JP2021123687A - Cured body, b-stage film, and multilayer printed wiring board - Google Patents

Abstract

To provide a cured body which can reduce sidelobes and can prevent occurrence of cracking or fracture of an insulating layer in the periphery of a via hole.SOLUTION: A cured body is a cured body of a resin material, and is a cured body used as an insulating material. The component contained in the cured body is separated into a hard component at 30°C, a middle component at 30°C, a soft component at 30°C, a hard component at 170°C, a middle component at 170°C, and a soft component at 170°C based on a free induction decay curve at 30°C and 170°C obtained using a pulse NMR, a content of the hard component at 170°C is 40% or more and 80% or less in 100% of the total of the contents of the hard component, the middle component and the soft component at 170°C, and a ratio of spin-spin relaxation time of the hard component at 170°C to spin-spin-relaxation time of the hard component at 30°C is 1.5 or less.SELECTED DRAWING: Figure 1

Description

The present invention relates to a cured product of a resin material and a B stage film. The present invention also relates to a multilayer printed wiring board using the cured product.

Conventionally, various resin materials have been used to obtain electronic components such as semiconductor devices, laminated boards and printed wiring boards. For example, in a multilayer printed wiring board, a resin material is used to form an insulating layer for insulating the internal layers and to form an insulating layer located on a surface layer portion. Wiring, which is generally a metal, is laminated on the surface of the insulating layer. Further, in order to form the insulating layer, a resin film obtained by forming the resin material into a film may be used. The resin material and the resin film are used as an insulating material for a multilayer printed wiring board including a build-up film.

Patent Document 1 below discloses a resin composition containing a compound having a maleimide group, a divalent group having at least two imide bonds, and a saturated or unsaturated divalent hydrocarbon group. .. Patent Document 1 describes that a cured product of this resin composition can be used as an insulating layer for a multilayer printed wiring board or the like.

Patent Document 2 below includes (A) epoxy resin, (B) active ester compound, (C) carbodiimide compound, (D) thermoplastic resin, and (E) inorganic filler, and contains (E) component. However, when the non-volatile component in the resin composition is 100% by mass, a resin composition having a non-volatile component of 40% by mass or more is disclosed.

WO2016 / 114286A1 Japanese Unexamined Patent Publication No. 2016-027097

When manufacturing a multilayer printed wiring board, an insulating layer is formed by heating and curing the resin material. Further, a via hole is formed at the time of manufacturing the multilayer printed wiring board.

In the conventional resin material as described in Patent Documents 1 and 2, the resin material is deteriorated by the heat of a laser or the like at the time of forming the via hole, and the side lobe may be relatively large around the formed via hole.

Further, in the conventional resin materials as described in Patent Documents 1 and 2, the flexibility of the insulating layer is small, and when the insulating layer is exposed to a high temperature, the insulating layer is liable to crack or crack around the via hole. ..

An object of the present invention is to provide a cured product of a resin material and a B-stage film capable of reducing side lobes and suppressing cracks or cracks in an insulating layer around a via hole. The present invention also provides a multilayer printed wiring board using the cured product.

According to a broad aspect of the present invention, it is a cured product of a resin material, which is a cured product used as an insulating material, and is said to be a cured product based on a free induction decay curve at 30 ° C. obtained by using pulse NMR. The components contained in the above are separated into three components in ascending order of spin-spin relaxation time: a hard component at 30 ° C., a middle component at 30 ° C., and a soft component at 30 ° C., and obtained by using pulse NMR. Based on the free induction decay curve at 170 ° C., the components contained in the cured product are arranged in ascending order of spin-spin relaxation time: hard component at 170 ° C., middle component at 170 ° C., and soft at 170 ° C. When separated into the three components, the content of the hard component at 170 ° C., the content of the middle component at 170 ° C., and the content of the soft component at 170 ° C. are 100% in total. The content of the hard component at 170 ° C. is 40% or more and 80% or less, and the ratio of the spin-spin relaxation time of the hard component at 170 ° C. to the spin-spin relaxation time of the hard component at 30 ° C. is A cured product of 1.5 or less is provided.

In certain aspects of the cured product according to the present invention, the spin-spin relaxation time of the hard component at 170 ° C. is 0.016 ms or less.

In a specific aspect of the cured product according to the present invention, a total of 100% of the content of the hard component at 30 ° C., the content of the middle component at 30 ° C., and the content of the soft component at 30 ° C. Among them, the content of the hard component at 30 ° C. is 70% or more and 90% or less.

In certain aspects of the cured product according to the present invention, the resin material comprises a thermosetting compound and an inorganic filler.

In a specific aspect of the cured product according to the present invention, the resin material contains a thermosetting compound and a curing agent, the thermosetting compound contains an epoxy compound, and the curing agent is an active ester compound. including.

According to a broad aspect of the present invention, which is a B-stage film, which is a B-stage film used as an insulating material, the B-stage film is prepared at 130 ° C. for 30 minutes, 170 ° C. for 30 minutes, and 200 ° C. for 1 hour. A cured product of the B stage film is obtained by heating in this order, and the components contained in the cured product have a short spin-spin relaxation time based on the free induction decay curve at 30 ° C. obtained by pulse NMR. In order, it is separated into three components, a hard component at 30 ° C., a middle component at 30 ° C., and a soft component at 30 ° C., and based on a free induction decay curve at 170 ° C. obtained by pulse NMR. When the components contained in the cured product are separated into three components, a hard component at 170 ° C., a middle component at 170 ° C., and a soft component at 170 ° C., in ascending order of spin-spin relaxation time, the 170 ° C. Of the total 100% of the content of the hard component at 170 ° C., the content of the middle component at 170 ° C., and the content of the soft component at 170 ° C., the content of the hard component at 170 ° C. is 40% or more. A B-stage film is provided in which the ratio of the spin-spin relaxation time of the hard component at 170 ° C. to the spin-spin relaxation time of the hard component at 30 ° C. is 1.5 or less, which is 80% or less. NS.

In a particular aspect of the B-stage film according to the present invention, the spin-spin relaxation time of the hard component at 170 ° C. is 0.016 ms or less.

In a specific aspect of the B-stage film according to the present invention, a total of 100 of the content of the hard component at 30 ° C., the content of the middle component at 30 ° C., and the content of the soft component at 30 ° C. The content of the hard component at 30 ° C. is 70% or more and 90% or less.

The B stage film according to the present invention is suitably used for forming an insulating layer in a multilayer printed wiring board.

According to a broad aspect of the present invention, a circuit board, a plurality of insulating layers arranged on the surface of the circuit board, and a metal layer arranged between the plurality of insulating layers are provided, and the plurality of insulating layers are provided. A multilayer printed wiring board is provided in which the material of at least one of the insulating layers is the cured product described above.

The cured product according to the present invention is a cured product made of a resin material and is a cured product used as an insulating material. In the present invention, based on the free induction decay curve at 30 ° C. obtained by pulse NMR, the components contained in the cured product are divided into hard components at 30 ° C. and 30 ° C. in ascending order of spin-spin relaxation time. It is separated into three components, a middle component at 30 ° C and a soft component at 30 ° C. In the present invention, based on the free induction decay curve at 170 ° C. obtained by pulse NMR, the components contained in the cured product are divided into hard components at 170 ° C. and 170 ° C. in ascending order of spin-spin relaxation time. It is separated into three components, a middle component at 170 ° C and a soft component at 170 ° C. In the cured product according to the present invention, 170 ° C. is out of a total of 100% of the content of the hard component at 170 ° C., the content of the middle component at 170 ° C. The content of the hard component in the above is 40% or more and 80% or less. In the cured product according to the present invention, the ratio of the spin-spin relaxation time of the hard component at 170 ° C. to the spin-spin relaxation time of the hard component at 30 ° C. is 1.5 or less. Since the cured product according to the present invention has the above-mentioned structure, the side lobes can be made small, and cracks or cracks in the insulating layer around the via holes can be suppressed.

The B-stage film according to the present invention is a B-stage film used as an insulating material. In the present invention, the B stage film is heated at 130 ° C. for 30 minutes, 170 ° C. for 30 minutes, and 200 ° C. for 1 hour in this order to obtain a cured product of the B stage film. In the present invention, based on the free induction decay curve at 30 ° C. obtained by pulse NMR, the components contained in the cured product are divided into hard components at 30 ° C. and 30 ° C. in ascending order of spin-spin relaxation time. It is separated into three components, a middle component at 30 ° C and a soft component at 30 ° C. In the present invention, based on the free induction decay curve at 170 ° C. obtained by pulse NMR, the components contained in the cured product are divided into hard components at 170 ° C. and 170 ° C. in ascending order of spin-spin relaxation time. It is separated into three components, a middle component at 170 ° C and a soft component at 170 ° C. In the B stage film according to the present invention, 170 out of a total of 100% of the content of the hard component at 170 ° C., the content of the middle component at 170 ° C., and the content of the soft component at 170 ° C. The content of the hard component at ° C. is 40% or more and 80% or less. In the B-stage film according to the present invention, the ratio of the spin-spin relaxation time of the hard component at 170 ° C. to the spin-spin relaxation time of the hard component at 30 ° C. is 1.5 or less. Since the B stage film according to the present invention has the above-mentioned structure, the side lobes can be made small, and cracks or cracks in the insulating layer around the via holes can be suppressed.

FIG. 1 is a cross-sectional view schematically showing a multilayer printed wiring board using a cured product according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

The cured product according to the present invention is a cured product made of a resin material and is a cured product used as an insulating material.

