JP2021017505A - Resin material and multilayer printed wiring board - Google Patents

Abstract

To provide a resin material capable of 1) lowering dielectric tangent of a cured material, 2) enhancing a thermal dimensional stability of the cured material, 3) enhancing elongation characteristics of the cured material, and 4) effectively removing smear by a desmear treatment.SOLUTION: A resin material according to the present invention includes a thermosetting compound, a compound A having two or more reactive functional groups capable reacting with the thermosetting compound, and a hydrophobic unit having two or more in total of oxygen atom, nitrogen atom and sulfur atom, and an inorganic filler, in the compound A, each of two or more of the reactive functional groups binds with the hydrophilic unit via a chain-like skeleton, respectively, in the compound A, a number of atoms of a straight chain part of the chain-like skeleton connecting the reactive functional group and the hydrophilic unit is 4 or lager, and, in a component 100 wt% excluding a solvent in the resin material, a content of the inorganic filler is 10 mass% or larger.SELECTED DRAWING: Figure 1

Description

The present invention relates to resin materials including inorganic fillers. The present invention also relates to a multilayer printed wiring board using the above resin material.

Conventionally, various resin materials have been used in order 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 inner 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.

The following Patent Document 1 describes (A) a liquid thermosetting resin having a refractive index of 1.40 to 1.55, and (B) an alkyl having an average primary particle size of 1 nm to 50 nm and having 4 or more carbon atoms. A transparent liquid thermosetting resin composition containing nanosilica treated with an alkylsilyl treated with an alkoxysilane having a group is disclosed. In Patent Document 1, it is preferable to use a silicone compound having a specific structure as (A) a liquid thermosetting resin, and (B) the content of alkylsilyl-treated nanosilica is (A) liquid heat. It is described that it is preferably 1 part by mass to 10 parts by mass with respect to 100 parts by mass of the curable resin.

Patent Document 2 below discloses a resin composition containing (A) an epoxy resin having an ester skeleton, (B) an active ester type curing agent, and (C) an inorganic filler. In this resin composition, when the non-volatile component in the resin composition is 100% by mass, the content of (C) the inorganic filler is 50% by mass or more, and (C) the inorganic filler is 100 parts by mass. In the case, the epoxy resin having the (A) ester skeleton is 1 to 20 parts by mass.

Japanese Unexamined Patent Publication No. 2019-090017 JP-A-2017-171925

In order to enhance the electrical characteristics of the cured product (insulating layer), a compound having a small polarity may be added to the resin material (resin composition). However, when a cured product (insulating layer) is formed using a resin material containing a compound having a low polarity, smear may not be effectively removed by the desmear treatment.

Further, in the conventional resin material designed to enhance the thermal dimensional stability of the cured product, the elongation characteristics of the cured product are not sufficiently high, and as a result, the insulating layer is cracked or cracked, and the plating peel strength is increased. It may not be high enough. On the other hand, it is difficult to improve the thermal dimensional stability of the cured product with a conventional resin material containing a resin having a small glass transition temperature in order to enhance the elongation characteristics of the cured product.

The object of the present invention is that 1) the dielectric loss tangent of the cured product can be lowered, 2) the thermal dimensional stability of the cured product can be improved, 3) the elongation characteristics of the cured product can be improved, and 4) It is to provide a resin material which can effectively remove smear by desmear treatment. Another object of the present invention is to provide a multilayer printed wiring board using the above resin material.

According to a broad aspect of the present invention, hydrophilicity having a thermocurable compound, two or more reactive functional groups capable of reacting with the thermocurable compound, and a total of two or more oxygen, nitrogen and sulfur atoms. Compound A having a sex unit and an inorganic filler are contained, and in the compound A, two or more of the reactive functional groups are each bonded to the hydrophilic unit via a chain skeleton. In the compound A, the number of atoms of the linear portion of the chain skeleton connecting the reactive functional group and the hydrophilic unit is 4 or more, and the content excluding the solvent in the resin material is 100% by weight. Provided is a resin material having a content of the inorganic filler of 10% by weight or more.

In certain aspects of the resin material according to the invention, the chain skeleton has a hydrolyzable bond.

In certain aspects of the resin material according to the present invention, the hydrolyzable bond is an ester bond.

In certain aspects of the resin material according to the present invention, the hydrophilic unit has rotational symmetry.

In certain aspects of the resin material according to the present invention, the hydrophilic unit has an isocyanuric acid skeleton or a diphenyl sulfone skeleton.

In certain aspects of the resin material according to the present invention, the reactive functional group is an epoxy group, a maleimide group, an active ester group, a phenolic hydroxyl group, a thiol group, or a vinyl group.

In certain aspects of the resin material according to the present invention, the thermosetting compound is an epoxy compound, a maleimide compound, a benzoxazine compound, or a vinyl compound.

In certain aspects of the resin material according to the invention, the thermosetting compound is an epoxy compound and the epoxy compound comprises a glycidyl ester epoxy compound.

In a specific aspect of the resin material according to the present invention, the content of the compound A is 25% by weight or less in a total of 100% by weight of the thermosetting compound and the compound A.

In certain aspects of the resin material according to the invention, it comprises a curing agent, wherein the curing agent comprises at least one component of a phenolic compound, an active ester compound, a cyanate ester compound, and a carbodiimide compound.

In certain aspects of the resin material according to the present invention, the curing agent comprises a bifunctional curing agent having a molecular weight of 500 or less.

In a specific aspect of the resin material according to the present invention, the average particle size of the inorganic filler is 100 nm or more.

In certain aspects of the resin material according to the present invention, the inorganic filler is silica.

In a specific aspect of the resin material according to the present invention, the content of the inorganic filler is 50% by weight or more in 100% by weight of the components excluding the solvent in the resin material.

