Resin material, cured product, method for producing laminate, and multilayer printed wiring board

Abstract

The invention provides a resin material which has good lamination performance and can reduce the dielectric constant and the dielectric loss tangent of a cured product. A resin material according to the present invention contains: a maleimide compound (A) having two or more maleimide groups; a thermosetting compound (B) that is a thermosetting compound having one maleimide group, or a thermosetting compound that has a functional group capable of reacting with a maleimide group and does not have a maleimide group; hollow inorganic particles (C); and a curing accelerator (D), the content of the maleimide compound (A) being 20-70% by weight (inclusive) relative to 100% by weight of components other than the solvent in the resin material.

Description

Technical Field

[0001] The present invention relates to a resin material containing a maleimide compound. Further, the present invention relates to a cured product of the resin material. Further, the present invention relates to a method for manufacturing a laminate including the cured product of the resin material and a metal layer. Further, the present invention relates to a multilayer printed wiring board using the resin material. Background Art

[0002] Conventionally, various resin materials have been used to obtain electronic components such as semiconductor devices, laminates, and printed wiring boards. For example, in a multilayer printed wiring board, a resin material is used to form an insulating layer for insulating between internal layers or an insulating layer located on the surface layer portion. A circuit made of a metal is usually laminated on the surface of the insulating layer. Further, in order to form the insulating layer, a film-like resin material (resin film) is sometimes used. The resin material is used as an insulating material for a multilayer printed wiring board including a build-up film.

[0003] Patent Document 1 below discloses a resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) hollow inorganic particles, and (C) the hollow inorganic particles satisfy specific configurations.

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2020-083966 Summary of the Invention

[0007] Technical Problem to be Solved by the Invention

[0008] As described in Patent Document 1, a resin material containing an epoxy compound and hollow inorganic particles is known. By using hollow inorganic particles, the dielectric constant and the dielectric loss tangent of the cured product of the resin material can be reduced to some extent.

[0009] However, since the specific gravity of the hollow inorganic particles is relatively small, it is difficult to improve the dispersibility of the hollow inorganic particles in the conventional resin material containing the hollow inorganic particles. When a resin material with low dispersibility of hollow inorganic particles is laminated on a laminated object part having an uneven surface, unevenness or the like sometimes occurs on the surface of the laminated resin material (the surface on the side opposite to the laminated object part), and the laminating property is reduced.

[0010] An object of the present invention is to provide a resin material that can have good lamination properties and can reduce the dielectric constant and the tangent of the dielectric loss angle of the cured product. In addition, an object of the present invention is to provide a cured product of the resin material. In addition, an object of the present invention is to provide a method for manufacturing a laminate including the cured product of the resin material and a metal layer. In addition, an object of the present invention is to provide a multilayer printed wiring board using the resin material.

[0011] Technical means for solving the problem

[0012] In this specification, the following resin materials, cured products, methods for manufacturing laminates, and multilayer printed wiring boards are disclosed.

[0013] Item 1. A resin material comprising:

[0014] A maleimide compound (A) having two or more maleimide groups; a thermosetting compound (B) which is a thermosetting compound having one maleimide group or a thermosetting compound having a functional group capable of reacting with a maleimide group and not having a maleimide group; hollow inorganic particles (C); and a curing accelerator (D). In 100% by weight of the components other than the solvent in the resin material, the content of the maleimide compound (A) is 20% by weight or more and 70% by weight or less.

[0015] Item 2. The resin material according to Item 1, wherein

[0016] The thermosetting compound (B) includes a thermosetting compound that is liquid at 25°C.

[0017] Item 3. The resin material according to Item 1 or 2, wherein

[0018] The inorganic substance forming the hollow inorganic particles (C) includes silica, aluminosilicate, or silsesquioxane.

[0019] Item 4. The resin material according to any one of Items 1 to 3, wherein

[0020] In 100% by weight of the components other than the solvent in the resin material, the content of the hollow inorganic particles (C) is 60% by weight or less.

[0021] Item 5. The resin material according to any one of Items 1 to 4, wherein

[0022] The thermosetting compound (B) includes a thermosetting compound having an epoxy group, a vinyl group, a styryl group, a benzoxazinyl group, a cyanate ester group, an allyl group, a methacryloyl group, an acryloyl group, or a maleimide group. The thermosetting compound (B) includes a thermosetting compound having an epoxy group, a vinyl group, a styryl group, a benzoxazinyl group, a cyanate ester group, an allyl group, a methacryloyl group, an acryloyl group, or a maleimide group.