In the present invention, based on the free induction decay curve at 30 ° C. obtained by pulse NMR, the components contained in the cured product are divided into hard components at 30 ° C. and 30 ° C. in ascending order of spin-spin relaxation time. It is separated into three components, a middle component at 30 ° C and a soft component at 30 ° C. In the present invention, based on the free induction decay curve at 170 ° C. obtained by pulse NMR, the components contained in the cured product are divided into hard components at 170 ° C. and 170 ° C. in ascending order of spin-spin relaxation time. It is separated into three components, a middle component at 170 ° C and a soft component at 170 ° C. In the cured product according to the present invention, 170 ° C. is out of a total of 100% of the content of the hard component at 170 ° C., the content of the middle component at 170 ° C. The content of the hard component in the above is 40% or more and 80% or less. In the cured product according to the present invention, the ratio of the spin-spin relaxation time of the hard component at 170 ° C. to the spin-spin relaxation time of the hard component at 30 ° C. is 1.5 or less.

The B-stage film according to the present invention is a B-stage film used as an insulating material.

In the present invention, the B stage film is heated at 130 ° C. for 30 minutes, 170 ° C. for 30 minutes, and 200 ° C. for 1 hour in this order to obtain a cured product of the B stage film. In the present invention, based on the free induction decay curve at 30 ° C. obtained by pulse NMR, the components contained in the cured product are divided into hard components at 30 ° C. and 30 ° C. in ascending order of spin-spin relaxation time. It is separated into three components, a middle component at 30 ° C and a soft component at 30 ° C. In the present invention, based on the free induction decay curve at 170 ° C. obtained by pulse NMR, the components contained in the cured product are divided into hard components at 170 ° C. and 170 ° C. in ascending order of spin-spin relaxation time. It is separated into three components, a middle component at 170 ° C and a soft component at 170 ° C. In the B stage film according to the present invention, 170 out of a total of 100% of the content of the hard component at 170 ° C., the content of the middle component at 170 ° C., and the content of the soft component at 170 ° C. The content of the hard component at ° C. is 40% or more and 80% or less. In the B-stage film according to the present invention, the ratio of the spin-spin relaxation time of the hard component at 170 ° C. to the spin-spin relaxation time of the hard component at 30 ° C. is 1.5 or less.

Since the cured product and the B stage film according to the present invention have the above-mentioned structure, the side lobes can be made small, and cracks or cracks in the insulating layer around the via holes can be suppressed. Further, in the cured product and the B stage film according to the present invention, cracks or cracks in the insulating layer in a region other than the vicinity of the via hole can be suppressed. Further, in the cured product and the B stage film according to the present invention, even when the cured product and the B stage film contain an inorganic filler, the inorganic filler is unlikely to fall off during via hole formation. Therefore, in the cured product and the B stage film according to the present invention, the connection reliability can be improved in the thermal cycle test.

In the cured product and B stage film according to the present invention, the total content of the hard component at 170 ° C., the middle component content at 170 ° C., and the soft component content at 170 ° C. is 100%. The content of the hard component at 170 ° C. is 40% or more and 80% or less. In the present invention, since the content of the hard component at 170 ° C. is 40% or more, for example, the thermosetting compound and the inorganic filler can be satisfactorily interacted with each other, and as a result, the side lobes can be reduced. In addition, it is possible to prevent the inorganic filler from falling off during the formation of the via hole. Further, in the present invention, since the content of the hard component at 170 ° C. is 80% or less, the stress relaxation of the cured product can be made appropriate, and as a result, the insulating layer around the via hole is cracked or cracked. It can be suppressed. The total of the content of the hard component at 170 ° C., the content of the middle component at 170 ° C., and the content of the soft component at 170 ° C. is the total content of the cured product at 170 ° C. The quantity.

In the cured product and B stage film according to the present invention, the total content of the hard component at 170 ° C., the middle component content at 170 ° C., and the soft component content at 170 ° C. is 100%. The content of the hard component at 170 ° C. is preferably 45% or more, more preferably 50% or more, still more preferably 55% or more, preferably 75% or less. When the content of the hard component at 170 ° C. is equal to or higher than the above lower limit, the side lobes can be further reduced, and the inorganic filler can be more effectively prevented from falling off during the formation of via holes. .. When the content of the hard component at 170 ° C. is not more than the above upper limit, cracks or cracks in the insulating layer around the via hole can be suppressed more effectively.

In the cured product and B stage film according to the present invention, the total content of the hard component at 30 ° C., the middle component content at 30 ° C., and the soft component content at 30 ° C. is 100%. The content of the hard component at 30 ° C. is preferably 70% or more, more preferably 75% or more, still more preferably 80% or more. In the cured product and B stage film according to the present invention, the total content of the hard component at 30 ° C., the middle component content at 30 ° C., and the soft component content at 30 ° C. is 100%. The content of the hard component at 30 ° C. is preferably 90% or less, more preferably 88% or less, still more preferably 85% or less. When the content of the hard component at 30 ° C. is equal to or higher than the above lower limit, the side lobes can be further reduced, and the inorganic filler can be more effectively prevented from falling off during the formation of via holes. .. When the content of the hard component at 30 ° C. is not more than the above upper limit, cracks or cracks in the insulating layer around the via hole can be suppressed more effectively. The total of the content of the hard component at 30 ° C., the content of the middle component at 30 ° C., and the content of the soft component at 30 ° C. is the total content of the cured product at 30 ° C. The quantity.

In the cured product and B-stage film according to the present invention, the ratio of the spin-spin relaxation time of the hard component at 170 ° C. to the spin-spin relaxation time of the hard component at 30 ° C. (of the hard component at 170 ° C.). Spin-spin relaxation time / spin-spin relaxation time of the hard component at 30 ° C.) is 1.5 or less. In the cured product and B-stage film according to the present invention, the spin-spin relaxation time of the hard component at 170 ° C. and the spin-spin relaxation time of the hard component at 30 ° C. are relatively close. Therefore, for example, even when the cured product is exposed to a high temperature, the expansion and contraction of the cured product is small, and as a result, cracks or cracks in the insulating layer around the via hole can be suppressed.

In the cured product and B-stage film according to the present invention, the ratio of the spin-spin relaxation time of the hard component at 170 ° C. to the spin-spin relaxation time of the hard component at 30 ° C. (of the hard component at 170 ° C.). The spin-spin relaxation time / spin-spin relaxation time of the hard component at 30 ° C.) is preferably 1 or more, more preferably 1.05 or more. In the cured product and the B-stage film according to the present invention, the above ratio (spin-spin relaxation time of the hard component at 170 ° C./spin-spin relaxation time of the hard component at 30 ° C.) is preferably 1.25 or less. More preferably, it is 1.2 or less. When the above ratio (spin-spin relaxation time of hard component at 170 ° C./spin-spin relaxation time of hard component at 30 ° C.) is equal to or more than the above lower limit and below the above upper limit, the insulating layer around the via hole is cracked or cracked. Can be suppressed even more effectively.

In the cured product and B-stage film according to the present invention, the spin-spin relaxation time of the hard component at 170 ° C. is preferably 0.01 ms or more, more preferably 0.012 ms or more, preferably 0. It is 016 ms or less, more preferably 0.015 ms or less, still more preferably 0.014 ms or less. When the spin-spin relaxation time of the hard component at 170 ° C. is not less than the above lower limit and not more than the above upper limit, the side lobe can be further reduced.

In the cured product and B-stage film according to the present invention, the spin-spin relaxation time of the hard component at 30 ° C. is preferably 0.01 ms or more, more preferably 0.011 ms or more, preferably 0. It is 014 ms or less, more preferably 0.013 ms or less. When the spin-spin relaxation time of the hard component at 30 ° C. is not less than the above lower limit and not more than the above upper limit, the side lobe can be further reduced.

The contents of the hard component, the middle component and the soft component at 30 ° C., the contents of the hard component, the middle component and the soft component at 170 ° C., and the spin-spin relaxation time of the hard component at 170 ° C. and the above. The spin-spin relaxation time of the hard component at 30 ° C. is specifically determined by the method described in Examples.

The contents of the hard component at 170 ° C. and the hard component at 30 ° C., the ratio (spin-spin relaxation time of the hard component at 170 ° C./spin-spin relaxation time of the hard component at 30 ° C.), the above. Examples of the method for controlling the spin-spin relaxation time of the hard component at 170 ° C. and the hard component at 30 ° C. within the above-mentioned preferable range include the following methods. (1) By phase-separating the soft component, the content of the hard component at 170 ° C. can be increased. (2) By reducing the polarity of the residual solvent in the cured body during pre-curing, the content of the hard component at 170 ° C. is increased, and the relaxation time can be sufficiently shortened. (3) The liquid thermosetting compound and the inorganic filler treated with the silane coupling agent are stirred in advance so that the thermosetting compound is sufficiently blended on the surface of the inorganic filler, and then other components are added. As a result, the thermosetting compound and the surface of the inorganic filler interact strongly. As a result, the content of the hard component at 170 ° C. is increased, and the relaxation time can be sufficiently shortened.

Hereinafter, the details of the cured product according to the present invention and each component used in the resin material for obtaining the cured product, the use of the cured product according to the present invention, and the like will be described. In addition, the details of each component used in the B-stage film according to the present invention, the use of the B-stage film according to the present invention, and the like will be described below. The B stage film is a resin material.

[Thermosetting compound]
The resin material preferably contains a thermosetting compound. The cured product is preferably a thermosetting product of the resin material. Examples of the thermosetting compound include epoxy compounds, maleimide compounds, styrene compounds, phenoxy compounds, oxetane compounds, episulfide compounds, (meth) acrylic compounds, phenol compounds, amino compounds, unsaturated polyester compounds, polyurethane compounds, and silicone compounds. Can be mentioned. Only one type of the thermosetting compound may be used, or two or more types may be used in combination.

From the viewpoint of further enhancing the thermal dimensional stability of the cured product, the thermosetting compound preferably contains the epoxy compound or the maleimide compound, and more preferably contains the epoxy compound.