In certain aspects of the resin material according to the present invention, the resin material is a resin film.

The resin material 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, the plurality of insulating layers include 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. A multilayer printed wiring board is provided in which at least one of the layers is a cured product of the resin material described above.

The resin material according to the present invention is hydrophilic having a thermosetting compound, two or more reactive functional groups capable of reacting with the thermosetting compound, and a total of two or more oxygen atoms, nitrogen atoms and sulfur atoms. It contains compound A having a unit and an inorganic filler. In the resin material according to the present invention, in the compound A, two or more reactive functional groups are each bonded to the hydrophilic unit via a chain skeleton, and in the compound A, the reactivity is described. The number of atoms in the linear portion of the chain skeleton connecting the functional group and the hydrophilic unit is 4 or more. In the resin material according to the present invention, the content of the inorganic filler is 10% by weight or more in 100% by weight of the components excluding the solvent in the resin material. Since the resin material according to the present invention has the above-mentioned structure, 1) the dielectric loss tangent of the cured product can be lowered, 2) the thermal dimensional stability of the cured product can be improved, and 3) the cured product can be cured. The elongation characteristics of the object can be enhanced, and 4) smear can be effectively removed by the desmear treatment.

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

Hereinafter, the present invention will be described in detail.

The resin material according to the present invention is hydrophilic having a thermosetting compound, two or more reactive functional groups capable of reacting with the thermosetting compound, and a total of two or more oxygen atoms, nitrogen atoms and sulfur atoms. It contains compound A having a unit and an inorganic filler. In the resin material according to the present invention, in the compound A, two or more reactive functional groups are each bonded to the hydrophilic unit via a chain skeleton, and in the compound A, the reactivity is described. The number of atoms in the linear portion of the chain skeleton connecting the functional group and the hydrophilic unit is 4 or more. In the resin material according to the present invention, the content of the inorganic filler is 10% by weight or more in 100% by weight of the components excluding the solvent in the resin material.

Since the resin material according to the present invention has the above-mentioned structure, 1) the dielectric loss tangent of the cured product can be lowered, 2) the thermal dimensional stability of the cured product can be improved, and 3) the cured product can be cured. It is possible to enhance the elongation characteristics of an object, and to exert all the effects of 1) to 4) that 4) smear can be effectively removed by desmear treatment.

Further, in the resin material according to the present invention, since the elongation characteristics of the cured product can be enhanced, the occurrence of cracks or cracks in the cured product can be suppressed, and the plating peel strength can be enhanced.

The resin material according to the present invention may be a resin composition or a resin film. The resin composition has fluidity. The resin composition may be in the form of a paste. The paste form contains a liquid. The resin material according to the present invention is preferably a resin film because it is excellent in handleability.

The resin material according to the present invention is preferably a thermosetting resin material. When the resin material is a resin film, the resin film is preferably a thermosetting resin film.

Hereinafter, the details of each component used in the resin material according to the present invention, the use of the resin material according to the present invention, and the like will be described. In addition, a preferable structure and the like capable of exerting the effect of the present invention more effectively will be specifically described below.

[Thermosetting compound]
The resin material contains a thermosetting compound. The thermosetting compound is different from the compound A. Only one type of the thermosetting compound may be used, or two or more types may be used in combination.

Examples of the thermosetting compound include epoxy compounds, maleimide compounds, benzoxazine compounds, vinyl compounds, styrene compounds, phenoxy compounds, oxetane compounds, polyarylate compounds, diallylphthalate compounds, acrylate compounds, episulfide compounds, and (meth) acrylic compounds. Examples thereof include amino compounds, unsaturated polyester compounds, polyurethane compounds, silicone compounds and the like.

The thermosetting compound is preferably an epoxy compound, a maleimide compound, a benzoxazine compound or a vinyl compound, more preferably an epoxy compound or a vinyl compound, and even more preferably an epoxy compound. In this case, the dielectric loss tangent of the cured product can be further lowered, and the thermal dimensional stability of the cured product can be further improved.

<Epoxy compound>
As the epoxy compound, a conventionally known epoxy compound can be used. The epoxy compound is an organic compound having at least one epoxy group. 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, adamantan skeleton epoxy compound, tricyclodecane skeleton epoxy compound, naphthylene ether type Examples thereof include epoxy compounds and epoxy compounds having a triazine nucleus as a skeleton.

From the viewpoint of further lowering the dielectric loss tangent and enhancing the thermal dimensional stability and flame retardancy of the cured product, the epoxy compound preferably contains an epoxy compound having an aromatic skeleton, and has a naphthalene skeleton or a phenyl skeleton. It is preferable to contain an epoxy compound having an epoxy compound, and more preferably an epoxy compound having an aromatic skeleton. Further, from the viewpoint of further enhancing the desmear property, the epoxy compound preferably contains a glycidyl ester epoxy compound.

From the viewpoint of further lowering the dielectric loss tangent and improving the coefficient of linear expansion (CTE) of the cured product, the epoxy compound contains a liquid epoxy compound at 25 ° C. and a solid epoxy compound at 25 ° C. Is preferable.

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.

The viscosity of the epoxy compound can be measured using, for example, a dynamic viscoelasticity measuring device (“VAR-100” manufactured by Leologica Instruments) or the like.

The molecular weight of the epoxy compound is more preferably 1000 or less. In this case, even if the content of the inorganic filler is 50% by weight or more in 100% by weight of the component excluding the solvent in the resin material, 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 enhancing the thermal dimensional stability of the cured product, the content of the epoxy compound is preferably 4% by weight or more, more preferably 7% by weight or more, based on 100% by weight of the components excluding the solvent in the resin material. , Preferably 20% by weight or less, more preferably 15% by weight or less.