[0023] Item 6. The resin material according to any one of Items 1 to 5, wherein,

[0024] The hollow inorganic particles (C) are surface-treated hollow inorganic particles.

[0025] Item 7. The resin material according to any one of Items 1 to 6, wherein,

[0026] When a cured product of the resin material is obtained by heating the resin material at 180°C for 30 minutes and then heating it at 200°C for 60 minutes, the dielectric constant of the obtained cured product at 10 GHz is 2.5 or less, and the average coefficient of linear expansion of the obtained cured product at 25°C or higher and 150°C or lower is 40 ppm / °C or less.

[0027] Item 8. The resin material according to any one of Items 1 to 7, which is a resin film.

[0028] Item 9. The resin material according to any one of Items 1 to 8, which is used to form an insulating layer in a multilayer printed wiring board.

[0029] Item 10. A cured product of a resin material, wherein the resin material is the resin material according to any one of Items 1 to 9.

[0030] Item 11. A method for manufacturing a laminate including a cured product of a resin material and a metal layer, which includes:

[0031] A step of forming a metal layer on the surface of the cured product of the resin material by a sputtering method,

[0032] The resin material is the resin material according to any one of Items 1 to 9.

[0033] Item 12. A multilayer printed wiring board, which includes: a circuit board, a plurality of insulating layers disposed on the surface of the circuit board, and a metal layer disposed between the plurality of insulating layers, and at least one layer of the plurality of insulating layers is a cured product of the resin material according to any one of Items 1 to 9.

[0034] Advantages of the Invention

[0035] The resin material of the present invention comprises: a maleimide compound (A) having two or more maleimide groups; a thermosetting compound (B) which is a thermosetting compound having one maleimide group or a thermosetting compound having a functional group capable of reacting with a maleimide group and not having a maleimide group; hollow inorganic particles (C); and a curing accelerator (D). In the resin material of the present invention, based on 100% by weight of the components other than the solvent in the resin material, the content of the maleimide compound (A) is 20% by weight or more and 70% by weight or less. In the resin material of the present invention, due to the above constitution, good laminability can be achieved, and the dielectric constant and the dielectric loss tangent of the cured product can be reduced. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 Figure 1 is a schematic cross-sectional view of a multilayer printed wiring board using the resin material of one embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0037] Hereinafter, the details of the present invention will be described.

[0038] (Resin Material)

[0039] The resin material of the present invention comprises: a maleimide compound (A) having two or more maleimide groups; a thermosetting compound (B) which is a thermosetting compound having one maleimide group or a thermosetting compound having a functional group capable of reacting with a maleimide group and not having a maleimide group; hollow inorganic particles (C); and a curing accelerator (D). In the resin material of the present invention, based on 100% by weight of the components other than the solvent in the resin material, the content of the maleimide compound (A) is 20% by weight or more and 70% by weight or less. The resin material of the present invention may optionally contain the solvent.

[0040] In the resin material of the present invention, due to the above constitution, good laminability can be achieved, and the dielectric constant and the dielectric loss tangent of the cured product can be reduced.

[0041] In the resin material of the present invention, since the hollow inorganic particles (C) are used, the dielectric constant and the dielectric loss tangent of the cured product can be reduced. Further, in the resin material of the present invention, in addition to the hollow inorganic particles (C), the thermosetting compound (B) and a specific content of the maleimide compound (A) are also used, so that good laminability can be achieved.

[0042] ​​In addition, in the resin material of the present invention, the surface roughness after the roughening treatment can be reduced, and the deviation of the surface roughness after the roughening treatment can also be suppressed. In addition, in the resin material of the present invention, the plating peeling strength of the cured product can also be improved. Therefore, the resin material of the present invention can be suitably used for applications (such as printed circuit board applications, etc.) that require these properties.

[0043] The resin material of the present invention can be a resin composition or a resin film. The resin composition has fluidity. The resin composition can be in a paste form. The paste contains a liquid phase. From the aspect of excellent operability, the resin material of the present invention is preferably a resin film.

[0044] The resin material of 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.

