of the cured body obtained by peeling and removing the organic support, and curing the thermosetting resin composition layer of the adhesive sheet is exposed. Step (C) can be carried out before step (E) at the latest, but preferably after step (D) and before step (E).

(Step (D))

Step (D) is a step of punching the formed laminated board, and forming a through hole through the laminated board by the punching process. Step (D) can be performed by means of, for example, a drilling machine, a laser (a carbon dioxide gas laser, a YAG laser, etc.), a plasma, or the like. The formed through holes are used, for example, to electrically connect conductor layers (wiring layers) provided on both main surface sides of the laminated board to each other. Step (D) may be carried out before step (E) at the latest, preferably before step (C).

(Step (E))

Step (E) is a step of roughening the laminated board, that is, the surface of the exposed hardened body. Step (E) is performed slowest before step (G), preferably after steps (C) and (D).

The order and conditions of the roughening treatment are not particularly limited, and can be used Any preferred order and conditions known in the past. For example, step (E) can be performed by sequentially performing a swelling treatment of a swelling liquid, a roughening treatment of an oxidizing agent, and a neutralizing treatment of a neutralizing agent. The swelling liquid is not particularly limited, and examples thereof include an alkali solution, a surfactant solution, and the like, preferably an alkali solution, and the alkali solution is preferably a sodium hydroxide solution or a potassium hydroxide solution. Commercially available swelling liquids include, for example, Swelling Dip Securiganth P, Swelling Dip Securiganth SBU, manufactured by ATOTECH Japan. The swelling treatment with the swelling liquid is not particularly limited. For example, it can be performed by immersing the hardened body in a swelling liquid at 30 ° C to 90 ° C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the hardened body to a moderate degree, it is preferable to immerse it in a swelling liquid at 40 ° C to 80 ° C for 5 seconds to 15 minutes. The oxidizing agent is not particularly limited, and examples thereof include a basic permanganic acid solution obtained by dissolving potassium permanganate and sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidant such as an alkaline permanganic acid solution is preferably performed by immersing in an oxidant solution heated to 60 ° C to 80 ° C for 10 minutes to 30 minutes. In addition, the permanganate concentration in the alkaline permanganic acid solution is preferably 5% to 10% by mass. Commercially available oxidizing agents include, for example, alkaline permanganic acid solutions such as Concentrate Compact P and Doesing Solution Securiganth P manufactured by ATOTECH Japan. The neutralizing solution is preferably an acidic aqueous solution, and commercially available products include, for example, Reduction Solution Securiganth P manufactured by ATOTECH Japan. The treatment with the neutralizing solution can be performed by immersing the treated surface roughened with the oxidant solution in a neutralizing solution at 30 ° C to 80 ° C for 5 to 30 minutes. In terms of workability and the like, a hardened body that is roughened with an oxidant solution is preferred. Method of immersing in 40 ℃ ~ 70 ℃ neutralizing solution for 5 ~ 20 minutes.

(Step (F))

Step (F) is a step of forming a conductor layer on the roughened surface by plating. Step (F) is performed after step (E).

The material of the conductive layer is not particularly limited. Preferred embodiment The conductor layer includes one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer may be a single metal layer or an alloy layer. As the alloy layer, for example, an alloy formed of two or more metals selected from the above group (for example, a nickel-chromium alloy, a copper-nickel alloy, and a copper-titanium alloy) is listed. Floor. Among these, from the viewpoints of versatility, cost, and ease of patterning of the formation step of the conductor layer, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper is preferred, Or an alloy layer of nickel-chromium alloy, copper-nickel alloy, copper-titanium alloy, more preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy, and More preferably, it is a single metal layer of copper.

The conductor layer can be a single layer structure, or it can be laminated with two or more layers The multilayer structure is composed of a single metal layer or an alloy layer made of different kinds of metals or alloys. When the conductor layer has a multilayer structure, the layer adjacent to the insulating layer is preferably a single metal layer of chromium, zinc, or titanium, or an alloy layer of a nickel-chromium alloy.