The content of the epoxy compound in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material is preferably 15% by weight or more, more preferably 25% by weight or more, preferably 60% by weight or less, more preferably. Is 40% by weight or less. When the content of the epoxy 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.

Weight ratio of the content of all epoxy compounds contained in the resin material to the total content of the curing agent described later (content of all epoxy compounds contained in the resin material / total content of the curing agent described later) The amount) is preferably 0.5 or more, more preferably 0.8 or more, preferably 1.5 or less, and more preferably 1.2 or less. When the weight ratio is at least the above lower limit and at least the above upper limit, the dielectric loss tangent can be further lowered and the thermal dimensional stability can be further improved. The content of all the epoxy compounds contained in the resin material is the total content of the epoxy compound which is the compound A and the epoxy compound which is the thermosetting compound when the compound A is an epoxy compound. Means. Further, the content of all the epoxy compounds contained in the resin material means the epoxy compound which is the thermosetting compound when the compound A is different from the epoxy compound.

<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 preferably has an aromatic ring.

In the above 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 of the cured product, the content of the maleimide compound is preferably 0.5% by weight or more, more preferably 1% by weight, based on 100% by weight of the components excluding the solvent in the resin material. % Or more, preferably 20% 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 polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC) when the maleimide compound is a polymer.

Examples of commercially available products of the maleimide compound include "BMI4000" and "BMI5100" manufactured by Daiwa Kasei Kogyo Co., Ltd., and Designer Molecules Inc. Manufactured by "BMI-3000" and the like.

<Benzoxazine compound>
As the benzoxazine compound, a conventionally known benzoxazine compound can be used. Only one kind of the benzoxazine compound may be used, or two or more kinds thereof may be used in combination.

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 benzoxazine compound in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material is preferably 1% by weight or more, more preferably 5% by weight or more, still more preferably 10% by weight or more. It is preferably 60% by weight or less, more preferably 50% by weight or less. When the content of the benzoxazine 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.

<Vinyl compound>
As the vinyl compound, a conventionally known vinyl compound can be used. The vinyl compound is an organic compound having at least one vinyl group. Only one kind of the vinyl compound may be used, or two or more kinds thereof may be used in combination.

Examples of the vinyl compound include a divinylbenzyl ether compound.

The content of the vinyl compound in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material is preferably 5% by weight or more, more preferably 10% by weight or more, still more preferably 20% by weight or more. Is 70% by weight or less, more preferably 60% by weight or less. When the content of the vinyl 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.

[Compound A]
The resin material according to the present invention contains compound A. The compound A has two or more reactive functional groups capable of reacting with the thermosetting compound. The compound A has a hydrophilic unit having two or more oxygen atoms, nitrogen atoms and sulfur atoms in total. In the compound A, each of the two or more reactive functional groups is attached to the hydrophilic unit via a chain skeleton. In the compound A, the number of atoms in the linear portion of the chain skeleton connecting the reactive functional group and the hydrophilic unit is 4 or more. As the compound A, only one kind may be used, or two or more kinds may be used in combination.

The compound A is preferably a thermosetting compound or a curing agent. Therefore, it is preferable that the resin material according to the present invention contains the above-mentioned thermosetting compound as the first thermosetting compound and the above-mentioned compound A as the second thermosetting compound. Further, it is also preferable that the resin material according to the present invention contains the above-mentioned compound A as a first curing agent and a curing agent described later as a second curing agent.

Examples of the reactive functional group include an epoxy group, a maleimide group, an active ester group, a phenolic hydroxyl group, a thiol group, a vinyl group and the like.

From the viewpoint of effectively exerting the effects of 1) to 4) above, the reactive functional group is preferably an epoxy compound, a maleimide compound, a benzoxazine compound, or a vinyl compound, and is preferably an epoxy group or a maleimide group. Is more preferable.

From the viewpoint of exerting the effects of 1) to 4) above, the number of the reactive functional groups contained in the compound A is two or more. From the viewpoint of effectively exerting the effects of 1) to 4) above, the number of the reactive functional groups is preferably 3 or more, preferably 6 or less, and more preferably 5 or less.

The reactive functional group is preferably located at the terminal of the compound A.

The hydrophilic unit is a unit having two or more oxygen atoms, nitrogen atoms and sulfur atoms in total. The hydrophilic unit may have only one kind of atom among oxygen atom, nitrogen atom and sulfur atom, may have two kinds of atoms, and may have three kinds of atoms. You may. In the compound A, the number of the hydrophilic units may be one or two or more.

The hydrophilic unit preferably has 3 or more oxygen atoms, nitrogen atoms, and sulfur atoms in total, and more preferably 4 or more. When the total number of the atoms is equal to or greater than the lower limit, the effects 1) to 4) above can be effectively exerted, and in particular, smear can be effectively removed by the desmear treatment.

The hydrophilic unit preferably has a structure in which the oxygen atom, the nitrogen atom and the sulfur atom are adjacent to each other, or are bonded via one atom. The one atom is an atom different from the oxygen atom, the nitrogen atom and the sulfur atom.

The hydrophilic unit preferably has a cyclic skeleton.

From the viewpoint of effectively exerting the effects of the above 1) to 4), particularly from the viewpoint of enhancing the elongation characteristics of the cured product, the hydrophilic unit is preferably a unit having rotational symmetry. The hydrophilic unit has an isocyanuric acid skeleton or a diphenylsulfone skeleton from the viewpoint of exerting the effects of 1) to 4) more effectively, particularly from the viewpoint of further enhancing the elongation characteristics of the cured product. Is preferable, and it is more preferable to have an isocyanuric acid skeleton.