[0045] It should be noted that in the following description, "100% by weight of the components other than the solvent in the resin material" means 100% by weight of the components other than the solvent in the resin material when the resin material contains a solvent, and means 100% by weight of the resin material when the resin material does not contain a solvent. "100% by weight of the components other than the solvent in the resin material" means 100% by weight of the non-volatile components in the resin material. In addition, in the following description, when the resin material contains hollow inorganic particles (C) and a solvent, "100% by weight of the components other than the hollow inorganic particles (C) and the solvent in the resin material" means 100% by weight of the components other than the hollow inorganic particles (C) and the solvent in the resin material. When the resin material contains hollow inorganic particles (C) and does not contain a solvent, "100% by weight of the components other than the hollow inorganic particles (C) and the solvent in the resin material" means 100% by weight of the components other than the hollow inorganic particles (C) in the resin material. "100% by weight of the components other than the hollow inorganic particles (C) and the solvent in the resin material" means 100% by weight of the non-volatile components other than the hollow inorganic particles (C) in the resin material.

[0046] Hereinafter, the details of each component used in the resin material of the present invention, the uses of the resin material of the present invention, etc. will be described.

[0047] [Maleimide compound (A)]

[0048] The resin material contains a maleimide compound having two or more maleimide groups (maleimide compound (A)). The maleimide compound (A) is a maleimide compound having two or more maleimide groups. Only one kind of maleimide compound (A) may be used, or two or more kinds may be used in combination.

[0049] The maleimide compound (A) may have two maleimide groups, may have three or more, may have four or more, may have 800 or less, may have 500 or less, may have 300 or less.

[0050] From the viewpoint of further reducing the dielectric constant and the dielectric loss tangent of the cured product, the maleimide compound (A) is preferably a maleimide compound having two maleimide groups. Therefore, the maleimide compound (A) is preferably a bismaleimide compound.

[0051] The maleimide compound (A) preferably has an aliphatic skeleton or an alicyclic skeleton, more preferably has an aliphatic skeleton and an alicyclic skeleton. In this case, the effects of the present invention can be more effectively exerted. In addition, the scum removal property and the plating peeling strength can also be good.

[0052] Examples of the aliphatic skeleton include a chain aliphatic skeleton, etc., and examples thereof include a saturated hydrocarbon group and an unsaturated hydrocarbon group. The aliphatic skeleton is preferably an aliphatic skeleton having 4 or more carbon atoms. The number of carbon atoms of the aliphatic skeleton having 4 or more carbon atoms is preferably 5 or more, more preferably 6 or more, further preferably 7 or more, preferably 60 or less, more preferably 50 or less, further preferably 40 or less. More specifically, examples of the aliphatic skeleton include an alkyl group having 4 or more and 60 or less carbon atoms (preferably an alkyl group having 6 or more and 40 or less carbon atoms). The maleimide compound (A) may have only one kind of the aliphatic skeleton, or may have two or more kinds.

[0053] Examples of the alicyclic skeleton include a monocycloalkane ring, a bicycloalkane ring, a tricycloalkane ring, a tetracycloalkane ring, and a dicyclopentadiene ring. The maleimide compound (A) may have only one kind of the alicyclic skeleton, or may have two or more kinds.

[0054] From the viewpoint of further increasing the glass transition temperature of the cured product, the maleimide compound (A) preferably has an aromatic skeleton.

[0055] Examples of the aromatic skeleton include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a tetracene ring, a chrysene ring, a triphenylene ring, a benzanthracene ring, a pyrene ring, a pentacene ring, ring and Rings and the like. The maleimide compound (A) may have only one type of the aromatic skeleton or may have two or more types.

[0056] The maleimide compound (A) preferably has a skeleton derived from a dimer diamine. The maleimide compound (A) having a skeleton derived from a dimer diamine has an aliphatic skeleton and an alicyclic skeleton. Therefore, by using the maleimide compound (A), the dielectric constant and the dielectric loss tangent of the cured product can be further reduced.

[0057] Examples of the dimer diamine (commercially available products of the dimer diamine) include "Versamine 551" (3,4-bis(1-aminoheptyl)-6-hexyl-5-(1-octenyl)cyclohexene) manufactured by BASF JAPAN Co., Ltd., "Versamine 552" (hydride of Versamine 551) manufactured by COGNEX JAPAN Co., Ltd., "PRIAMINE 1075" and "PRIAMINE 1074" manufactured by CRODA JAPAN Co., Ltd., and the like. Only one type of the dimer diamine may be used, or two or more types may be used in combination.