<Epoxy compound>
As the epoxy compound, a conventionally known epoxy compound can be used. Only one type of the epoxy compound may be used, or two or more types may be used in combination.

Examples of the epoxy compound include bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, phenol novolac type epoxy compound, biphenyl type epoxy compound, biphenyl novolac type epoxy compound, biphenol type epoxy compound, and naphthalene type epoxy compound. , Fluorene type epoxy compound, phenol aralkyl type epoxy compound, naphthol aralkyl type epoxy compound, dicyclopentadiene type epoxy compound, anthracene type epoxy compound, epoxy compound with adamantan skeleton, epoxy compound with tricyclodecane skeleton, naphthylene ether type Examples thereof include an epoxy compound and an epoxy compound having a triazine nucleus as a skeleton.

The epoxy compound preferably contains an epoxy compound having an aromatic skeleton, more preferably contains an epoxy compound having a naphthalene skeleton or a phenyl skeleton, further preferably an epoxy compound having an aromatic skeleton, and a naphthalene skeleton. It is particularly preferable that it is an epoxy compound having. In this case, the dielectric loss tangent can be further lowered, and heat resistance, flame retardancy, and thermal dimensional stability can be improved.

From the viewpoint of further lowering the dielectric loss tangent and improving the coefficient of linear thermal expansion (CTE), the epoxy compound preferably contains an epoxy compound that is liquid at 25 ° C. and an epoxy compound that is solid at 25 ° C. ..

The viscosity of the epoxy compound liquid at 25 ° C. at 25 ° C. is preferably 1000 mPa · s or less, and more preferably 500 mPa · s or less.

When measuring the viscosity of the epoxy compound, for example, a dynamic viscoelasticity measuring device (“VAR-100” manufactured by Leologica Instruments) or the like is used.

The molecular weight of the epoxy compound is more preferably 1000 or less. In this case, even if the component excluding the solvent in the resin material is 100% by weight and the content of the inorganic filler is 50% by weight or more, a resin material having high fluidity at the time of forming the insulating layer can be obtained. Therefore, when the uncured resin material or the B-staged product is laminated on the circuit board, the inorganic filler can be uniformly present.

The molecular weight of the epoxy compound means a molecular weight that can be calculated from the structural formula when the epoxy compound is not a polymer and the structural formula of the epoxy compound can be specified. When the epoxy compound is a polymer, it means the weight average molecular weight.

From the viewpoint of further increasing the adhesive strength between the insulating layer and the metal layer, the content of the epoxy compound is preferably 5% by weight or more, more preferably 5% by weight or more, based on 100% by weight of the components excluding the inorganic filler and the solvent in the resin material. It is preferably 25% by weight or more, preferably 60% by weight or less, and more preferably 50% by weight or less.

<Maleimide compound>
As the maleimide compound, a conventionally known maleimide compound can be used. Only one type of the maleimide compound may be used, or two or more types may be used in combination.

The maleimide compound may be a bismaleimide compound.

Examples of the maleimide compound include N-phenylmaleimide and N-alkylbismaleimide.

The maleimide compound may or may not have an aromatic ring. The maleimide compound preferably has an aromatic ring.

In the maleimide compound, it is preferable that the nitrogen atom in the maleimide skeleton and the aromatic ring are bonded.

From the viewpoint of further enhancing the thermal dimensional stability, the content of the maleimide compound is preferably 0.5% by weight or more, more preferably 1% by weight or more, based on 100% by weight of the components excluding the solvent in the resin material. It is preferably 15% by weight or less, more preferably 10% by weight or less.

The content of the maleimide compound in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material is preferably 2.5% by weight or more, more preferably 5% by weight or more, still more preferably 7.5% by weight. % Or more, preferably 50% by weight or less, more preferably 35% by weight or less. When the content of the maleimide compound is at least the above lower limit and at least the above upper limit, the thermal dimensional stability of the cured product can be further enhanced.

From the viewpoint of effectively exerting the effects of the present invention, the molecular weight of the maleimide compound is preferably 500 or more, more preferably 1000 or more, preferably less than 30,000, and more preferably less than 20,000.

The molecular weight of the maleimide compound means a molecular weight that can be calculated from the structural formula when the maleimide compound is not a polymer and when the structural formula of the maleimide compound can be specified. The molecular weight of the maleimide compound indicates the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) when the maleimide compound is a polymer.

Examples of commercially available maleimide compounds include "BMI-4000" and "BMI-5100" manufactured by Daiwa Kasei Kogyo Co., Ltd., and Designer Molecules Inc. Examples thereof include "BMI-3000" and "BMI-1500" manufactured by the same company.

[Inorganic filler]
The resin material preferably contains an inorganic filler. By using the inorganic filler, the dielectric loss tangent can be further lowered, and the thermal dimensional stability can be further improved. Only one kind of the above-mentioned inorganic filler may be used, or two or more kinds may be used in combination.

Examples of the inorganic filler include silica, talcite, clay, mica, hydrotalcite, alumina, magnesium oxide, aluminum hydroxide, aluminum nitride, and boron nitride.

The surface roughness of the surface of the insulating layer is reduced, the adhesive strength between the insulating layer and the metal layer is further increased, finer wiring is formed on the surface of the insulating layer, and the insulating reliability is better than that of the insulating layer. From the viewpoint of imparting, the inorganic filler is preferably silica or alumina, more preferably silica, and even more preferably molten silica. By using silica, the coefficient of thermal expansion of the insulating layer is further lowered, the surface roughness of the surface of the insulating layer is effectively reduced, and the adhesive strength between the insulating layer and the metal layer is effectively increased. The shape of silica is preferably spherical.

The inorganic filler is spherical silica from the viewpoint of advancing the curing of the resin regardless of the curing environment, effectively increasing the glass transition temperature of the cured product, and effectively reducing the coefficient of linear thermal expansion of the cured product. Is preferable.

The average particle size of the inorganic filler is preferably 10 nm or more, more preferably 50 nm or more, further preferably 100 nm or more, preferably 5 μm or less, more preferably 3 μm or less, still more preferably 1 μm or less, and particularly preferably 0.5 μm. It is as follows. When the average particle size of the inorganic filler is not less than the above lower limit and not more than the above upper limit, the adhesive strength between the insulating layer and the metal layer is further increased.

As the average particle size of the inorganic filler, a value of median diameter (d50) of 50% is adopted. The average particle size can be measured using a laser diffraction / scattering type particle size distribution measuring device.

The inorganic filler is preferably spherical, more preferably spherical silica. In this case, the surface roughness of the surface of the insulating layer is effectively reduced, and the adhesive strength between the insulating layer and the metal layer is effectively increased. When the inorganic filler is spherical, the aspect ratio of the inorganic filler is preferably 2 or less, more preferably 1.5 or less.

The inorganic filler is preferably surface-treated, more preferably a surface-treated product with a coupling agent, and even more preferably a surface-treated product with a silane coupling agent. As a result, the surface roughness of the surface of the roughened and cured product is further reduced, the adhesive strength between the insulating layer and the metal layer is further increased, and finer wiring is formed on the surface of the cured product, and more. Even better inter-wiring insulation reliability and interlayer insulation reliability can be imparted to the cured product.

Examples of the coupling agent include a silane coupling agent, a titanium coupling agent, an aluminum coupling agent, and the like. Examples of the silane coupling agent include methacrylsilane, acrylicsilane, aminosilane, imidazolesilane, vinylsilane, and epoxysilane.

The content of the inorganic filler in 100% by weight of the component excluding the solvent in the resin material is preferably 30% by weight or more, more preferably 40% by weight or more, still more preferably 50% by weight or more, and particularly preferably 60% by weight. % Or more, most preferably 70% by weight or more. The content of the inorganic filler in 100% by weight of the component excluding the solvent in the resin material is preferably 90% by weight or less, more preferably 85% by weight or less, still more preferably 83% by weight or less, and particularly preferably 80% by weight. It is less than% by weight. When the content of the inorganic filler is not less than the above lower limit and not more than the above upper limit, the surface roughness of the surface of the cured product is further reduced, the adhesive strength between the insulating layer and the metal layer is further increased, and the cured product is cured. Finer wiring is formed by the surface of the object. Further, with this amount of the inorganic filler, it is possible to reduce the coefficient of thermal expansion of the cured product and at the same time to improve the smear removability. When the content of the inorganic filler is at least the above lower limit, the dielectric loss tangent is effectively lowered. Further, in the present invention, since the amount of resin existing in the vicinity of the inorganic filler increases as the surface area of the inorganic filler increases, it may be possible to further increase the hard components at room temperature and high temperature.

[Curing agent]
The resin material preferably contains a curing agent. The curing agent is not particularly limited. Conventionally known curing agents can be used as the curing agent. Only one kind of the above-mentioned curing agent may be used, or two or more kinds may be used in combination.

Examples of the curing agent include cyanate ester compound (cyanate ester curing agent), amine compound (amine curing agent), thiol compound (thiol curing agent), phosphine compound, dicyandiamide, phenol compound (phenol curing agent), acid anhydride, and activity. Examples thereof include an ester compound, a carbodiimide compound (carbodiimide curing agent), and a benzoxazine compound (benzoxazine curing agent). The curing agent preferably has a functional group capable of reacting with the epoxy group of the epoxy compound.

From the viewpoint of lowering the dielectric adjacency and increasing the thermal dimensional stability, the curing agent is at least one of a phenol compound, a cyanate ester compound, an acid anhydride, an active ester compound, a carbodiimide compound, and a benzoxazine compound. It preferably contains an ingredient. That is, the resin material preferably contains a curing agent containing at least one component of a phenol compound, a cyanate ester compound, an acid anhydride, an active ester compound, a carbodiimide compound, and a benzoxazine compound.