In the compound A, each of the two or more reactive functional groups is attached to the hydrophilic unit via a chain skeleton. The chain skeleton is a skeleton that connects the reactive functional group and the hydrophilic unit. The chain skeleton does not contain the reactive functional groups and the hydrophilic units.

The chain skeleton may or may not have a branched structure.

From the viewpoint of effectively exerting the effects of 1) to 4) above, when the compound A has the isocyanuric acid skeleton as the hydrophilic unit, the chain skeleton has the isocyanuric acid skeleton. It is preferably bonded to each of the constituent nitrogen atoms.

From the viewpoint of effectively exerting the effects of 1) to 4) above, and particularly from the viewpoint of enhancing the elongation characteristics of the cured product, in the compound A, the reactive functional group and the hydrophilic unit are connected. The number of atoms in the linear portion of the chain skeleton is 4 or more. From the viewpoint of exerting the effects of 1) to 4) more effectively, particularly from the viewpoint of further enhancing the elongation characteristics of the cured product, the reactive functional group and the hydrophilic unit are used. The number of atoms in the linear portion of the chain skeleton to be connected is preferably 5 or more, more preferably 6 or more.

The number of atoms in the linear portion of the chain skeleton that connects the reactive functional group and the hydrophilic unit means the number of atoms that connect the reactive functional group and the hydrophilic unit in the shortest time. Since the chain skeleton does not contain the reactive functional group and the hydrophilic unit, the hydrophilic unit and the atoms constituting the reactive functional group are the reactive functional group and the hydrophilic unit. It is not counted as an atom of the linear part of the above chain skeleton that connects

The chain skeleton preferably has a hydrolyzable bond. That is, the compound A preferably has a hydrolyzable bond between the hydrophilic unit and the reactive functional group. In this case, in the desmear treatment step, the solubility of the resin material can be enhanced, and smear can be removed even more effectively.

Examples of the hydrolyzable bond include an ester bond and a carbonate bond. The hydrolyzable bond may be a carbon-carbon double bond that is easily decomposed during desmear treatment.

From the viewpoint of removing smear even more effectively by the desmear treatment, the hydrolyzable bond is preferably an ester bond.

Examples of the compound A include compounds represented by the following formulas (A1) and the following formula (A2).

The compound represented by the above formula (A1) has 6 epoxy groups as the above reactive functional groups. The compound represented by the above formula (A1) has a hydrophilic unit having a total of 6 oxygen atoms, nitrogen atoms and sulfur atoms. More specifically, the compound represented by the above formula (A1) has a hydrophilic unit having 3 oxygen atoms and 3 nitrogen atoms. The hydrophilic unit has rotational symmetry. In addition, the hydrophilic unit has an isocyanuric acid skeleton. In the compound represented by the above formula (A1), each of the six epoxy groups (reactive functional groups) is bonded to the hydrophilic unit via a chain skeleton. The chain skeleton has a branched structure. In the compound represented by the above formula (A1), the number of atoms in the linear portion of the chain skeleton connecting the epoxy group which is the reactive functional group and the hydrophilic unit is 9 (7 carbon atoms and oxygen). 2 atoms). Further, in the compound represented by the above formula (A1), the chain skeleton has an ester bond as a hydrolyzable bond.

The compound represented by the above formula (A2) has three epoxy groups as the above reactive functional groups. The compound represented by the above formula (A2) has a hydrophilic unit having a total of 6 oxygen atoms, nitrogen atoms and sulfur atoms. More specifically, the compound represented by the above formula (A2) has a hydrophilic unit having 3 oxygen atoms and 3 nitrogen atoms. The hydrophilic unit has rotational symmetry. In addition, the hydrophilic unit has an isocyanuric acid skeleton. In the compound represented by the above formula (A2), each of the three epoxy groups (reactive functional groups) is bonded to the above hydrophilic unit via a chain skeleton. The chain skeleton does not have a branched structure. In the compound represented by the above formula (A2), the number of atoms in the linear portion of the chain skeleton connecting the epoxy group which is the reactive functional group and the hydrophilic unit is 6 (6 carbon atoms). is there. Further, in the compound represented by the above formula (A2), the chain skeleton does not have a hydrolyzable bond.

From the viewpoint of further enhancing the elongation characteristics of the cured product and the viewpoint of removing smear more effectively by the desmear treatment, the compound A is a compound represented by the above formula (A1) or the above formula (A2). It is preferable that the compound is represented by the above formula (A1), and more preferably.

A commercially available product can also be used as the compound A. Examples of commercially available products of the compound A include "TEPIC-UC" and "TEPIC-FL" manufactured by Nissan Chemical Industries, Ltd. "TEPIC-UC" manufactured by Nissan Chemical Industries, Ltd. is a compound represented by the above formula (A1). "TEPIC-FL" manufactured by Nissan Chemical Industries, Ltd. is a compound represented by the above formula (A2).

Of the total 100% by weight of the thermosetting compound and the compound A, the content of the compound A is preferably 1% by weight or more, more preferably 2% by weight or more, preferably 25% by weight or less, more preferably 10%. By weight or less, more preferably 6% by weight or less. When the content of the compound A is not less than the above lower limit and not more than the above upper limit, the effects of the above 1) to 4) can be effectively exhibited.

The content of the compound A in 100% by weight of the component excluding the solvent in the resin material is preferably 0.05% by weight or more, more preferably 0.1% by weight or more, preferably 2% by weight or less, more preferably. It is 1.5% by weight or less. When the content of the compound A is not less than the above lower limit and not more than the above upper limit, the effects of the above 1) to 4) can be effectively exhibited.