The thickness of the conductor layer is generally 3 μm to 35 μm, preferably 5μm ~ 30μm.

In this embodiment, the conductive layer is formed by plating. For example Any preferred plating conventionally known by electrolytic plating, electroless plating, etc. The step of forming a conductor layer on the surface of the hardened body.

(Step (G))

Step (G) is a step of forming a wiring layer based on the formed conductor layer. Step (G) is performed after step (F). In step (G), for example, a semi-additive method or a full-additive method for forming a wiring layer on the formed conductor layer (plating seed layer) can be used to pattern the formed conductive layer into a subtractive method for the wiring layer. get on.

Here, an example in which the wiring layer is formed by a semi-additive method will be described. First, a conductive layer (plating seed layer) is formed on the roughened surface of the cured body derived from the thermosetting resin composition layer of the subsequent sheet by the electroless plating method. Next, a mask pattern is formed on the formed plating seed layer so that a part of the plating seed layer corresponding to a desired wiring pattern is exposed. After forming a thick film conductive layer on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Subsequently, an unnecessary seed layer is removed by an etching step or the like to form a wiring layer having a desired wiring pattern.

With these steps (F) and (G), also with step (D) Plating is performed in the formed through holes to form wirings in the through holes. Through the wiring in the through hole, the conductor layers or wiring layers respectively provided on the two main surface sides of the laminated board can be electrically connected to each other.

According to the method for manufacturing a laminated board according to the present invention, An organic support having a glass transition temperature of 90 ° C or higher, preferably 100 ° C or higher, and an adhesive sheet of a thermosetting resin composition layer having a pencil hardness of 2B or higher can be implemented even with a vacuum hot pressing device used in the past. It can effectively use the existing equipment to reduce costs, and can provide It is an excellent laminated board that can maintain the mechanical strength and make the wiring more fine.

〈Use of laminated board〉

The laminate of the present invention can be used as a material for wiring boards such as insulating substrates such as core substrates used in the manufacture of semiconductor devices, and multilayer printed wiring boards.

Hereinafter, an example of the manufacturing process of the wiring board using the laminated board of this invention is demonstrated.

The wiring board can be manufactured by the method including the following steps (I) and (II) using the laminated board of the present invention.

(I) First, a method of preparing a laminate of the present invention in which a wiring layer is provided as described above, and a method of bonding a resin composition layer and a wiring layer with a support film including a support and a resin composition layer provided on the support The steps of fit,

(II) A step of hardening the resin composition layer to form an insulating layer.

The bonding of the bonding film and the laminate in the step (I) can be carried out using the same method as described for the bonding of the bonding film and the prepreg.

The hardening of the resin composition layer in the step (II) can be arbitrarily and preferably performed according to the composition of the resin composition.

After step (II), a roughening process is performed to form a wiring layer. The formation of the wiring layer can be performed by a known method such as the semi-additive method described above.

The laminated board obtained by the manufacturing method of the present invention can be used as, for example, electrical products (e.g., computers, mobile phones, digital cameras, televisions, etc.) and vehicles (e.g., locomotives, automobiles, trams, ships, and airplanes) Various types of semiconductor device components used in operation control, etc.

[Example]

Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to the following examples. In addition, unless otherwise specified, "part" and "%" in the following examples and comparative examples mean "mass part" and "mass%", respectively.

<Organic support>

To prepare a solvent containing toluene and isopropanol in a ratio of 4: 1, an alkyd resin (manufactured by Hitachi Chemical Co., Ltd., TESFINE 303, 48% by mass of nonvolatile matter), and toluene and 100 parts by mass of a solvent mixture of isopropanol and a solution of p-toluenesulfonic acid (Hitachi Kasei Polymers, DRYER 900, 50% by mass of non-volatile content, containing toluene and isopropyl in a ratio of 4: 1 A mixed solution of a solvent of propanol) 2.5 parts by mass of a mixed solution prepared by diluting a nonvolatile matter concentration of 1.5% by mass as a release agent, and coated on the organic support so that the thickness of the release agent after drying becomes 0.1 μm. On the body, it was dried at 150 ° C for 1 minute to obtain an organic support (organic support 1, 2) with a release layer of an organic support having a glass transition temperature of 90 ° C or higher.