In the present specification, "at least one component of a phenol compound, a cyanate ester compound, an acid anhydride, an active ester compound, a carbodiimide compound, and a benzoxazine compound" may be referred to as "component X".

Therefore, the resin material preferably contains a curing agent containing the component X. The resin material more preferably contains a curing agent containing an active ester compound or a phenol compound, and further preferably contains a curing agent containing an active ester compound. The curing agent preferably contains the component X, more preferably contains an active ester compound or a phenol compound, and further preferably contains an active ester compound. As the component X, only one kind may be used, or two or more kinds may be used in combination.

Examples of the phenol compound include novolak-type phenol, biphenol-type phenol, naphthalene-type phenol, dicyclopentadiene-type phenol, aralkyl-type phenol, and dicyclopentadiene-type phenol.

Commercially available products of the above phenol compounds include novolak-type phenol (“TD-2091” manufactured by DIC), biphenyl novolac-type phenol (“MEH-7851” manufactured by Meiwakasei Co., Ltd.), and aralkyl-type phenol compound (“MEH” manufactured by Meiwakasei Co., Ltd.). -7800 "), and phenols having an aminotriazine skeleton ("LA1356" and "LA3018-50P" manufactured by DIC) and the like can be mentioned.

Examples of the cyanate ester compound include a novolak type cyanate ester resin, a bisphenol type cyanate ester resin, and a prepolymer in which these are partially triquantized. Examples of the novolak type cyanate ester resin include phenol novolac type cyanate ester resin and alkylphenol type cyanate ester resin. Examples of the bisphenol type cyanate ester resin include bisphenol A type cyanate ester resin, bisphenol E type cyanate ester resin, and tetramethyl bisphenol F type cyanate ester resin.

Commercially available products of the above cyanate ester compounds include a phenol novolac type cyanate ester resin (“PT-30” and “PT-60” manufactured by Lonza Japan Co., Ltd.) and a prepolymer in which a bisphenol type cyanate ester resin is triquantized (Lonza Japan). Examples thereof include "BA-230S", "BA-3000S", "BTP-1000S" and "BTP-6020S") manufactured by the same company.

Examples of the acid anhydride include tetrahydrophthalic anhydride, alkylstyrene-maleic anhydride copolymer and the like.

Examples of commercially available products of the acid anhydride include "Recasid TDA-100" manufactured by Shin Nihon Rika Co., Ltd.

The active ester compound refers to a compound containing at least one ester bond in the structure and having aromatic rings bonded to both sides of the ester bond. The active ester compound is obtained, for example, by a condensation reaction of a carboxylic acid compound or a thiocarboxylic acid compound with a hydroxy compound or a thiol compound. Examples of the active ester compound include a compound represented by the following formula (1).

In the above formula (1), X1 represents a group containing an aliphatic chain, a group containing an aliphatic ring or a group containing an aromatic ring, and X2 represents a group containing an aromatic ring. Preferred examples of the group containing an aromatic ring include a benzene ring which may have a substituent and a naphthalene ring which may have a substituent. Examples of the substituent include a hydrocarbon group. The hydrocarbon group has preferably 12 or less carbon atoms, more preferably 6 or less carbon atoms, and even more preferably 4 or less carbon atoms.

The combination of X1 and X2 includes a combination of a benzene ring which may have a substituent and a benzene ring which may have a substituent, a benzene ring which may have a substituent, and a substitution. Examples thereof include a combination with a naphthalene ring which may have a group. Further, examples of the combination of X1 and X2 include a combination of a naphthalene ring which may have a substituent and a naphthalene ring which may have a substituent.

The active ester compound is not particularly limited. From the viewpoint of further enhancing thermal dimensional stability and flame retardancy, the active ester compound is preferably an active ester compound having two or more aromatic skeletons. From the viewpoint of lowering the dielectric loss tangent and increasing the thermal dimensional stability, it is more preferable that the active ester compound has a naphthalene ring in the skeleton of the main chain.

Examples of commercially available products of the active ester compound include "HPC-8000-65T", "EXB9416-70BK", "EXB8100-65T", and "HPC-8150-60T" manufactured by DIC Corporation.

The carbodiimide compound is a compound having a structural unit represented by the following formula (2). In the following formula (2), the right end and the left end are binding sites for other groups. Only one kind of the above-mentioned carbodiimide compound may be used, or two or more kinds may be used in combination.

In the above formula (2), X is an alkylene group, a group in which a substituent is bonded to an alkylene group, a cycloalkylene group, a group in which a substituent is bonded to a cycloalkylene group, an arylene group, or a substituent bonded to an arylene group. It represents a group and p represents an integer of 1-5. When a plurality of X's exist, the plurality of X's may be the same or different.

In one preferred form, at least one X is an alkylene group, a group with a substituent attached to an alkylene group, a cycloalkylene group, or a group with a substituent attached to a cycloalkylene group.

Commercially available products of the above carbodiimide compounds include "carbodilite V-02B", "carbodilite V-03", "carbodilite V-04K", "carbodilite V-07", "carbodilite V-09", and "carbodilite" manufactured by Nisshinbo Chemical Co., Ltd. Examples thereof include "10M-SP" and "carbodilite 10M-SP (revised)", and "Stavaxol P", "Stavaxol P400" and "Hikazil 510" manufactured by Rheinchemy.

Examples of the benzoxazine compound include Pd-type benzoxazine and Fa-type benzoxazine.

Examples of commercially available products of the benzoxazine compound include "Pd type" manufactured by Shikoku Chemicals Corporation.

The content of the component X is preferably 70 parts by weight or more, more preferably 85 parts by weight or more, preferably 150 parts by weight or less, and more preferably 120 parts by weight or less with respect to 100 parts by weight of the epoxy compound. When the content of the component X is not less than the above lower limit and not more than the above upper limit, the curability is further improved, the thermal dimensional stability is further enhanced, and the volatilization of the residual unreacted component can be further suppressed.

The total content of the epoxy compound and the component X in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material is preferably 50% by weight or more, more preferably 60% by weight or more, preferably 60% by weight or more. It is 95% by weight or less, more preferably 90% by weight or less. When the total content of the epoxy compound and the component X is not less than the above lower limit and not more than the above upper limit, the curability is further improved and the thermal dimensional stability can be further improved.

[Curing accelerator]
The resin material preferably contains a curing accelerator. By using the above-mentioned curing accelerator, the curing rate becomes even faster. By rapidly curing the resin material, the crosslinked structure in the cured product becomes uniform, the number of unreacted functional groups decreases, and as a result, the crosslinked density increases. The curing accelerator is not particularly limited, and conventionally known curing accelerators can be used. Only one type of the curing accelerator may be used, or two or more types may be used in combination.

Examples of the curing accelerator include anionic curing accelerators such as imidazole compounds, cationic curing accelerators such as amine compounds, and curing accelerators other than anionic and cationic curing accelerators such as phosphorus compounds and organic metal compounds. , And radical curing accelerators such as peroxides.

Examples of the imidazole compound include 2-undecylimidazole, 2-heptadecylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-. 2-Methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-un Decylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimerite, 1-cyanoethyl-2-phenylimidazolium trimerite, 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'-methylimidazolyl- (1')]-ethyl-s -Triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-dihydroxymethylimidazole And so on.

Examples of the amine compound include diethylamine, triethylamine, diethylenetetramine, triethylenetetramine, 4,4-dimethylaminopyridine and the like.

Examples of the phosphorus compound include triphenylphosphine compounds.

Examples of the organic metal compound include zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, bisacetylacetonate cobalt (II) and trisacetylacetonate cobalt (III).

The content of the curing accelerator is not particularly limited. The content of the curing accelerator is preferably 0.01% by weight or more in 100% by weight of the component excluding the inorganic filler and the solvent in the resin material and in 100% by weight of the component excluding the inorganic filler in the cured product. , More preferably 0.05% by weight or more, preferably 5% by weight or less, and more preferably 3% by weight or less. When the content of the curing accelerator is not less than the above lower limit and not more than the above upper limit, the resin material is efficiently cured. When the content of the curing accelerator is in a more preferable range, the storage stability of the resin material is further increased, and a more favorable cured product can be obtained.

[Thermoplastic resin]
The resin material preferably contains a thermoplastic resin. Examples of the thermoplastic resin include polyvinyl acetal resin, polyimide resin, and phenoxy resin. Only one type of the above-mentioned thermoplastic resin may be used, or two or more types may be used in combination.

The thermoplastic resin is preferably a phenoxy resin from the viewpoint of effectively lowering the dielectric loss tangent and effectively improving the adhesion of the metal wiring regardless of the curing environment. By using the phenoxy resin, deterioration of embedding property in holes or irregularities of the circuit board of the resin film and non-uniformity of the inorganic filler can be suppressed. Further, by using the phenoxy resin, the melt viscosity can be adjusted, so that the dispersibility of the inorganic filler is improved, and the resin material or the B-staged product is less likely to wet and spread in an unintended region during the curing process.

The phenoxy resin contained in the resin material is not particularly limited. As the phenoxy resin, a conventionally known phenoxy resin can be used. Only one type of the phenoxy resin may be used, or two or more types may be used in combination.

Examples of the phenoxy resin include phenoxy resins having skeletons such as bisphenol A type skeleton, bisphenol F type skeleton, bisphenol S type skeleton, biphenyl skeleton, novolak skeleton, naphthalene skeleton and imide skeleton.

Examples of commercially available phenoxy resins include "YP50", "YP55" and "YP70" manufactured by Nippon Steel & Sumitomo Metal Corporation, and "1256B40", "4250", "4256H40" and "4256H40" manufactured by Mitsubishi Chemical Corporation. 4275 ”,“ YX6954BH30 ”,“ YX8100BH30 ”and the like.

From the viewpoint of obtaining a resin material having more excellent storage stability, the weight average molecular weight of the thermoplastic resin is preferably 5,000 or more, more preferably 10,000 or more, preferably 100,000 or less, and more preferably 50,000 or less.