[Inorganic filler]
The resin material includes an inorganic filler. By using the above-mentioned inorganic filler, the dielectric loss tangent of the cured product can be further lowered. Further, by using the above-mentioned inorganic filler, the dimensional change due to heat of the cured product is further reduced. Only one kind of the above-mentioned inorganic filler may be used, or two or more kinds may be used in combination.

From the viewpoint of enhancing the insulating property, the inorganic filler is preferably an insulating inorganic filler.

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

The surface roughness of the surface of the cured product is reduced, the adhesive strength between the cured product and the metal layer is further increased, finer wiring is formed on the surface of the cured product, and the cured product has better insulation reliability. From the viewpoint of imparting, the inorganic filler is preferably silica or alumina, more preferably silica, and even more preferably fused silica. Due to the use of silica, the coefficient of thermal expansion of the cured product is further reduced, and the dielectric loss tangent of the cured product is further reduced. Further, by using silica, the surface roughness of the surface of the cured product is effectively reduced, and the adhesive strength between the cured product 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.

From the viewpoint of increasing the thermal conductivity and the insulating property, the inorganic filler is preferably alumina.

The average particle size of the inorganic filler is preferably 50 nm or more, more preferably more than 50 nm, still more preferably 100 nm or more, particularly preferably 500 nm or more, preferably 5 μm or less, more preferably 3 μm or less, still more preferably 1 μm or less. Is. 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 surface roughness after etching can be reduced and the plating peel strength can be increased, and the insulating layer and the metal layer can be combined. Adhesion can be further improved.

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, and more preferably spherical silica. In this case, the surface roughness of the surface of the cured product is effectively reduced, and the adhesive strength between the cured product 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. By surface-treating the inorganic filler, the surface roughness of the surface of the roughened cured product is further reduced, and the adhesive strength between the cured product and the metal layer is further increased. Further, since the inorganic filler is surface-treated, finer wiring can be formed on the surface of the cured product, and even better inter-wiring insulation reliability and interlayer insulation reliability can be obtained in the cured product. Can be granted.

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.

From the viewpoint of lowering the dielectric loss tangent of the cured product, in the resin material according to the present invention, the content of the inorganic filler is 10% by weight or more in 100% by weight of the components excluding the solvent in the resin material.

The content of the inorganic filler in 100% by weight of the component excluding the solvent in the resin material is preferably 25% by weight or more, more preferably 50% by weight or more, still more preferably 60% by weight or more, and particularly preferably 65% by weight. % Or more, most preferably 68% 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 80% by weight or less, and particularly preferably 75% by weight. % Or less. When the content of the inorganic filler is at least the above lower limit, the dielectric loss tangent becomes even more effective. When the content of the inorganic filler is not more than the above upper limit, the thermal dimensional stability can be improved and the warpage of the cured product can be effectively suppressed. When the content of the inorganic filler is at least the above lower limit and at least the above upper limit, the surface roughness of the surface of the cured product can be further reduced, and finer wiring can be formed on the surface of the cured product. Can be done. Further, the content of this inorganic filler makes it possible to reduce the coefficient of thermal expansion of the cured product and at the same time improve the smear removability.

[Hardener]
The resin material preferably contains a curing agent. The curing agent is not particularly limited. A conventionally known curing agent 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 phenol compound (phenol curing agent), active ester compound, cyanate ester compound (cyanate ester curing agent), carbodiimide compound (carbodiimide curing agent), amine compound (amine curing agent), and thiol compound (thiol curing agent). ), Phosphine compounds, dicyandiamides, acid anhydrides and the like. The curing agent preferably has a functional group capable of reacting with the epoxy group of the epoxy compound.

From the viewpoint of further enhancing the thermal dimensional stability and further lowering the dielectric adjacency, the curing agent contains at least one component of a phenol compound, an active ester compound, a cyanate ester compound, a carbodiimide compound and an acid anhydride. It is preferable to include it. The curing agent may contain at least one component of a phenol compound, an active ester compound, a cyanate ester compound, and a carbodiimide compound from the viewpoint of further enhancing the thermal dimensional stability and further lowering the dielectric adjacency. More preferably, it further preferably contains an active ester compound.

From the viewpoint of effectively exerting the effects of 1) to 4) above, the curing agent preferably has a molecular weight of 500 or less and contains a bifunctional curing agent. Further, in this case, when the compound A is a compound having a relatively large number of reactive functional groups as represented by the above formula (1A), the compound A can be sufficiently reacted and cured. The dielectric loss tangent of the product can be further lowered, and the elongation characteristics of the cured product can be further improved.

From the viewpoint of further enhancing the thermal dimensional stability, it is preferable that the thermosetting compound contains an epoxy compound and the curing agent contains both a phenol compound and an active ester compound.

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 novolac-type phenol (“TD-2091” manufactured by DIC), biphenyl novolac-type phenol (“MEH-7851” manufactured by Meiwa Kasei Co., Ltd.), and aralkyl-type phenol compound (“MEH” manufactured by Meiwa Kasei Co., Ltd. -7800 "), and phenols having an aminotriazine skeleton ("LA-1356" and "LA-3018-50P" manufactured by DIC) and the like can be mentioned.

The active ester compound refers to a compound containing at least one ester bond in the structure and having an aliphatic chain, an aliphatic ring or an aromatic ring 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.

In the above formula (1), 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, and a substituent. Examples thereof include a combination of a benzene ring and a naphthalene ring which may have a substituent. Further, in the above formula (1), 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 of the cured product and increasing the thermal dimensional stability of the cured product, it is more preferable to have a naphthalene ring in the main chain skeleton of the active ester compound.

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

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 cyanate ester compound include a phenol novolac type cyanate ester resin (“PT-30” and “PT-60” manufactured by Lonza Japan) 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.