Organic support 1: PEN film ("TEONEX Q83" manufactured by Teijin Dupont Film Co., Ltd., thickness 25 μm, glass transition temperature 120 ° C) on one of its main surfaces is provided with an organic support with a release layer and a release layer

Organic support 2: Polyimide film ("APICAL AH" manufactured by KANEKA Co., Ltd., thickness 25 μm, glass transition temperature 300 ° C or higher) on one of the main surfaces is provided with the same release layer as the organic support 1 Organic support with release layer

<Resin Paint 1>

Bien type epoxy resin ("ZX1059" manufactured by Nippon Steel Chemical Co., Ltd., a 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent 169) 8 Parts, naphthalene-type epoxy resin ("HP4032SS" manufactured by DIC (stock), epoxy equivalent of about 144), 3 parts, biphenyl epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, and epoxy equivalent of about 185) ) 6 parts, 15 parts for biphenyl epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 288), phenoxy resin ("YX6954BH30" manufactured by Mitsubishi Chemical Co., Ltd., non-volatile components 30% by mass (mixed solution with 1: 1 solution of MEK and cyclohexanone) 30 parts are dissolved in 5 parts of solvent naphtha with stirring and heating. After cooling to room temperature, the triazine skeleton-containing solution is mixed therein. 12 parts of phenol novolac-based hardener ("LA-7054" manufactured by DIC Corporation, hydroxyl equivalent 125, MEK solution with 60% non-volatile content), naphthol-based hardener (produced by Nippon Steel Chemical Co., Ltd.) "SN485", hydroxyl equivalent 215, MEK solution with 60% non-volatile content) 10 parts, hardening accelerator (4-dimethylaminopyridine (DMAP), MEK solution with 5 mass% non-volatile content), addition molding Hardening promotion ("P200H50" manufactured by Mitsubishi Chemical Corporation, 50% non-volatile content) 2 parts of polyethylene, 15% non-volatile ethanol of polyethylene acetal resin ("KS-1" manufactured by Sekisui Chemical Industry Co., Ltd.) 20 parts of 1: 1 solution with toluene), spherical silica (average particle size: 0.5 μm, Adomatech (average particle size: 0.5 μm, Adomatech ( 20 parts of "SOC2" made of carbon, 0.39 mg / m ² carbon per unit area), 8 parts of rubber particles of organic filler ("STAFYROID AC3816N" made of MICA Industrial Co., Ltd.) (inorganic filler), The resin paint 1 is prepared by uniformly dispersing with a high-speed rotary kneader. The composition of the resin varnish 1 in terms of nonvolatile content is shown in Table 1.

<Next to film 1>

The resin varnish 1 was evenly coated on the release layer side of the organic support 1, and dried at 80 ° C to 140 ° C (average 120 ° C) for 3 minutes, and then dried at 180 ° C for 4 minutes to produce a thermosetting resin composition. Adhesive sheet 1 with a layer thickness of 3 μm. The thickness of the thermosetting resin composition layer was measured using a contact layer thickness meter ("MCD-25MJ" manufactured by MitsuToyo Co., Ltd.) (the same applies to the following examples).