The weight average molecular weight of the thermoplastic resin indicates the polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

The contents of the thermoplastic resin and the phenoxy resin are not particularly limited. The content of the thermoplastic resin (content of the phenoxy resin when the thermoplastic resin is a phenoxy resin) is preferably 1% by weight or more in 100% by weight of the components excluding the inorganic filler in the resin material. It is more preferably 5% by weight or more, preferably 30% by weight or less, and more preferably 15% by weight or less. When the content of the thermoplastic resin is at least the above lower limit and at least the above upper limit, the embedding property of the resin material in the holes or irregularities of the circuit board is improved. When the content of the thermoplastic resin is at least the above lower limit, the formation of the resin film becomes easier and a better insulating layer can be obtained. When the content of the thermoplastic resin is not more than the above upper limit, the coefficient of thermal expansion of the cured product becomes even lower. When the content of the thermoplastic resin is not more than the above upper limit, the surface roughness of the surface of the cured product is further reduced, and the adhesive strength between the insulating layer and the metal layer is further increased.

[solvent]
The resin material does not contain or contains a solvent. By using the above solvent, the viscosity of the resin material can be controlled in a suitable range, and the coatability of the resin material can be improved. Further, the solvent may be used to obtain a slurry containing the inorganic filler. Only one type of the solvent may be used, or two or more types may be used in combination.

Examples of the solvent include acetone, methanol, ethanol, butanol, 2-propanol, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 2-acetoxy-1-methoxypropane, toluene, xylene, methyl ethyl ketone, and the like. Examples thereof include N, N-dimethylformamide, methyl isobutyl ketone, N-methyl-pyrrolidone, n-hexane, cyclohexane, cyclohexanone and naphtha as a mixture.

Most of the solvent is preferably removed when the resin composition is formed into a film. Therefore, the boiling point of the solvent is preferably 200 ° C. or lower, more preferably 180 ° C. or lower. The content of the solvent in the resin composition is not particularly limited. The content of the solvent can be appropriately changed in consideration of the coatability of the resin composition and the like.

[Other ingredients]
For the purpose of improving impact resistance, heat resistance, resin compatibility, workability, etc., the above resin materials include leveling agents, flame retardants, coupling agents, colorants, antioxidants, ultraviolet deterioration inhibitors, and defoamers. Foaming agents, thickeners, rocking denaturing agents and the like may be added.

Examples of the coupling agent include a silane coupling agent, a titanium coupling agent, an aluminum coupling agent, and the like. Examples of the silane coupling agent include vinylsilane, aminosilane, imidazolesilane, and epoxysilane.

(Resin film and laminated film)
A resin film (B-staged product / B-stage film) can be obtained by molding the above-mentioned resin material into a film. The resin material is preferably a resin film. The resin film is preferably a B stage film. By curing the resin film, a film-like cured product can be obtained. The cured product is preferably in the form of a film.

Examples of the method for obtaining a resin film by molding the resin composition into a film form include the following methods. An extrusion molding method in which a resin composition is melt-kneaded using an extruder, extruded, and then molded into a film by a T-die, a circular die, or the like. A casting molding method in which a resin composition containing a solvent is cast and molded into a film. Other conventionally known film forming methods. An extrusion molding method or a casting molding method is preferable because it can be made thinner. The film includes a sheet.

A resin film, which is a B-stage film, can be obtained by molding the resin composition into a film and heating and drying it at 50 ° C. to 150 ° C. for 1 minute to 10 minutes to the extent that curing by heat does not proceed too much. can.

The film-like resin material that can be obtained by the drying step as described above is referred to as a B stage film. The B stage film is in a semi-cured state. The semi-cured product is not completely cured and can be further cured.

The resin film does not have to be a prepreg. When the resin film is not a prepreg, migration does not occur along the glass cloth or the like. Further, when the resin film is laminated or pre-cured, unevenness due to the glass cloth does not occur on the surface. The resin film can be used in the form of a laminated film including a metal foil or a base material and a resin film laminated on the surface of the metal foil or the base material. The metal foil is preferably a copper foil.

The laminated film has a base film and the resin film laminated on the first surface of the base film. A protective film may be laminated on the surface of the resin film opposite to the base film.

Examples of the base film of the laminated film include polyester resin films such as polyethylene terephthalate film and polybutylene terephthalate film, olefin resin films such as polyethylene film and polypropylene film, and polyimide resin films. The surface of the base material may be subjected to a mold release treatment, if necessary.

From the viewpoint of controlling the degree of curing of the resin film more uniformly, the thickness of the resin film is preferably 5 μm or more, preferably 200 μm or less. When the resin film is used as the insulating layer of the circuit, the thickness of the insulating layer formed by the resin film is preferably equal to or larger than the thickness of the conductor layer (metal layer) forming the circuit. The thickness of the insulating layer is preferably 5 μm or more, and preferably 200 μm or less.

(Semiconductor devices, printed wiring boards, copper-clad laminates and multilayer printed wiring boards)
The cured product and the B stage film are used as an insulating material. The cured product and the B stage film are suitably used as an insulating material in electronic components such as semiconductor devices, laminated boards and printed wiring boards.

The resin material, the B stage film, and the cured product are suitably used for forming an insulating layer in a printed wiring board.

The printed wiring board can be obtained, for example, by heat-press molding the resin material.

A metal foil can be laminated on one side or both sides of the resin film. The method of laminating the resin film and the metal foil is not particularly limited, and a known method can be used. For example, the resin film can be laminated on a metal foil while being pressurized or not heated by using an apparatus such as a parallel flat plate press or a roll laminator.

The resin material, the B stage film, and the cured product are suitably used for obtaining a copper-clad laminate. An example of the copper-clad laminate is a copper-clad laminate comprising a copper foil and a resin film laminated on one surface of the copper foil.

The thickness of the copper foil of the copper-clad laminate is not particularly limited. The thickness of the copper foil is preferably in the range of 1 μm to 50 μm. Further, in order to increase the adhesive strength between the cured product of the resin material and the copper foil, it is preferable that the copper foil has fine irregularities on the surface. The method of forming the unevenness is not particularly limited. Examples of the method for forming the unevenness include a method for forming the unevenness by a treatment using a known chemical solution.

The resin material, the B stage film, and the cured product are suitably used for obtaining a multilayer substrate.

An example of the multilayer board is a multilayer board including a circuit board and an insulating layer laminated on the circuit board. The material of the insulating layer of this multilayer substrate is the cured product described above. Further, the insulating layer of the multilayer substrate may be formed of the resin film of the laminated film by using the laminated film. The insulating layer is preferably laminated on the surface of the circuit board on which the circuit is provided. It is preferable that a part of the insulating layer is embedded between the circuits.

In the multilayer board, it is preferable that the surface of the insulating layer opposite to the surface on which the circuit board is laminated is roughened.

As the roughening treatment method, a conventionally known roughening treatment method can be used and is not particularly limited. The surface of the insulating layer may be swelled before the roughening treatment.

Further, it is preferable that the multilayer substrate further includes a copper plating layer laminated on the roughened surface of the insulating layer.

Further, as another example of the multilayer board, the circuit board, the insulating layer laminated on the surface of the circuit board, and the insulating layer are laminated on the surface opposite to the surface on which the circuit board is laminated. Examples thereof include a multilayer substrate provided with a copper foil. The material of the insulating layer of this multilayer substrate is the cured product described above. It is preferable that the insulating layer is formed by curing the resin film using a copper-clad laminate having a copper foil and a resin film laminated on one surface of the copper foil. Further, the copper foil is etched and preferably a copper circuit.

As another example of the multilayer board, there is a multilayer board including a circuit board and a plurality of insulating layers laminated on the surface of the circuit board. At least one of the plurality of insulating layers arranged on the circuit board is formed by using the resin material. The material of the insulating layer of this multilayer substrate is the cured product described above. It is preferable that the multilayer substrate further includes a circuit laminated on at least one surface of the insulating layer formed by using the resin film.

The resin material, the B stage film, and the cured product are suitably used for forming an insulating layer in a multilayer printed wiring board.

The multilayer printed wiring board includes, for example, a circuit board, a plurality of insulating layers arranged on the surface of the circuit board, and a metal layer arranged between the plurality of insulating layers. The material of at least one of the insulating layers is the cured product described above.

FIG. 1 is a cross-sectional view schematically showing a multilayer printed wiring board using a cured product according to an embodiment of the present invention.

In the multilayer printed wiring board 11 shown in FIG. 1, a plurality of insulating layers 13 to 16 are laminated on the upper surface 12a of the circuit board 12. The insulating layers 13 to 16 are cured product layers. A metal layer 17 is formed in a part of the upper surface 12a of the circuit board 12. Of the plurality of insulating layers 13 to 16, metal layers 17 are formed in a part of the upper surface of the insulating layers 13 to 15 other than the insulating layer 16 located on the outer surface opposite to the circuit board 12 side. Has been done. The metal layer 17 is a circuit. A metal layer 17 is arranged between the circuit board 12 and the insulating layer 13 and between the layers of the laminated insulating layers 13 to 16, respectively. The lower metal layer 17 and the upper metal layer 17 are connected to each other by at least one of a via hole connection and a through hole connection (not shown).

In the multilayer printed wiring board 11, the insulating layers 13 to 16 are formed of the cured product. In the multilayer printed wiring board 11, the material of the insulating layers 13 to 16 is the cured product. In the present embodiment, since the surfaces of the insulating layers 13 to 16 are roughened, fine holes (not shown) are formed on the surfaces of the insulating layers 13 to 16. Further, the metal layer 17 reaches the inside of the fine pores. Further, in the multilayer printed wiring board 11, the width direction dimension (L) of the metal layer 17 and the width direction dimension (S) of the portion where the metal layer 17 is not formed can be reduced. Further, in the multilayer printed wiring board 11, good insulation reliability is imparted between the upper metal layer and the lower metal layer which are not connected by via hole connection and through hole connection (not shown).