The content of the cyanate ester compound in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material is preferably 10% by weight or more, more preferably 15% by weight or more, still more preferably 20% by weight or more. It is preferably 85% by weight or less, more preferably 75% by weight or less. When the content of the cyanate ester 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.

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 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. 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 having a substituent attached to an alkylene group, a cycloalkylene group, or a group having 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 acid anhydride include tetrahydrophthalic anhydride, alkylstyrene-maleic anhydride copolymer and the like.

Examples of commercially available products of the acid anhydride include "Ricacid TDA-100" manufactured by New Japan Chemical Co., Ltd.

The content of the curing agent with respect to a total of 100 parts by weight of the compound A and the thermosetting compound 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. It is less than a part by weight. When the content of the curing agent 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 compound A, the thermosetting compound, and the curing agent 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 98% by weight or less, more preferably 95% by weight or less. When the total content 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-undecyl imidazole, 2-heptadecyl imidazole, 2-methyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 2-phenyl-4-methyl imidazole and 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 and 4,4-dimethylaminopyridine.

Examples of the phosphorus compound include triphenylphosphine compounds.

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

Examples of the peroxide include dicumyl peroxide and perhexyl 25B.

From the viewpoint of further suppressing the curing temperature and effectively suppressing the warpage of the cured product, the curing accelerator preferably contains the anionic curing accelerator, and more preferably contains the imidazole compound.

From the viewpoint of further suppressing the curing temperature and effectively suppressing the warp of the cured product, the content of the anionic curing accelerator is preferably 20% by weight or more, more preferably 20% by weight or more, based on 100% by weight of the curing accelerator. Is 50% by weight or more, more preferably 70% by weight or more, and most preferably 100% by weight (total amount). Therefore, the curing accelerator is most preferably the anionic curing accelerator.

When the vinyl compound is used as the thermosetting compound, radical curing proceeds, so that the curing accelerator preferably contains the radical curing accelerator.

The content of the curing accelerator is not particularly limited. The content of the curing accelerator is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, and preferably 5% by weight in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material. Hereinafter, it is more preferably 3% by weight or less. When the content of the curing accelerator is at least the above lower limit and at least the above upper limit, the resin material is efficiently cured. If the content of the curing accelerator is in a more preferable range, the storage stability of the resin material becomes even higher, and a better 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. The use of the phenoxy resin suppresses deterioration of the embedding property of the resin film in the holes or irregularities of the circuit board and non-uniformity of the inorganic filler. 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 composition 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 & Sumikin Chemical Corporation, and "1256B40", "4250", "4256H40" and "4275" manufactured by Mitsubishi Chemical Corporation. , "YX6954BH30" and "YX8100BH30" and the like.

The thermoplastic resin is preferably a polyimide resin (polyimide compound) from the viewpoint of improving handleability, plating peel strength at low roughness, and adhesion between the insulating layer and the metal layer.

From the viewpoint of improving the solubility, the polyimide compound is preferably a polyimide compound obtained by a method of reacting a tetracarboxylic dianhydride with a dimer diamine.

Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenylsulfonetetra. Carcarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3', 4,4'-biphenyl ether Tetetracarboxylic dianhydride, 3,3', 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2 , 3,4-Flantetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl Sethylene dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3', 4,4'-perfluoroisopropyridenediphthalic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphinoxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenyl) Examples thereof include phthalic dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, and bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride.

Examples of the dimer diamine include Versamine 551 (trade name: 3,4-bis (1-aminoheptyl) -6-hexyl-5- (1-octenyl) cyclohexene manufactured by BASF Japan Ltd.) and Versamine 552 (trade name: Examples thereof include Cognix Japan (manufactured by Cognix Japan, hydrogenated Versamine 551), PRIAMINE1075, PRIAMINE1074 (trade name, all manufactured by Crowder Japan) and the like.

The polyimide compound may have an acid anhydride structure, a maleimide structure, or a citraconimide structure at the terminal. In this case, the polyimide compound and the epoxy compound can be reacted. By reacting the polyimide compound with the epoxy compound, the thermal dimensional stability of the cured product can be improved.

From the viewpoint of obtaining a resin material having more excellent storage stability, the weight average molecular weights of the thermoplastic resin, the polyimide resin and the phenoxy resin are preferably 5000 or more, more preferably 10000 or more, preferably 100,000 or less. It is preferably 50,000 or less.

The weight average molecular weights of the thermoplastic resin, the polyimide resin, and the phenoxy resin indicate the polystyrene-equivalent weight average molecular weights measured by gel permeation chromatography (GPC).

The contents of the thermoplastic resin, the polyimide resin, and the phenoxy resin are not particularly limited. The content of the thermoplastic resin in 100% by weight of the component excluding the inorganic filler and the solvent in the resin material (when the thermoplastic resin is a polyimide resin or a phenoxy resin, the content of the polyimide resin or the phenoxy resin). ) Is preferably 1% by weight or more, more preferably 2% by weight or more, preferably 30% by weight or less, and more preferably 20% 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 cured product 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, and methyl ethyl ketone. 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.

When the resin material is a B stage film, the content of the solvent in 100% by weight of the B stage film is preferably 1% by weight or more, more preferably 2% by weight or more, and preferably 10% by weight or less. , More preferably 5% by weight or less.

[Other ingredients]
For the purpose of improving impact resistance, heat resistance, resin compatibility, workability, etc., the above resin materials are leveling agents, flame retardants, coupling agents, colorants, antioxidants, ultraviolet deterioration inhibitors, defoamers. It may contain an agent, a thickener, a rock denaturing agent and the like.