[0058] The maleimide compound (A) preferably has a skeleton derived from a dimer diamine and a skeleton derived from a second diamine compound other than the dimer diamine. In this case, the effects of the present invention can be more effectively exerted.

[0059] Examples of the second diamine compound include tricyclodecane diamine, norbornane diamine, isophorone diamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, bis(aminomethyl)norbornane, 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.02,6]decane, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4'-methylenebis(cyclohexylamine), 4,4'-methylenebis(2-methylcyclohexylamine), 1,4-diaminobutane, 1,10-diaminodecane, 1,12-diaminododecane, 1,7-diaminoheptane, 1,6-diaminohexane, 1,5-diaminopentane, 1,8-diaminooctane, 1,3-diaminopropane, 1,11-diaminoundecane, 2-methyl-1,5-diaminopentane, 1,1-bis(4-aminophenyl)cyclohexane, 2,7-diaminofluorene, 4,4'-ethylenedianiline, 4,4'-methylenebis(2,6-diethylaniline), and 4,4'-methylenebis(2-ethyl-6-methylaniline). Only one type of the second diamine compound may be used, or two or more types may be used in combination.

[0060] The second diamine compound may or may not have an aliphatic skeleton. The second diamine compound may or may not have an alicyclic skeleton. The second diamine compound may or may not have an aromatic skeleton.

[0061] The second diamine compound preferably contains a diamine compound having an alicyclic skeleton other than the dimer diamine. The maleimide compound (A) preferably has a skeleton derived from the dimer diamine and a skeleton derived from a diamine compound having an alicyclic skeleton other than the dimer diamine. In this case, the effects of the present invention can be more effectively exhibited.

[0062] The diamine compound having an alicyclic skeleton other than the dimer diamine is preferably tricyclodecane diamine, norbornane diamine, or isophorone diamine. In this case, the effects of the present invention can be more effectively exhibited.

[0063] The maleimide compound (A) preferably has a skeleton derived from the acid dianhydride, more preferably has a skeleton derived from the reaction product of the diamine compound and the acid dianhydride, and further preferably has a skeleton derived from the reaction product of the dimer diamine and the acid dianhydride.

[0064] Examples of the acid dianhydride include tetracarboxylic dianhydrides. Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3',4,4'-biphenylether tetracarboxylic dianhydride, 3,3',4,4'-dimethyl diphenylsilane tetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) diphenyl sulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) diphenyl propane dianhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylether dianhydride, and bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride. The acid dianhydride may be used alone or in combination of two or more.

[0065] The molecular weight of the maleimide compound (A) is preferably 200 or more, more preferably 500 or more, further preferably 1000 or more, preferably 200,000 or less, more preferably 100,000 or less, and further preferably 50,000 or less. When the molecular weight is within the above lower limit and upper limit, a resin material having high fluidity is easily obtained during the formation of the insulating layer, and the laminating property can be made good. In addition, since the laminating property can be made good, the plating peeling strength of the cured product can be further improved.

[0066] When the maleimide compound (A) is not a polymer and the structural formula of the maleimide compound (A) can be determined, the molecular weight of the maleimide compound (A) refers to the molecular weight that can be calculated from the structural formula. In addition, when the maleimide compound (A) is a polymer, it refers to the weight-average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

[0067] Examples of commercially available products of the maleimide compound (A) include "NE-X-9470S" manufactured by DIC Corporation, "MIR-5000-60T" and "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., "BMI-3000J", "BMI-2500", "BMI-1500" and "BMI-689" manufactured by Designer Molecules Inc., and "BMI", "BMI-70" and "BMI-80" manufactured by KI-Chemical Co., Ltd. etc.

[0068] In addition, the maleimide compound (A) can be obtained, for example, by reacting an acid dianhydride such as a tetracarboxylic dianhydride with a diamine compound to obtain a reaction product, and then reacting the reaction product with maleic anhydride.

[0069] In 100% by weight of the components other than the solvent in the resin material, the content of the maleimide compound (A) is 20% by weight or more and 70% by weight or less. When the content of the maleimide compound (A) is less than 20% by weight or exceeds 70% by weight, the laminability sometimes decreases. In addition, the surface roughness after the roughening treatment sometimes becomes relatively large, or the plating peel strength of the cured product does not become high enough.