(Roughening treatment and swelling treatment)
The resin material is preferably used to obtain a cured product to be roughened or desmeared. The cured product also includes a pre-cured product that can be further cured. From the viewpoint of easily forming the sea-island structure, the cured product is preferably a pre-cured product that can be further cured. Further, in order to obtain the pre-cured product, the curing temperature when curing the resin material is preferably 120 ° C. or higher and 180 ° C. or lower.

In order to form fine irregularities on the surface of the cured product obtained by pre-curing the resin material, the cured product is preferably roughened. Prior to the roughening treatment, the cured product is preferably swelled. It is preferable that the cured product is swelled and further cured after the roughening treatment after the pre-curing and before the roughening treatment. However, the cured product does not necessarily have to be swelled.

As the method of the swelling treatment, for example, a method of treating the cured product with an aqueous solution of a compound containing ethylene glycol or the like as a main component, an organic solvent dispersion solution, or the like is used. The swelling liquid used for the swelling treatment generally contains an alkali as a pH adjuster or the like. The swelling liquid preferably contains sodium hydroxide. Specifically, for example, the swelling treatment is carried out by treating the cured product at a treatment temperature of 30 ° C. to 85 ° C. for 1 minute to 30 minutes using a 40 wt% ethylene glycol aqueous solution or the like. The temperature of the swelling treatment is preferably in the range of 50 ° C. to 85 ° C. If the temperature of the swelling treatment is too low, the swelling treatment takes a long time, and the adhesive strength between the cured product and the metal layer tends to be low.

For the roughening treatment, for example, a chemical oxidizing agent such as a manganese compound, a chromium compound or a persulfate compound is used. These chemical oxidizing agents are used as an aqueous solution or an organic solvent dispersion solution after water or an organic solvent is added. The roughening liquid used for the roughening treatment generally contains an alkali as a pH adjuster or the like. The roughening liquid preferably contains sodium hydroxide.

Examples of the manganese compound include potassium permanganate and sodium permanganate. Examples of the chromium compound include potassium dichromate and anhydrous potassium chromate. Examples of the persulfate compound include sodium persulfate, potassium persulfate, ammonium persulfate and the like.

The arithmetic mean roughness Ra of the surface of the cured product is preferably 10 nm or more, preferably less than 300 nm, more preferably less than 200 nm, and further preferably less than 150 nm. In this case, the adhesive strength between the insulating layer and the metal layer is increased, and the surface of the insulating layer forms finer wiring. Further, the conductor loss can be suppressed, and the signal loss can be suppressed low. The arithmetic mean roughness Ra is measured according to JIS B0601: 1994.

(Desmia processing)
Through holes may be formed in the cured product obtained by pre-curing the resin material. Vias, through holes, and the like are formed as through holes in the multilayer substrate and the like. For example, vias can be formed by irradiation with a laser such as _{a CO 2 laser.} The diameter of the via is not particularly limited, but is about 60 μm to 80 μm. Due to the formation of the through holes, smear, which is a residue of the resin derived from the resin component contained in the cured product, is often formed at the bottom of the via.

In order to remove the smear, the surface of the cured product is preferably desmear-treated. The desmear treatment may also serve as the roughening treatment.

In the desmear treatment, for example, a chemical oxidizing agent such as a manganese compound, a chromium compound or a persulfate compound is used in the same manner as in the roughening treatment. These chemical oxidizing agents are used as an aqueous solution or an organic solvent dispersion solution after water or an organic solvent is added. The desmear treatment liquid used for the desmear treatment generally contains an alkali. The desmear treatment liquid preferably contains sodium hydroxide.

By using the above resin material, the surface roughness of the surface of the desmear-treated insulating layer is sufficiently reduced.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited to the following examples. The content of each component shown in the table is the part by weight of the solid content excluding the solvent.

The following materials were prepared.

(Thermosetting compound)
Epoxy compound:
Biphenyl type epoxy compound ("NC-3000" manufactured by Nippon Kayaku Co., Ltd.)
Naphthol aralkyl type epoxy compound ("TX-1507B" manufactured by Nippon Steel & Sumitomo Metal Corporation) Resorcinol diglycidyl ester ("EX-201" manufactured by Nagase ChemteX Corporation)
Dicyclopentadiene type epoxy compound ("EP4088S" manufactured by ADEKA CORPORATION)

Maleimide compound:
N-alkylbismaleimide compound 1 (“BMI-3000” manufactured by Designer Moleculars Inc.)
N-alkylbismaleimide compound 2 (“BMI-1500” manufactured by Designer Moleculars Inc.)

(Inorganic filler)
Silica filler ("C4" manufactured by Admatex, powder, average particle size 1.0 μm, aminosilane treatment)
Silica-containing slurry (silica 75% by weight: "SC4050-HOA" manufactured by Admatex, average particle size 1.0 μm, aminosilane treatment, cyclohexanone 25% by weight)

(Hardener)
Ingredient X:
Phenol compound-containing liquid ("LA-1356" manufactured by DIC Corporation, solid content 60% by weight)
Liquid containing 1 active ester compound ("EXB-8" manufactured by DIC Corporation, solid content 100% by weight)
Active ester compound 2 containing liquid ("HPC8150-62T" manufactured by DIC Corporation, solid content 62% by weight)

(Curing accelerator)
Dimethylaminopyridine ("DMAP" manufactured by Wako Pure Chemical Industries, Ltd.)
2-Phenyl-4-methylimidazole ("2P4MZ" manufactured by Shikoku Chemicals Corporation, anionic curing accelerator)

(Thermoplastic resin)
Phenoxy resin ("YX6954BH30" manufactured by Mitsubishi Chemical Corporation)
Polyimide compound (polyimide resin):
A polyimide compound-containing solution (nonvolatile content 26.8% by weight), which is a reaction product of tetracarboxylic dianhydride and dimerdiamine, was synthesized according to the following Synthesis Example 1.

(Synthesis Example 1)
300.0 g of tetracarboxylic acid dianhydride (“BizDA-1000” manufactured by SABIC Japan LLC) and 665.5 g of cyclohexanone were placed in a reaction vessel equipped with a stirrer, a water divider, a thermometer and a nitrogen gas introduction tube. And the solution in the reaction vessel was heated to 60 ° C. Next, 89.0 g of dimer diamine (“PRIAMINE 1075” manufactured by Croda Japan) and 54.7 g of 1,3-bisaminomethylcyclohexane (manufactured by Mitsubishi Gas Chemical Company) were added dropwise to the reaction vessel. Next, 121.0 g of methylcyclohexane and 423.5 g of ethylene glycol dimethyl ether were added to the reaction vessel, and an imidization reaction was carried out at 140 ° C. for 10 hours. In this way, a polyimide compound-containing solution (nonvolatile content 26.8% by weight) was obtained. The molecular weight (weight average molecular weight) of the obtained polyimide compound was 20000. The molar ratio of the acid component / amine component was 1.04.

The molecular weight of the polyimide compound synthesized in Synthesis Example 1 was determined as follows.

GPC (Gel Permeation Chromatography) Measurement:
A high performance liquid chromatograph system manufactured by Shimadzu Corporation was used, and measurement was carried out using tetrahydrofuran (THF) as a developing medium at a column temperature of 40 ° C. and a flow velocity of 1.0 ml / min. "SPD-10A" was used as a detector, and two columns of "KF-804L" (exclusion limit molecular weight: 400,000) manufactured by Shodex were connected in series. "TSK standard polystyrene" manufactured by Tosoh Corporation is used as the standard polystyrene, and the weight average molecular weight Mw = 354,000, 189,000, 98,900, 37,200, 17,100, 9,830, 5,870, 2, Calibration curves were made using 500, 1,050, and 500 materials and the molecular weight was calculated.

(solvent)
Methyl ethyl ketone Anisole Cyclohexanone naphtha ("T-sol 150" manufactured by JXTG Energy Co., Ltd.)

(Example 1)
Preparation of resin film:
Of the components shown in Table 1 below, the components excluding the N-alkylbismaleimide compound 1 (“BMI-3000” manufactured by Designer Moleculars Inc.) are blended in the amounts shown in Table 1 below (units are solids excluding solvents). By weight, the solvent was mixed by weight of the solvent), and the mixture was stirred at room temperature until a uniform solution was obtained. Next, N-alkylbismaleimide compound 1 was added to this solution and stirred to obtain a resin material.

After applying the obtained resin material on the release-treated surface of the release-treated PET film (Toray Industries, Inc. "XG284", thickness 25 μm) using an applicator, the temperature is 75 ° C to 100 ° C in a gear oven. The temperature was raised to 5 ° C. per minute to volatilize the solvent. In this way, a laminated film (laminated film of PET film and resin film) in which a resin film (B stage film) having a thickness of 40 μm is laminated on the PET film was obtained.

(Example 2)
Preparation of resin film:
Of the components shown in Table 1 below, resorcinol diglycidyl ester (“EX-201” manufactured by Nagase ChemteX Corporation) and silica filler are placed in a bottle, stirred with Awatori Rentaro for 15 minutes, and then at 25 ° C. for 24 hours. It was cured. Next, cyclohexanone was added to the bottle and stirred, and then the remaining components were added and stirred to obtain a resin material.

After applying the obtained resin material on the release-treated surface of the release-treated PET film (Toray Industries, Inc. "XG284", thickness 25 μm) using an applicator, it is placed in a gear oven at 100 ° C. for 2 minutes. The solvent was volatilized by heating for 30 seconds. In this way, a laminated film (laminated film of PET film and resin film) in which a resin film (B stage film) having a thickness of 40 μm is laminated on the PET film was obtained.