<Resin Paint 2>

A bisphenol epoxy resin ("ZX1059" manufactured by Nippon Steel Chemical Co., Ltd., a 1: 1 mixture of bisphenol A epoxy resin and bisphenol F epoxy resin, epoxy equivalent of about 169) 5 Parts, biphenyl epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), 12 parts, dicyclopentadiene epoxy resin ("HP-7200H" manufactured by DIC, Inc.) , Epoxy equivalent of about 275) 9 parts, phenoxy resin ("YL7553BH30" made by Mitsubishi Chemical Corporation), 30% by mass of nonvolatile matter (mixed solution with 1: 1 solution of MEK and cyclohexanone) in 20 parts Dissolve in 30 parts of solvent oil with heating while stirring. After cooling to room temperature, mix active ester-based hardener ("HPC-8000-65T" manufactured by DIC Corporation) with an active group equivalent of about 223 and a non-volatile content of 65 masses. % Toluene solution) 40 parts, hardening accelerator ("TBPDA (tetrabutylphosphonium decanoate)" manufactured by Beixing Chemical Co., Ltd., 6 parts MEK solution of non-volatile content 5 mass%, phenylamine group Silane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.) for surface treatment of spherical silicon dioxide (average particle size 0.24 μm, "SOC1" manufactured by Adomatech (stock), 0.36 mg of carbon per unit area / m ² ) (Inorganic filler) 100 parts, 5 parts of rubber particles ("STAFYROID AC3816N" manufactured by Mica Industrial Co., Ltd.) as organic filler, uniformly dispersed with a high-speed rotary kneader to prepare resin paint 2. Resin paint 2 The nonvolatile content conversion composition is shown in Table 1.

<Next to film 2>

The resin varnish 2 was evenly coated on the release layer side of the organic support 2 and dried at 80 ° C. to 140 ° C. (average 120 ° C.) for 3 minutes to prepare a bonding sheet 2 having a thermosetting resin composition layer thickness of 5 μm. .

<Next to film 3>

The resin varnish 1 was evenly coated on the release layer side of the organic support 1 and dried at 80 ° C. to 140 ° C. (average 120 ° C.) for 3 minutes to prepare a bonding sheet 3 having a thickness of 3 μm of a thermosetting resin composition layer. .

<Resin Paint 3>

A bisphenol epoxy resin ("ZX1059" manufactured by Nippon Steel Chemical Co., Ltd., a 1: 1 mixture of bisphenol A epoxy resin and bisphenol F epoxy resin, epoxy equivalent of about 169) 5 Parts, biphenyl epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), 12 parts, dicyclopentadiene epoxy resin ("HP-7200H" manufactured by DIC, Inc.) , 9 parts of epoxy equivalent, phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Corporation, 30% by mass of nonvolatile matter (mixed solution with 1: 1 solution of MEK and cyclohexanone)) 20 parts Heat and dissolve in 30 parts of solvent oil while stirring. After cooling to room temperature, 40 parts of an active ester-based hardener ("HPC-8000-65T" manufactured by DIC Corporation, active group equivalent of about 223, and 65% by mass of a non-volatile matter in toluene solution) was mixed therein, and hardening was promoted. Agent (6 parts of "TBPDA (tetrabutylphosphonium decanoate) manufactured by Beixing Chemical Co., Ltd., non-volatile content of 5% by mass MEK solution), and a phenylaminosilane-based coupling agent (Shin-Etsu Chemical Industry Co., Ltd. ) made of "KBM573") for surface treatment of spherical silicon dioxide (average particle size of 0.24μm, Adomatech (shares) manufactured by the "SOC1", the carbon amount per unit area of 0.36mg / m ²⁾ (inorganic filler) 220 5 parts of rubber particles ("STAFYROID AC3816N" manufactured by Mica Industrial Co., Ltd.) as an organic filler, uniformly dispersed with a high-speed rotary kneader to prepare resin paint 3. The composition of the resin varnish 3 in terms of nonvolatile content is shown in Table 1.

<Next to film 4>

The resin varnish 3 was uniformly applied to the release layer side of the organic support 1 and dried three times at 180 ° C. for 5 minutes to prepare a bonding sheet 4 having a thickness of 5 μm of a thermosetting resin composition layer.

<Next to film 5>

The resin varnish 2 was evenly coated on the release layer side of the organic support 2 and dried at 80 ° C. to 120 ° C. (average 100 ° C.) for 2 minutes to prepare a bonding sheet 5 having a thickness of 5 μm of a thermosetting resin composition .