[0070] In 100% by weight of the components other than the solvent in the resin material, the content of the maleimide compound (A) is preferably 25% by weight or more, more preferably 30% by weight or more, preferably 65% by weight or less, more preferably 60% by weight or less, and further preferably 55% by weight or less. When the content of the maleimide compound (A) is above the lower limit and below the upper limit, the laminability can be made further better. In addition, the surface roughness after the roughening treatment can be further reduced, and in addition, the plating peel strength of the cured product can be further increased.

[0071] In 100% by weight of the components other than the hollow inorganic particles (C) and the solvent in the resin material, the content of the maleimide compound (A) is preferably 20% by weight or more, more preferably 30% by weight or more, preferably 90% by weight or less, and more preferably 80% by weight or less. When the content of the maleimide compound (A) is within the above lower limit and the above upper limit, the laminating property can be further improved. In addition, the surface roughness after the roughening treatment can be further reduced. Further, the plating peel strength of the cured product can be further improved.

[0072] [Thermosetting compound (B)]

[0073] The resin material contains a thermosetting compound (thermosetting compound (B)), and the thermosetting compound is a thermosetting compound having one maleimide group or a thermosetting compound having a functional group capable of reacting with a maleimide group and not having a maleimide group. The thermosetting compound (B) may be a thermosetting compound having one maleimide group, may be a thermosetting compound having a functional group capable of reacting with a maleimide group and not having a maleimide group, or may be both a thermosetting compound having one maleimide group and a thermosetting compound having a functional group capable of reacting with a maleimide group and not having a maleimide group. In the present specification, the "functional group capable of reacting with a maleimide group" possessed by the thermosetting compound (B) is sometimes referred to as "functional group (B)". Therefore, the thermosetting compound (B) is a thermosetting compound having one maleimide group or a thermosetting compound not having a maleimide group and having a functional group (B). The thermosetting compound (B) has one maleimide group or a functional group (B). The functional group (B) is different from the maleimide group. The functional group (B) is a functional group capable of reacting with a maleimide group. The thermosetting compound (B) has a functional group (maleimide group or functional group (B)) capable of reacting with the maleimide compound (A). When the thermosetting compound (B) has one maleimide group, the maleimide group possessed by the thermosetting compound (B) can react with the maleimide group possessed by the maleimide compound (A). When the thermosetting compound (B) has a functional group (B), the functional group (B) possessed by the thermosetting compound (B) can react with the maleimide group possessed by the maleimide compound (A). The thermosetting compound (B) may have one maleimide group, may have a functional group (B), or may have a functional group (B) and one maleimide group. The thermosetting compound (B) may not have a maleimide group or may not have a functional group (B). The thermosetting compound (B) may be used alone or in combination of two or more.

[0074] The thermosetting compound (B) may have 1 functional group (B), or may have 2, or may have more than 2, or may have more than 3, or may have more than 4, or may have 800 or less, or may have 500 or less, or may have 300 or less.

[0075] Examples of the functional group (B) include an epoxy group, a vinyl group, a styryl group, a benz oxazinyl group, a cyanate ester group, an allyl group, a methacryloyl group, an acryloyl group, a hydroxyl group, a thiol group, and an amino group, etc. The thermosetting compound (B) may have only 1 kind of functional group (B), or may have 2 or more kinds.

[0076] The thermosetting compound (B) preferably contains a thermosetting compound having an epoxy group, a vinyl group, a styryl group, a benz oxazinyl group, a cyanate ester group, an allyl group, a methacryloyl group, an acryloyl group, a hydroxyl group, a thiol group, an amino group or a maleimide group. The thermosetting compound (B) more preferably contains a thermosetting compound having an epoxy group, a vinyl group, a styryl group, a benz oxazinyl group, a cyanate ester group, an allyl group, a methacryloyl group, an acryloyl group or a maleimide group. The thermosetting compound (B) further preferably contains a thermosetting compound having an epoxy group, a vinyl group, a styryl group or a maleimide group, and particularly preferably contains a thermosetting compound having a styryl group. In this case, the effects of the present invention can be more effectively exerted.