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)
A resin film (B-staged product / B-stage film) can be obtained by molding the above-mentioned resin composition into a film. The resin material is preferably a resin film. The resin film is preferably a B stage film.

Examples of a 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 as 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. it can.

The film-like resin composition 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 film and a resin film laminated on the surface of the metal foil or the base film. The metal foil is preferably a copper foil.

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 film may be mold-released, 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 resin material is suitably used for forming a mold resin for embedding a semiconductor chip in a semiconductor device.

The resin material is preferably used as an insulating material. The resin material is preferably 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 member to be laminated having a metal layer on one side or both sides can be laminated on the resin film. A laminated structure comprising a member to be laminated having a metal layer on its surface and a resin film laminated on the surface of the metal layer, and the resin film being the resin material described above can be preferably obtained. The method of laminating the resin film and the member to be laminated having the metal layer on the surface is not particularly limited, and a known method can be used. For example, using a device such as a parallel flat plate press or a roll laminator, the resin film can be laminated on a member to be laminated having a metal layer on the surface while pressurizing with or without heating.

The material of the metal layer is preferably copper.

The member to be laminated having the metal layer on the surface may be a metal foil such as a copper foil.

The resin material is preferably used to obtain 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 is preferably used to obtain 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 insulating layer of this multilayer substrate is formed of the above resin material. 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. 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.

Another example of the multilayer board 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. 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.

Among multilayer boards, multilayer printed wiring boards are required to have low dielectric loss tangent and high insulation reliability due to the insulating layer. Therefore, the resin material according to the present invention is 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. At least one of the insulating layers is a cured product of the resin material.

FIG. 1 is a cross-sectional view schematically showing a multilayer printed wiring board using a resin material 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 products 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 of the resin material. 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.

The cured product is preferably roughened in order to form fine irregularities on the surface of the cured product obtained by pre-curing the resin material. 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 or an organic solvent dispersion solution 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 solution used for the roughening treatment generally contains an alkali as a pH adjuster or the like. The roughening solution 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 cured product 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 solution preferably contains sodium hydroxide.

By using the above resin material, the surface roughness of the surface of the desmear-treated cured product 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 following materials were prepared.

(Compound A)
Compound A1 (“TEPIC-UC” manufactured by Nissan Chemical Industries, Ltd., compound represented by the above formula (A1))
Compound A2 (“TEPIC-FL” manufactured by Nissan Chemical Industries, Ltd., compound represented by the above formula (A2))

(Compound not corresponding to Compound A (Compound B))
Compound B1 ("TEPIC-VL" manufactured by Nissan Chemical Industries, Ltd.)
Compound B2 ("JER871" manufactured by Mitsubishi Chemical Corporation)
Compound B3 ("PB3600" manufactured by Daicel Corporation)

(Thermosetting compound)
Biphenyl type epoxy compound ("NC-3000L" manufactured by Nippon Kayaku Co., Ltd.)
Naphthalene type epoxy compound ("TX-1507BEK75" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)
Glycidylamine type epoxy compound ("630" manufactured by Mitsubishi Chemical Corporation))
Resorcinol diglycidyl ether (“EX-201” manufactured by Nagase ChemteX Corporation)

(Inorganic filler)
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)
Active ester compound 1 (“EXB-8” manufactured by DIC Corporation, solid content 100% by weight)
Active ester compound 2 containing liquid (DIC Corporation "HPC-8150-62T", solid content 62% by weight)
Phenol compound-containing liquid ("LA-1356" manufactured by DIC Corporation, solid content 60% 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)
Polyimide compound (polyimide resin):
A polyimide compound-containing solution (nonvolatile content 26.8% by weight), which is a reaction product of tetracarboxylic dianhydride and dimer diamine, was synthesized according to the following Synthesis Example 1.

<Synthesis example 1>
300.0 g of tetracarboxylic dianhydride (“BisDA-1000” manufactured by SABIC Japan GK) 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. Tosoh's "TSK standard polystyrene" 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 created using 500, 1,050, and 500 materials and the molecular weight was calculated.

(Examples 1 to 3 and Comparative Examples 1 to 3)
The components shown in Table 2 below were blended in the blending amounts shown in Table 2 below (unit: parts by weight of solid content) and stirred at room temperature until a uniform solution was obtained to obtain a resin material.

Preparation of resin film:
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, 2 minutes in a gear oven at 100 ° C. It was dried for 30 seconds 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.

(Evaluation)
(1) Dielectric Dissipation Factor The obtained resin film was heated at 190 ° C. for 90 minutes to obtain a cured product. The obtained cured product was cut into a size of 2 mm in width and 80 mm in length, and 10 sheets were superposed, and "Cavity Resonance Permittivity Measuring Device CP521" manufactured by Kanto Denshi Applied Development Co., Ltd. and "Keysight Technology Co., Ltd." Using a network analyzer N5224A PNA, the dielectric loss tangent was measured by the cavity resonance method at room temperature (23 ° C.) and at a frequency of 5.8 GHz.

[Criteria for determining dielectric loss tangent]
◯: Dissipation factor is less than 3 × 10 ^-3 ×: Dissipation factor is 3 × 10 ^-3 or more

(2) Thermal dimensional stability (coefficient of linear expansion (CTE))
The obtained resin film (B stage film) having a thickness of 40 μm was heated at 190 ° C. for 90 minutes, and the obtained cured product was cut into a size of 3 mm × 25 mm. Using a thermomechanical analyzer (“EXSTAR TMA / SS6100” manufactured by SII Nanotechnology Co., Ltd.), the cured product was cut at 25 ° C to 150 ° C under the conditions of a tensile load of 33 mN and a heating rate of 5 ° C / min. The coefficient of linear expansion (ppm / ° C.) up to was calculated.