<Next to film 6>

The resin varnish 2 was uniformly applied to the release layer side of the organic support 2, and dried at 80 ° C. to 140 ° C. (average 120 ° C.) for 3 minutes to prepare a bonding sheet 6.

<Resin Paint 4>

A bisphenol epoxy resin ("ZX1059" manufactured by Nippon Steel Chemical Co., Ltd., a 1: 1 mixture of bisphenol A epoxy resin and bisphenol F epoxy resin, epoxy equivalent of about 169) 5 Parts, biphenyl epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), 12 parts, dicyclopentadiene epoxy resin ("HP-7200H" manufactured by DIC, Inc.) , Epoxy equivalent of about 275) 9 parts, phenoxy resin ("YL7553BH30" made by Mitsubishi Chemical Corporation), 30% by mass of nonvolatile matter (mixed solution with 1: 1 solution of MEK and cyclohexanone) in 20 parts Dissolve in 30 parts of solvent oil with heating while stirring. After cooling to room temperature, mix active ester-based hardener ("HPC-8000-65T" manufactured by DIC Corporation) with an active group equivalent of about 223 and a non-volatile content of 65 masses. % Toluene solution) 40 parts, hardening accelerator ("TBPDA (tetrabutylphosphonium decanoate)" manufactured by Beixing Chemical Co., Ltd., 6 parts MEK solution of non-volatile content 5 mass%, phenylamine group Silane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.) for surface treatment of spherical silicon dioxide (average particle size 0.24 μm, "SOC1" manufactured by Adomatech (stock), 0.36 mg of carbon per unit area / m ² ) (Inorganic filler) 280 parts, 5 parts of rubber particles ("STAFYROID AC3816N" manufactured by Mica Industrial Co., Ltd.) as organic filler, uniformly dispersed with a high-speed rotary kneader to prepare resin paint 4. Resin paint 4 The nonvolatile content conversion composition is shown in Table 1.

<Next to film 7>

The resin varnish 4 was uniformly coated on the release layer side of the organic support 2, and dried at 80 ° C. to 140 ° C. (average 120 ° C.) for 3 minutes to prepare a bonding sheet 7 having a thickness of 5 μm.

〈Determination of minimum melt viscosity〉

The minimum melt viscosity of each thermosetting resin composition layer of the adhesive sheet 1 to 5 was measured. "Rheosol-G3000" made by UBM (stock) was used, the resin amount was set to 1 g, and a parallel plate with a diameter of 18 mm was used. From the starting temperature of 60 ° C to the ending temperature of 200 ° C, the heating rate was set to 5 ° C / min. The minimum melting viscosity (poise) was measured under the measurement conditions of an interval of 2.5 ° C, a frequency of 1 Hz, and a skewness of 1 degree. The results are shown in Table 2.

<Measurement of pencil hardness>

The pencil hardness of each of the thermosetting resin composition layers of the above-mentioned adhesive sheets 1 to 5 was measured in accordance with JIS K5600-5-4. The results are shown in Table 2.

<Example 1> Roughening process steps of inner circuit board

250mm × 250mm square-shaped glass cloth substrate epoxy resin laminated board with inner layer circuit (inner layer circuit thickness is 18μm, substrate thickness is 0.3mm, and “R1515A” manufactured by Panasonic Co., Ltd.) are immersed on both sides In "CZ8100" manufactured by Merck, the copper surface is roughened.

(2) Vacuum hot pressing step

The adhesive sheet 1 was formed into a laminate using a vacuum hot-pressing device (trade name VH1-1603, manufactured by Kitagawa Seiki Co., Ltd.).

The vacuum hot-pressing step is performed in a group with the following structure, and is performed in a vacuum hot-pressing device in a state where the three groups overlap.

Structure: Buffer paper ("AACP-9N" made by Awa Paper Co., Ltd., thickness 800 μm) / SUS board (1 mm thick) / Release film ("AFLEX 50N NT" made by Asahi Glass Co., Ltd., 50 μm thickness) Sheet 1 / prepreg ("GEA-800G" manufactured by Hitachi Chemical Co., Ltd., thickness 0.06mm) / Inner circuit board / prepreg / adhesive sheet 1 / Release film / SUS board / Buffer paper

The implementation conditions of the vacuum hot pressing step are as follows.