[0077] From the viewpoint of further reducing the dielectric constant and the dielectric loss tangent of the cured product and making the coefficient of linear thermal expansion (CTE) of the cured product good, the thermosetting compound (B) preferably contains a thermosetting compound that is liquid at 25°C, and more preferably contains a thermosetting compound that is liquid at 25°C and a thermosetting compound that is solid at 25°C. Especially when the thermosetting compound (B) contains a thermosetting compound that is liquid at 25°C, it is easy to obtain a resin material with high fluidity when forming the insulating layer, and the laminating property can be made good. In addition, since the laminating property can be made good, the plating peeling strength of the cured product can be further improved.

[0078] The viscosity of the thermosetting compound that is liquid at 25°C is preferably 10000 mPa·s or less at 25°C, and more preferably 5000 mPa·s or less.

[0079] The viscosity of the thermosetting compound (B) can be measured, for example, using a dynamic viscoelasticity measuring device (such as "VAR-100" manufactured by REOLOGICA·INSTRUMENTS).

[0080] The molecular weight of the thermosetting compound (B) is preferably 100 or more, more preferably 200 or more, still more preferably 300 or more, preferably 200,000 or less, more preferably 100,000 or less, still more preferably 50,000 or less. When the molecular weight is within the above lower limit and the above upper limit, a resin material with high fluidity can be easily obtained during the formation of the insulating layer, and good laminability can be achieved. In addition, since good laminability can be achieved, the plating peel strength of the cured product can be further improved.

[0081] When the thermosetting compound (B) is not a polymer and the structural formula of the thermosetting compound (B) can be determined, the molecular weight refers to the molecular weight that can be calculated from the structural formula. In addition, when the thermosetting compound (B) is a polymer, it refers to the weight-average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

[0082] In 100% by weight of the components other than the solvent in the resin material, the content of the thermosetting compound (B) is preferably 1% by weight or more, more preferably 5% by weight or more, preferably 50% by weight or less, more preferably 40% by weight or less. When the content of the thermosetting compound (B) is within the above lower limit and the above upper limit, the dielectric constant and the dielectric loss tangent of the cured product can be further reduced, and in addition, the thermal dimensional stability of the cured product can be further improved.

[0083] In 100% by weight of the components other than the hollow inorganic particles (C) and the solvent in the resin material, the content of the thermosetting compound (B) is preferably 5% by weight or more, more preferably 10% by weight or more, preferably 80% by weight or less, more preferably 70% by weight or less. When the content of the thermosetting compound (B) is within the above lower limit and the above upper limit, the dielectric constant and the dielectric loss tangent of the cured product can be further reduced, and in addition, the thermal dimensional stability of the cured product can be further improved.

[0084] In the resin material, the weight ratio of the content of the thermosetting compound (B) to the content of the maleimide compound (A) (content of the thermosetting compound (B) / content of the maleimide compound (A)) is preferably 0.1 or more, more preferably 0.2 or more, preferably 4 or less, more preferably 3 or less. If the weight ratio (content of the thermosetting compound (B) / content of the maleimide compound (A)) is within the above lower limit and the above upper limit, the effects of the present invention can be more effectively exerted.

[0085] <Thermosetting compound having one maleimide group (monofunctional maleimide compound)>

[0086] The thermosetting compound (B) may contain a thermosetting compound having one maleimide group (monofunctional maleimide compound), or may be a thermosetting compound having one maleimide group (monofunctional maleimide compound). The monofunctional maleimide compound may be used alone or in combination of two or more kinds.

[0087] Examples of the monofunctional maleimide compound include N-phenylmaleimide, N-propylmaleimide, N-laurylmaleimide, and N-cyclohexylmaleimide.

[0088] The monofunctional maleimide compound is preferably N-phenylmaleimide. In this case, the effects of the present invention can be more effectively exerted.

[0089] In 100% by weight of the components other than the solvent in the resin material, the content of the monofunctional maleimide compound is preferably 1% by weight or more, more preferably 5% by weight or more, preferably 50% by weight or less, and more preferably 40% by weight or less. When the content of the monofunctional maleimide compound is above the lower limit and below the upper limit, the dielectric constant and the dielectric loss tangent of the cured product can be further reduced, and in addition, the thermal dimensional stability of the cured product can be further improved.

[0090] <Thermosetting compound having an epoxy group (epoxy compound)>

[0091] The thermosetting compound (B) may contain a thermosetting compound having an epoxy group (epoxy compound), or may be a thermosetting compound having an epoxy group (epoxy compound). The epoxy compound may be used alone or in combination of two or more kinds.