(Example 3)
A laminated film was produced in the same manner as in Example 2 except that the components shown in Table 1 below were blended in the blending amount (unit: parts by weight of solid content) shown in Table 1 below.

(Comparative Example 1)
A laminated film was produced in the same manner as in Example 2 except that the components shown in Table 1 below were blended in the blending amount (unit: parts by weight of solid content) shown in Table 1 below.

Using the laminated films obtained in Examples 1 to 3 and Comparative Example 1, a cured product and an evaluation substrate were prepared as follows.

<Preparation of cured product>
The obtained laminated film was pre-cured by heating at 130 ° C. for 30 minutes and then at 170 ° C. for 30 minutes, and then heated at 200 ° C. for 1 hour to prepare a cured resin film.

<Preparation of evaluation board>
An evaluation board (an evaluation board including a copper-clad laminate and a six-layer insulation-wiring circuit composite layer) was produced according to the following. In the evaluation substrate, the via holes formed in each layer are continuous. That is, the evaluation board is an evaluation board having a multi-stage stack via.

Formation of first layer of insulation-wiring circuit composite layer:
(A1) Laminating process:
A double-sided copper-clad laminate (CCL substrate) (copper foil thickness of 18 μm on each surface, substrate thickness of 0.7 mm, substrate size of 100 mm × 100 mm, “MCL-E679FG” manufactured by Hitachi Kasei Co., Ltd.) was prepared. Both sides of the copper foil surface of this double-sided copper-clad laminate were immersed in "Cz8101" manufactured by MEC to roughen the surface of the copper foil. The resin film (B stage film) side of the laminated film is copper-clad laminated on both sides of the roughened copper-clad laminate using "Batch type vacuum laminator MVLP-500 / 600-IIA" manufactured by Meiki Co., Ltd. It was laminated on a board. The laminating conditions were such that the pressure was reduced for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then the pressure was pressed at 100 ° C. and a pressure of 0.4 MPa for 30 seconds. After peeling off the PET film, the resin film was semi-cured (pre-cured) by heating at 130 ° C. for 60 minutes. In this way, a laminated body (1) in which a semi-cured product of a resin film was laminated on a CCL substrate was obtained.

(B1) Via hole forming step:
Using a CO ₂ laser machine (“LC-4KF212” manufactured by Via Mechanics, Ltd.), a via hole having a diameter of about 60 μm was formed under the conditions of burst mode, energy of 0.4 mJ, pulse of 27 μsec, and 3 shots.

(C1) Desmear treatment and roughening treatment:
(C1-1) Swelling treatment:
The obtained laminate (1) was placed in a swelling solution at 60 ° C. (“Swelling Dip Securigant P” manufactured by Atotech Japan Co., Ltd.) and shaken for 10 minutes. Then, it was washed with pure water.

(C1-2) Permanganate treatment (roughening treatment and desmear treatment):
The swelling-treated laminate (1) was placed in a crude aqueous solution of potassium permanganate (“Concentrate Compact CP” manufactured by Atotech Japan) at 80 ° C. and shaken for 30 minutes. Next, the mixture was treated with a cleaning solution at 25 ° C. (“Reduction Securigant P” manufactured by Atotech Japan Co., Ltd.) for 2 minutes and then washed with pure water to obtain a laminated body (1) after roughening treatment.

(C1-3) Measurement of surface roughness:
The surface of the laminated body (1) (roughened cured product) after the roughening treatment was 95.6 μm × using a non-contact three-dimensional surface shape measuring device (“Contour GT-K” manufactured by Bruker). The arithmetic mean roughness Ra was measured in a measurement area of 71.7 μm. The arithmetic mean roughness Ra was measured in accordance with JIS B0601: 1994. It was confirmed that the surface roughness of the surface of the roughened cured product was 200 nm or less.

(D1) Electroless plating treatment:
The surface of the cured product of the laminated body (1) after the roughening treatment was treated with an alkaline cleaner at 60 ° C. (“Cleaner Securigant 902” manufactured by Atotech Japan Co., Ltd.) for 5 minutes, and degreased and washed. After washing, the cured product was treated with a predip solution (“Predip Neogant B” manufactured by Atotech Japan) at 25 ° C. for 2 minutes. Then, the cured product was treated with an activator solution at 40 ° C. (“Activator Neogant 834” manufactured by Atotech Japan Co., Ltd.) for 5 minutes, and a palladium catalyst was attached. Next, the cured product was treated with a reducing solution at 30 ° C. (“Reducer Neogant WA” manufactured by Atotech Japan) for 5 minutes.

Next, the cured product was placed in a chemical copper solution (Atotech Japan's "Basic Print Gantt MSK-DK", "Copper Print Gantt MSK", "Stabilizer Print Gantt MSK", and "Reducer Cu") and electroless plated. Was carried out until the plating thickness became about 0.5 μm. After electroless plating, annealing treatment was performed at a temperature of 120 ° C. for 30 minutes in order to remove residual hydrogen gas. All the steps up to the electroless plating step were carried out with a beaker scale containing 2 L of the treatment liquid and shaking the cured product.

(E1) Resist formation:
A dry film resist (“RY5125” manufactured by Hitachi Kasei Co., Ltd.) was attached using a hot roll laminator. The laminating conditions were a temperature of 100 ° C., a pressure of 0.4 MPa, and a laminating speed of 1.5 m / min, and then held for 15 minutes. Then, after exposure at 85 mJ / cm ² , a 1 wt% sodium carbonate aqueous solution was spray-treated at 27 ° C. at a spray pressure of 1.2 MPa for 30 seconds for development.

(F1) Electroplating treatment:
Next, the cured product subjected to the electroless plating treatment was subjected to electrolytic plating until the plating thickness became 25 μm. Copper sulfate solution for electrolytic copper plating ("Copper sulfate pentahydrate" manufactured by Wako Pure Chemical Industries, Ltd., "Sulfate" manufactured by Wako Pure Chemical Industries, Ltd., "Basic leveler capallaside HL" manufactured by Atotech Japan, "Basic leveler capallaside HL" manufactured by Atotech Japan. Using the corrective agent Capalacid GS ”), ^{electrolytic plating was carried out by passing a current of 0.6 A / cm 2} until the plating thickness became about 25 μm.

(G1) DFR peeling and etching treatment:
The dry film resist (DFR) was peeled off by spray treatment with a 3 wt% sodium hydroxide aqueous solution. Next, quick etching was performed with a hydrogen peroxide-based acidic etching solution (“SAC process” manufactured by JCU).

(H1) Main curing step:
It was heated at 190 ° C. for 1.5 hours with respect to the peak temperature T.

In this way, the first insulating-wiring circuit composite layer was formed on the copper-clad laminate.

Formation of second insulation-wiring circuit composite layer:
(A2) Laminating process:
(A1) The roughening treatment of the first wiring circuit layer was performed in the same manner as the roughening treatment conditions carried out in the laminating step. Then, the resin film (B stage film) side of the laminated film was laminated on the first layer of the insulating-wiring circuit composite layer under the laminating conditions carried out in the laminating step (a1). Then, after peeling off the PET film, the resin film was semi-cured by heating at 130 ° C. for 60 minutes. In this way, a laminate (2) in which a semi-cured resin film was laminated on the first layer of the insulation-wiring circuit composite layer was obtained.

(B2) Via hole forming step:
(B1) A via hole was formed in the same manner as in the step carried out in the via hole forming step, except that the laminated body (1) was changed to the laminated body (2).

(C2) Desmear treatment and roughening treatment:
(C1) The steps carried out in the desmear treatment and the roughening treatment were carried out in the same manner except that the laminated body (1) was changed to the laminated body (2), and the laminated body (2) after the roughening treatment was obtained.

(D2) Electroless plating treatment:
(D1) The electroless plating treatment was performed in the same manner except that the step performed in the electroless plating treatment was changed from the laminated body (1) after the roughening treatment to the laminated body (2) after the roughening treatment. rice field.

(F2) Electroplating treatment:
After the (d2) electroless plating treatment, the electroless plating treatment was performed in the same manner as in the (f1) electrolytic plating treatment.

(H2) Main curing step:
(H1) In the same manner as in the main curing step, the mixture was heated at 190 ° C. for 1.5 hours.

In this way, the second layer of the insulation-wiring circuit composite layer was formed on the first layer of the insulation-wiring circuit composite layer.

Formation of third insulation-wiring circuit composite layer:
A third layer of insulation-wiring circuit composite layer was formed on the second layer of insulation-wiring circuit composite layer in the same manner as in the process performed in the formation of the second layer of insulation-wiring circuit composite layer.

Formation of 4th insulation-wiring circuit composite layer:
A fourth layer of insulation-wiring circuit composite layer was formed on the third layer of insulation-wiring circuit composite layer in the same manner as in the process performed in the formation of the second layer of insulation-wiring circuit composite layer.

Formation of 5th insulation-wiring circuit composite layer:
(A5) Laminating process:
(A2) In the same manner as in the step carried out in the laminating step, a laminated body (5) in which a semi-cured product of the resin film was laminated on the fourth layer of the insulating-wiring circuit composite layer was obtained.

(B5) Via hole forming step:
(B1) A via hole was formed in the same manner as in the step carried out in the via hole forming step, except that the laminated body (1) was changed to the laminated body (5).

(C5) Desmear treatment and roughening treatment:
(C1) The steps carried out in the desmear treatment and the roughening treatment were carried out in the same manner except that the laminated body (1) was changed to the laminated body (5), and the laminated body (5) after the roughening treatment was obtained.

(D5) Electroless plating treatment:
(D1) The electroless plating treatment was performed in the same manner except that the step performed in the electroless plating treatment was changed from the laminated body (1) after the roughening treatment to the laminated body (5) after the roughening treatment. rice field.