Temperature: The temperature is raised from room temperature (normal temperature) to 205 ° C at a temperature increase rate of 5 ° C / min, and maintained at 205 ° C for 90 minutes, and then the temperature is decreased at a temperature decrease rate of 5 ° C / min. To room temperature

Pressing pressure: Set the pressing pressure at the time of increasing the temperature from room temperature to 50kgf / cm ² and keep it until the end of the cooling

Ambient pressure: 70mm / hg ~ 74mm / hg (9.3 × 10 -3 MPa ~ 9.9 × 10 -3 MPa)

After the vacuum hot-pressing step was completed, the organic support 1 was peeled from the formed thermosetting resin composition layer, and the peelability was evaluated based on the following criteria. The results are shown in Table 2.

Peelable: ○

Cannot be stripped: ×

(3) Roughening treatment with desmear treatment

First, the obtained laminate was immersed in Swelling Dip Securiganth P containing diethylene glycol monobutyl ether manufactured by Japan ATOTECH Co., Ltd. at a swelling liquid at 60 ° C for 10 minutes. Next, it was immersed in a roughened solution of Concentrate Compact P (KMnO ₄ : 60 g / L and NaOH: 40 g / L aqueous solution) made by Japan ATOTECH Co., Ltd. at 80 ° C. for 20 minutes. After the laminate was washed with water, it was finally immersed in ATOTECH (strand) Reduction Solution Securiganth P for 5 minutes at 40 ° C. It was then dried at 130 ° C for 15 minutes. By the above treatment, the surface of the thermosetting resin composition layer is subjected to a roughening treatment (and a slag removing treatment).

[Measurement of arithmetic average roughness (Ra value) after roughening]

Non-contact type surface roughness meter ("WYKO NT3300" manufactured by VEECO Instrument Co., Ltd.) The surface roughness (Ra value) was obtained by using a VSI contact mode, a 50-fold lens, and a measurement range of 121 μm × 92 μm. For each of the three laminates obtained A total of 15 points were measured at each of the 5 points, and the difference between the average value of the 15 points of the Ra value and the maximum and minimum values of the surface roughness (surface roughness deviation) was obtained.

The smaller the surface roughness deviation, the closer it is to the conductor layer (wiring layer) The higher the adhesion, the finer the wiring can be made. The surface roughness deviation is preferably less than 150 nm.

The deviation determination is performed based on the following criteria. The results are shown in Table 2.

(Difference between the maximum value and the minimum value of the surface roughness) The laminate having a thickness of less than 150 nm was determined as ○.

A laminated plate (the difference between the maximum value and the minimum value of the surface roughness) of 150 nm or more was judged as ×.

(4) Formation of the conductor layer

In order to form a conductor layer on the surface of the roughened laminate, an electroless copper plating step (an electroless copper plating step using a chemical solution made by Japan ATOTECH Co., Ltd.) is performed. This step is performed so that the thickness of the electroless copper plating layer may be 1 μm. Details of the electroless copper plating step and the electrolytic copper plating step are as follows.

<Electroless copper plating process>

1. Alkali cleaning (cleaning and charge adjustment of laminate surface)

Using Cleaning cleaner Securigarth 902 (trade name), washing was performed at 60 ° C for 5 minutes.

2. Soft etching (cleaning of electroless copper plating layer)

It was washed with sulfuric acid acid sodium peroxodisulfate aqueous solution at 30 ° C for 1 minute.

3.Pre-impregnation (used to adjust the charge on the surface of the laminate of Pd)

Pre.Dip Neoganth B (trade name) was used and treated at room temperature for 1 minute.

4.Activator (Pd on the surface of the laminate)

Activator Neoganth 834 (trade name) was used for 5 minutes at 35 ° C.