[0092] Examples of the epoxy compound include: bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, bisphenol E type epoxy compound, phenol novolac type epoxy compound, cresol novolac type epoxy compound, biphenyl type epoxy compound, biphenol novolac type epoxy compound, biphenol type epoxy compound, 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 having an adamantane skeleton, epoxy compound having a tricyclodecane skeleton, naphthylene ether type epoxy compound, and epoxy compound having a triazine nucleus in the skeleton.

[0093] The epoxy compound may be a glycidyl ether compound. The glycidyl ether compound refers to a compound having at least one glycidyl ether group.

[0094] The epoxy compound preferably includes an epoxy compound having an aromatic ring, more preferably includes an epoxy compound having a naphthalene skeleton or a phenyl skeleton, and further preferably is an epoxy compound having an aromatic ring. In this case, the dielectric constant and the dielectric loss tangent of the cured product can be further reduced, and the thermal dimensional stability of the cured product can be further improved.

[0095] From the viewpoint of further reducing the dielectric constant and the dielectric loss tangent of the cured product and having a good coefficient of linear expansion (CTE) of the cured product, the epoxy compound preferably includes an epoxy compound that is liquid at 25°C, more preferably includes an epoxy compound that is liquid at 25°C and an epoxy compound that is solid at 25°C. In particular, when the epoxy compound includes an epoxy compound that is liquid at 25°C, it is easy to obtain a resin material with high fluidity when forming the insulating layer, and the laminating property can be made good. In addition, since the laminating property can be made good, the plating peeling strength of the cured product can be further improved.

[0096] The viscosity of the epoxy compound that is liquid at 25°C is preferably 10000 mPa·s or less, more preferably 5000 mPa·s or less at 25°C.

[0097] The viscosity of the epoxy compound can be measured using a dynamic viscoelasticity measuring device (such as "VAR-100" manufactured by REOLOGICA·INSTRUMENTS).

[0098] The molecular weight of the epoxy compound is more preferably 1000 or less. In this case, it is easy to obtain a resin material with high fluidity when forming the insulating layer, and the laminating property can be made good. In addition, since the laminating property can be made good, the plating peeling strength of the cured product can be further improved. The molecular weight of the epoxy compound can be 50 or more, and can also be 100 or more.

[0099] The molecular weight of the epoxy compound, in the case where the epoxy compound is not a polymer and the structural formula of the epoxy compound can be determined, refers to the molecular weight that can be calculated from the structural formula. In addition, when the epoxy compound is a polymer, it refers to the weight-average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

[0100] In 100% by weight of the components other than the solvent in the resin material, the content of the epoxy compound is preferably 1% by weight or more, more preferably 5% by weight or more, preferably 50% by weight or less, and more preferably 40% by weight or less. When the content of the epoxy compound is above the lower limit and below the upper limit, the dielectric constant and the dielectric loss tangent of the cured product can be further reduced, and in addition, the thermal dimensional stability of the cured product can be further improved.

[0101] <Thermosetting compound having a vinyl group (vinyl compound)>

[0102] The thermosetting compound (B) may contain a thermosetting compound having a vinyl group (vinyl compound), or may be a thermosetting compound having a vinyl group (vinyl compound). Only one kind of the vinyl compound may be used, or two or more kinds may be used in combination.

[0103] Examples of the vinyl compound include divinyl benzyl ether compounds.

[0104] In 100% by weight of the components other than the solvent in the resin material, the content of the vinyl compound is preferably 1% by weight or more, more preferably 5% by weight or more, preferably 50% by weight or less, and more preferably 40% by weight or less. When the content of the vinyl compound is within the above lower limit and upper limit, the dielectric constant and the dielectric loss tangent of the cured product can be further reduced, and in addition, the thermal dimensional stability of the cured product can be further improved.

[0105] <Thermosetting compound having a cyanate group (cyanate compound)>

[0106] The thermosetting compound (B) may contain a thermosetting compound having a cyanate group (cyanate compound), or may be a thermosetting compound having a cyanate group (cyanate compound). Only one kind of the cyanate compound may be used, or two or more kinds may be used in combination.

[0107] The cyanate compound is preferably a cyanate ester compound.

[0108] Examples of the cyanate compound include novolak type cyanate resin, bisphenol type cyanate resin, and prepolymers obtained by partially trimerizing them. Examples of the novolak type cyanate resin include phenol novolak type cyanate resin and alkylphenol type cyanate resin. Examples of the bisphenol type cyanate resin include bisphenol A type cyanate resin, bisphenol E type cyanate resin, and tetramethyl bisphenol F type cyanate resin.