(E5) Resist formation:
(E1) Development was carried out in the same manner as in the process carried out in resist formation.

(F5) Electroplating:
After the pattern of the dry film resist was formed, the electroless plating treatment was performed in the same manner as in the (f1) electrolytic plating treatment.

(G5) DFR peeling and etching treatment:
(G1) The DFR peeling and etching treatments were carried out in the same manner as in the steps carried out in the DFR peeling and etching treatments.

(H5) Main curing step:
(H1) In the same manner as in the main curing step, the mixture was heated at 190 ° C. for 1.5 hours.

In this way, the fifth layer of the insulation-wiring circuit composite layer was formed on the fourth layer of the insulation-wiring circuit composite layer.

Formation of 6th insulation-wiring circuit composite layer:
A sixth layer of insulation-wiring circuit composite layer was formed on the fifth layer of insulation-wiring circuit composite layer in the same manner as in the process performed in the formation of the second layer of insulation-wiring circuit composite layer.

In this way, an evaluation substrate in which the first to sixth layers of the insulation-wiring circuit composite layer were formed on the copper-clad laminate was produced. In the obtained evaluation substrate, among the wiring circuit layers of the first to sixth layers, only the first and fifth wiring circuit layers have a pattern.

(evaluation)
(1) Measurement by Pulse NMR The obtained cured product was cut into a length of 2 cm and introduced into a glass sample tube (manufactured by Bruker, product number 1824511, length 180 mm, flat bottom) having a diameter of 10 mm. The sample tube was installed in a pulse NMR device (“the minispec mq20” manufactured by BRUKER), and 30 ° C. (10 minutes holding), 70 ° C. (10 minutes holding), 100 ° C. (10 minutes holding), 150 ° C. (10 minutes holding). ), 170 ° C. (held for 10 minutes) and the temperature was raised stepwise.

In 30 ° C. and 170 ° C., was measured in Solid Echo under the following ^conditions, the spin of ¹ H - to give the free induction decay curve of spin relaxation.

<Solid Echo method>
Scans: 128times
Recycle Delay: 1sec
Acquisition scale: 1.0ms

The obtained ^{1 H} spin - the free induction decay curve of spin relaxation, and waveform separation into three curves derived from hard components, middle components, the three components of the soft component. Waveform separation was performed by fitting using both Gaussian type and exponential type. The ratio of each component was determined from the curves derived from the three components obtained in each measurement.

Using the analysis software "TD-NMRA (Version 4.3 Rev 0.8)" manufactured by BRUKER, the hard component is Gaussian type and the middle component and soft component are exponential type according to the product manual. rice field. In the analysis, fitting was performed using points up to 0.6 msec of the relaxation curve, and the amount of each component and the relaxation time were obtained.

The fitting was performed using the following formula (X).

Y = A1 * exp (-1 / w1 * (t / T2A) ^ w1) + B1 * exp (-1 / w2 * (t / T2B) ^ w2) + C1 * exp (-1 / w3 * (t / T2C)) ^ W3) ・ ・ ・ Equation (X)

In the above formula (X), w1, w2, and w3 are Weibull coefficients, w1 is 2, and w2 and w3 are 1. In the above formula (X), A1 is the content of the hard component, B1 is the content of the middle component, C1 is the content of the soft component, T2A is the relaxation time of the hard component, and T2B is the middle component. It is the relaxation time of the component, and T2C is the relaxation time of the soft component. In the above formula (X), t is time.

The following was determined by performing the above pulse NMR measurement and the above analysis using the obtained cured product.

The content of the hard component at 30 ° C (%) in the total of 100% of the content of the hard component at 30 ° C, the content of the middle component at 30 ° C, and the content of the soft component at 30 ° C.
The content of the hard component at 170 ° C (%) in the total of 100% of the content of the hard component at 170 ° C, the content of the middle component at 170 ° C, and the content of the soft component at 170 ° C.
Hard component spin-spin relaxation time at 30 ° C (milliseconds)
Spin-spin relaxation time of hard components at 170 ° C (milliseconds)
Ratio (hard component spin-spin relaxation time at 170 ° C / hard component spin-spin relaxation time at 30 ° C)

(2) Dropping of Inorganic Filler During Via Hole Formation In the via hole forming step in "Preparation of Evaluation Substrate", the dropout of the inorganic filler during via hole formation was evaluated according to the following criteria.

[Criteria for dropping inorganic filler during via hole formation]
○ ○: The number of inorganic fillers at the bottom of the via is 3 or less ○: The number of inorganic fillers at the bottom of the via is 4 or more and 10 or less ×: The number of inorganic fillers at the bottom of the via exceeds 10

(3) Side lobe The area around the via hole of the obtained evaluation substrate was observed with a scanning electron microscope (SEM), and the length of the side lobe around the via hole was measured.

[Criteria for side lobes]
○ ○: Maximum side lobe length is less than 15 μm ○: Maximum side lobe length is 15 μm or more and less than 30 μm ×: Maximum side lobe length is 30 μm or more

(4) Cracks or cracks in the insulating layer The obtained evaluation substrate was subjected to a liquid tank thermal shock test (cold heat cycle test) under the following two conditions.

Test condition 1: -55 ° C to 125 ° C, 5 minutes each, 1000 cycles Test condition 2: -65 ° C to 150 ° C, 5 minutes each, 1000 cycles

The insulating layer around the via hole was observed using a scanning electron microscope (SEM) on the evaluation substrate subjected to the liquid tank thermal shock test. In addition, the insulating layer and the wiring circuit layer in the region other than the area around the via hole were also observed.

[Criteria for cracks or cracks in the insulating layer (around the via hole)]
◯: No cracks or cracks in the insulating layer around the via hole ×: Cracks or cracks in the insulating layer around the via hole

[Criteria for determining cracks or cracks in the insulating layer (other than around the via hole)]
◯: No cracks or cracks occur in the insulating layer in the area other than the area around the via hole ×: Cracks or cracks occur in the insulating layer in the area other than the area around the via hole

In addition, no cracks or cracks in the wiring circuit layer were observed in the evaluation substrate obtained in the examples.

The composition and results are shown in Table 1 below.

11 ... Multi-layer printed wiring board 12 ... Circuit board 12a ... Top surface 13-16 ... Insulation layer 17 ... Metal layer

Claims (10)

It is a cured product of resin material.
It is a cured product used as an insulating material.
Based on the free induction decay curve at 30 ° C. obtained by pulse NMR, the components contained in the cured product are divided into hard components at 30 ° C. and middle components at 30 ° C. in ascending order of spin-spin relaxation time. , The components contained in the cured product, based on the free induction decay curve at 170 ° C. obtained by separating into three components of the soft component at 30 ° C. and using pulse NMR, with respect to the spin-spin relaxation time. When separated into three components, in ascending order, a hard component at 170 ° C, a middle component at 170 ° C, and a soft component at 170 ° C,
The content of the hard component at 170 ° C. is 100% of the total of the content of the hard component at 170 ° C., the content of the middle component at 170 ° C., and the content of the soft component at 170 ° C. 40% or more and 80% or less,
A cured product in which the ratio of the spin-spin relaxation time of the hard component at 170 ° C. to the spin-spin relaxation time of the hard component at 30 ° C. is 1.5 or less. The cured product according to claim 1, wherein the spin-spin relaxation time of the hard component at 170 ° C. is 0.016 ms or less. The content of the hard component at 30 ° C. is 100% of the total of the content of the hard component at 30 ° C., the content of the middle component at 30 ° C., and the content of the soft component at 30 ° C. The cured product according to claim 1 or 2, which is 70% or more and 90% or less. The cured product according to any one of claims 1 to 3, wherein the resin material contains a thermosetting compound and an inorganic filler. The resin material contains a thermosetting compound and a curing agent.
The thermosetting compound contains an epoxy compound and contains
The cured product according to any one of claims 1 to 3, wherein the curing agent contains an active ester compound. B stage film
B stage film used as an insulating material
The B stage film is heated at 130 ° C. for 30 minutes, 170 ° C. for 30 minutes, and 200 ° C. for 1 hour in this order to obtain a cured product of the B stage film, which is freely obtained at 30 ° C. by pulse NMR. Based on the induction decay curve, the components contained in the cured product are separated into three components in ascending order of spin-spin relaxation time: a hard component at 30 ° C., a middle component at 30 ° C., and a soft component at 30 ° C. In addition, based on the free induction decay curve at 170 ° C. obtained by pulse NMR, the components contained in the cured product are subjected to the hard components at 170 ° C. and 170 ° C. in ascending order of spin-spin relaxation time. When separated into three components, a middle component at 170 ° C and a soft component at 170 ° C,
The content of the hard component at 170 ° C. is 100% of the total of the content of the hard component at 170 ° C., the content of the middle component at 170 ° C., and the content of the soft component at 170 ° C. 40% or more and 80% or less,
A B-stage film in which the ratio of the spin-spin relaxation time of the hard component at 170 ° C. to the spin-spin relaxation time of the hard component at 30 ° C. is 1.5 or less. The B-stage film according to claim 6, wherein the spin-spin relaxation time of the hard component at 170 ° C. is 0.016 ms or less. The content of the hard component at 30 ° C. is 100% of the total of the content of the hard component at 30 ° C., the content of the middle component at 30 ° C., and the content of the soft component at 30 ° C. The B stage film according to claim 6 or 7, which is 70% or more and 90% or less. The B stage film according to any one of claims 6 to 8, which is used for forming an insulating layer in a multilayer printed wiring board. Circuit board and
A plurality of insulating layers arranged on the surface of the circuit board,
With a plurality of metal layers arranged between the insulating layers,
A multilayer printed wiring board in which the material of at least one of the insulating layers is the cured product according to any one of claims 1 to 5.

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