5. Reduction (reduction of Pd imparted to the laminate)

A mixed solution of Reducer Neoganth WA (trade name) and Reducer Acceralator 810 mod. (Trade name) was used and treated at 30 ° C for 5 minutes.

6. Electroless copper plating (to precipitate copper on the surface of the laminate (the surface imparted with Pd))

A mixed solution of Basic Solution Printganth MSK-DK (trade name), Copper Solution Printganth MSK (trade name), Stabilizer Printganth MSK-DK (trade name), and Reducer Cu (trade name) was treated at 35 ° C for 20 minutes.

<Electrolytic Copper Plating Procedure>

Next, an electrolytic copper plating step was performed to a total thickness of 30 μm. In this way, a thick film conductor layer (copper layer) is formed. Then, an annealing treatment was performed at 190 ° C for 60 minutes to manufacture a laminated board with a conductor layer.

[Determination of peel strength (peel strength) of conductor layer]

On the conductor layer of the laminated board with a conductor layer, a part of a region with a width of 10 mm and a length of 100 mm is cut. One end side was peeled off, and it was clamped with a jig (Autograph type testing machine "AC-50C-SL" made by DSI), and at room temperature (25 ° C), it was measured to be perpendicularly peeled off at a speed of 50 mm / min. Load at 35mm (kgf / cm (N / cm)). For the three laminated plates with conductor layers, 5 points / piece were measured for a total of 15 points, and the average and peel strength deviation of each laminated plate with conductor layers were determined (the maximum and minimum peel strengths). Value difference).

The smaller the deviation in peel strength is, the smaller the deviation from the conductor layer (wiring layer) is. The higher the adhesion, the finer the wiring can be. The deviation in peel strength is preferably less than 0.15 kgf / cm.

The deviation determination is performed based on the following criteria. The results are shown in Table 2.

(Difference between the maximum value and the minimum value of the peel strength) Less than 0.15 kgf / cm: ○

(The difference between the maximum and minimum peel strength) is 0.15kgf / cm or more: ×

[Evaluation of reflow resistance]

For laminates with a conductor layer, a reflow device with a peak temperature of 260 ° C ("HAS-6116" manufactured by Japan Antim Corporation) is used. The temperature distribution of IPC / JEDEC J-STD-020C repeats the reflow step for 10 simulations. Subsequently, the state of adhesion between the conductor layer and the thermosetting resin composition layer was visually confirmed, that is, whether there was abnormality in peeling. The evaluation was performed based on the following criteria. The results are shown in Table 2.

No exception: ○

Abnormal peeling: ×

<Example 2>

Except having used the adhesive sheet 2 instead of the adhesive sheet 1, it manufactured, measured, and evaluated similarly to Example 1. In the "(2) Vacuum Hot Pressing Step", the temperature is set to "first increase the temperature from room temperature to 230 ° C at a temperature increase rate of 5 ° C / min, maintain it at 230 ° C for 90 minutes, and then decrease the temperature at a temperature decrease rate of 5 ° C / min. To room temperature. "

<Example 3>

Production, measurement, and evaluation were performed in the same manner as in Example 1 except that the adhesive sheet 3 was used instead of the adhesive sheet 1. Also, in the "(2) vacuum hot pressing step", the temperature is set to "first increase the temperature from room temperature to 205 ° C at a temperature increase rate of 5 ° C / min, maintain it at 205 ° C for 90 minutes, and then cool down at a temperature decrease rate of 5 ° C / min To room temperature. "

<Example 4>

Production, measurement, and evaluation were performed in the same manner as in Example 1 except that the adhesive sheet 4 was used instead of the adhesive sheet 1. Also, "(2) Vacuum hot pressing In the step, the temperature is set to "first increase the temperature from room temperature to 205 ° C at a temperature increase rate of 5 ° C / min, maintain it at 205 ° C for 90 minutes, and then reduce the temperature to room temperature at a decrease rate of 5 ° C / min.