[Criteria for determining the coefficient of linear expansion]
○ ○: Average coefficient of linear expansion is 25 ppm / ° C or less ○: Average coefficient of linear expansion exceeds 25 ppm / ° C and is 29 ppm / ° C or less ×: Average coefficient of linear expansion exceeds 29 ppm / ° C

(3) Elongation characteristics The obtained resin film (B stage film) having a thickness of 40 μm was heated at 190 ° C. for 90 minutes, and the obtained cured product was cut into a size of 10 mm × 100 mm. Using a tensile tester (“AGS-J 100N” manufactured by SHIMADZU), measurements were made under the conditions of a distance between chucks of 60 mm and a tensile speed of 5 mm / min, and the maximum elongation was measured. The initial tension was 0.35 N. The measurement was repeated 5 times, and the average value of the elongation at break (average elongation at break) was calculated.

[Criteria for elongation characteristics]
○ ○: Average breaking elongation is 1.5% or more ○: Average breaking elongation is 1.2% or more and less than 1.5% ×: Average breaking elongation is less than 1.2%

(4) Desmia (removability of residue on the bottom of via)
Laminating / semi-hardening:
The obtained resin film was vacuum-laminated on a CCL substrate (“E679FG” manufactured by Hitachi Kasei Kogyo Co., Ltd.) and heated at 130 ° C. for 30 minutes and 170 ° C. for 30 minutes to be semi-cured. In this way, a laminated body A in which a semi-cured product of a resin film was laminated on a CCL substrate was obtained.

Via (through hole) formation:
Using a CO ₂ laser (manufactured by Hitachi Via Mechanics) on the semi-cured resin film of the obtained laminate A, a via (penetration) having a diameter of 60 μm at the upper end and a diameter of 40 μm at the lower end (bottom). A hole) was formed. In this way, a laminated body B in which the semi-cured product of the resin film was laminated on the CCL substrate and vias (through holes) were formed in the semi-cured product of the resin film was obtained.

Removal of residue on the bottom of the via:
(A) Swelling treatment The obtained laminate B was placed in a swelling solution at 60 ° C. (“Swelling Dip Securigant P” manufactured by Atotech Japan) and shaken for 10 minutes. Then, it was washed with pure water.

(B) Permanganate treatment (roughening treatment and desmear treatment)
The swelling-treated laminate B 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, after treating for 2 minutes with a cleaning solution at 25 ° C. (“Reduction Securigant P” manufactured by Atotech Japan), cleaning with pure water was performed to obtain evaluation sample 1.

The bottom of the via of the evaluation sample 1 was observed with a scanning electron microscope (SEM), and the maximum smear length from the wall surface of the bottom of the via was measured. The removability of the residue on the bottom of the via was judged according to the following criteria.

[Criteria for removing residue on the bottom of vias]
○ ○: Maximum smear length is less than 1 μm ○: Maximum smear length is 1 μm or more and less than 3 μm ×: Maximum smear length is 3 μm or more

The structures, compositions and results of Compound A and Compound B are shown in Tables 1 and 2 below.

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

Claims (17)

With thermosetting compounds
Compound A having two or more reactive functional groups capable of reacting with the thermosetting compound and a hydrophilic unit having a total of two or more oxygen atoms, nitrogen atoms and sulfur atoms.
Including with inorganic filler
In the compound A, two or more of the reactive functional groups are each bound to the hydrophilic unit via a chain skeleton.
In the compound A, the number of atoms in the linear portion of the chain skeleton connecting the reactive functional group and the hydrophilic unit is 4 or more.
A resin material in which the content of the inorganic filler is 10% by weight or more in 100% by weight of the component excluding the solvent in the resin material. The resin material according to claim 1, wherein the chain skeleton has a hydrolyzable bond. The resin material according to claim 2, wherein the hydrolyzable bond is an ester bond. The resin material according to any one of claims 1 to 3, wherein the hydrophilic unit has rotational symmetry. The resin material according to any one of claims 1 to 4, wherein the hydrophilic unit has an isocyanuric acid skeleton or a diphenyl sulfone skeleton. The resin material according to any one of claims 1 to 5, wherein the reactive functional group is an epoxy group, a maleimide group, an active ester group, a phenolic hydroxyl group, a thiol group, or a vinyl group. The resin material according to any one of claims 1 to 6, wherein the thermosetting compound is an epoxy compound, a maleimide compound, a benzoxazine compound, or a vinyl compound. The thermosetting compound is an epoxy compound.
The resin material according to any one of claims 1 to 7, wherein the epoxy compound contains a glycidyl ester epoxy compound. The resin material according to any one of claims 1 to 8, wherein the content of the compound A is 25% by weight or less in a total of 100% by weight of the thermosetting compound and the compound A. Contains hardener,
The resin material according to any one of claims 1 to 9, wherein the curing agent contains at least one component of a phenol compound, an active ester compound, a cyanate ester compound, and a carbodiimide compound. The resin material according to claim 10, wherein the curing agent has a molecular weight of 500 or less and contains a bifunctional curing agent. The resin material according to any one of claims 1 to 11, wherein the average particle size of the inorganic filler is 100 nm or more. The resin material according to any one of claims 1 to 12, wherein the inorganic filler is silica. The resin material according to any one of claims 1 to 13, wherein the content of the inorganic filler is 50% by weight or more in 100% by weight of the component excluding the solvent in the resin material. The resin material according to any one of claims 1 to 14, which is a resin film. The resin material according to any one of claims 1 to 15, which is used for forming an insulating layer in a multilayer printed wiring board. With the circuit board
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 at least one of the plurality of insulating layers is a cured product of the resin material according to any one of claims 1 to 16.

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