<Comparative Example 1>

Except having used the adhesive sheet 5 instead of the adhesive sheet 1, it manufactured, measured, and evaluated similarly to Example 1. Also, in the "(2) vacuum hot pressing step", the temperature is set to "first increase the temperature from room temperature to 230 ° C at a temperature increase rate of 5 ° C / min, maintain it at 230 ° C for 90 minutes, and then cool down at a temperature decrease rate of 5 ° C / min To room temperature. "

<Comparative Example 3>

Except having used the adhesive sheet 7 instead of the adhesive sheet 1, it manufactured, measured, and evaluated similarly to Example 1. In the "(2) Vacuum Hot Pressing Step", the temperature is set to "first increase the temperature from room temperature to 230 ° C at a temperature increase rate of 5 ° C / min, maintain it at 230 ° C for 90 minutes, and then decrease the temperature at a temperature decrease rate of 5 ° C / min. To room temperature. "

The composition of the resin paint used in the above examples and comparative examples is shown in Table 1 below, and the measurement results and evaluation results of the examples and comparative examples are shown in Table 2 below.

As can be understood from Table 2, the laminates of Examples 1, 2, 3, and 4 having a pencil hardness of a thermosetting resin composition layer of 2B or more were compared with Comparative Examples 1 and 3, and the deviations in surface roughness, that is, rough Both unevenness in variation and variation in peel strength were small. Therefore, it is taught that the use of the laminated board of the present invention can make the wiring finer. Moreover, compared with Comparative Example 3, the surface roughness of Examples 1, 2, 3, and 4 is small, the peeling strength is large, and the reflow resistance is excellent, so the reliability of the wiring formed is taught to be high.

Claims (14)

A method for manufacturing a laminated board, which includes the following steps (A) and (B). The step (A) is prepared on an organic support to set a thermosetting property with a thickness of 1 μm to 10 μm and a pencil hardness of 2B to 7H. In the step of bonding the resin composition layer, in step (B), one or more prepregs are arranged between the two bonding sheets arranged such that the thermosetting resin composition layers face each other. It is a step of integrally molding by heating and pressing at 200 ° C or higher under reduced pressure. The method for manufacturing a laminated board according to claim 1, wherein the thermosetting resin composition contains an inorganic filler, and when the non-volatile content in the thermosetting resin composition is 100% by mass, the inorganic filler The content is 15 mass% or more and 80 mass% or less. The method for manufacturing a laminated board according to claim 2, wherein the content of the inorganic filler is 35% by mass or more and 60% by mass or less. The method for manufacturing a laminated board according to claim 1, wherein the thermosetting resin composition contains an epoxy resin and a hardener. The method for manufacturing a laminated board according to claim 1, wherein the thermosetting resin composition includes an organic filler, and when the non-volatile component in the thermosetting resin composition is 100% by mass, the content of the organic filler It is 1 mass% or more and 10 mass% or less. The method for manufacturing a laminated board according to claim 1, wherein the glass transition temperature of the organic support is 90 ° C or higher. The method for manufacturing a laminated board according to claim 1, wherein the thickness of the organic support is 5 μm to 50 μm. For example, the method for manufacturing a laminated board according to claim 1, wherein the aforementioned step (B) is a step of using two or more prepregs, and the prepregs are further formed by integrally disposing an inner-layer circuit substrate. The method for manufacturing a laminated board according to claim 1, wherein the minimum melt viscosity of the aforementioned thermosetting resin composition layer is 20,000 poise or more. The method for manufacturing a laminated board according to claim 1, further comprising a step (C) of peeling the organic support. The method for manufacturing a laminated board according to claim 1, further comprising a step (D) of forming a through hole. For example, the method for manufacturing a laminated board according to claim 10, further comprising a step (E) of roughening the laminated board after the aforementioned step (C). For example, the method for manufacturing a laminated board according to claim 12, further comprising a step (F) of forming a conductor layer by plating after the foregoing step (E). The method for manufacturing a laminated board according to claim 13, further comprising a step (G) of forming a wiring layer using the aforementioned conductor layer.