[0109] Examples of commercially available products of the cyanate compound include bisphenol A type cyanate resin ("P-201" manufactured by MITSUBISHI GAS CHEMICAL), phenol novolak type cyanate resin ("PT-30" and "PT-60" manufactured by LONZA JAPAN), and prepolymers obtained by trimerizing bisphenol type cyanate resin ("BA-230S", "BA-3000S", "BTP-1000S", and "BTP-6020S" manufactured by LONZA JAPAN), etc.

[0110] In 100% by weight of the components other than the solvent in the resin material, the content of the cyanate ester compound is preferably 1% by weight or more, more preferably 5% by weight or more, preferably 50% by weight or less, and more preferably 40% by weight or less. When the content of the cyanate ester compound is above the lower limit and below the upper limit, the dielectric constant and the tangent of the dielectric loss angle of the cured product can be further reduced, and in addition, the thermal dimensional stability of the cured product can be further improved.

[0111] <Having a benzo thermosetting compound with a triazine group (benzo triazine compound)>

[0112] The thermosetting compound (B) may contain a thermosetting compound having a benzo triazine group (benzo triazine compound), or may be a thermosetting compound having a benzo triazine group (benzo triazine compound). The benzo triazine compound may be used alone or in combination of two or more.

[0113] As the benzo triazine compound, examples include: P-d type benzo triazine and F-a type benzo triazine, etc.

[0114] As a commercially available product of the benzo triazine compound, examples include "P-d type" manufactured by Shikoku Kasei Kogyo Co., Ltd.

[0115] In 100% by weight of the components other than the solvent in the resin material, the content of the benzo triazine compound is preferably 1% by weight or more, more preferably 5% by weight or more, preferably 50% by weight or less, and more preferably 40% by weight or less. When the content of the benzo triazine compound is above the lower limit and below the upper limit, the dielectric constant and the tangent of the dielectric loss angle of the cured product can be further reduced, and in addition, the thermal dimensional stability of the cured product can be further improved.

[0116] <Thermosetting compound having a styryl group (styryl compound)>

[0117] The thermosetting compound (B) may contain a thermosetting compound having a styryl group (styryl compound), or may be a thermosetting compound having a styryl group (styryl compound). The styryl compound may be used alone or in combination of two or more.

[0118] As commercially available products of the styrenic compound, “OPE-2St,” “OPE-1200,” etc. manufactured by MITSUBISHI GAS CHEMICAL COMPANY can be cited.

[0119] In 100% by weight of the components other than the solvent in the resin material, the content of the styrenic compound is preferably 1% by weight or more, more preferably 5% by weight or more, preferably 50% by weight or less, and more preferably 40% by weight or less. When the content of the styrenic compound is within the above lower limit and upper limit, the dielectric constant and the dielectric loss tangent of the cured product can be further reduced, and in addition, the thermal dimensional stability of the cured product can be further improved.

[0120] <Thermosetting compound having a methacryloyl group (methacrylic acid compound)>

[0121] The thermosetting compound (B) may contain a thermosetting compound having a methacryloyl group (methacrylic acid compound), or may be a thermosetting compound having a methacryloyl group (methacrylic acid compound). Only one kind of the methacrylic acid compound may be used, or two or more kinds may be used in combination.

[0122] As commercially available products of the methacrylic acid compound, “SA9000-111” etc. manufactured by SABIC can be cited.

[0123] In 100% by weight of the components other than the solvent in the resin material, the content of the methacrylic acid compound is preferably 1% by weight or more, more preferably 5% by weight or more, preferably 50% by weight or less, and more preferably 40% by weight or less. If the content of the methacrylic acid compound is within the above lower limit and upper limit, the dielectric constant and the dielectric loss tangent of the cured product can be further reduced, and in addition, the thermal dimensional stability of the cured product can be further improved.

[0124] [Hollow inorganic particles (C)]

[0125] The resin material contains hollow inorganic particles (hollow inorganic particles (C)). Only one kind of hollow inorganic particles (C) may be used, or two or more kinds may be used in combination.

[0126] The hollow inorganic particles (C) are inorganic particles having a hollow. The hollow inorganic particles (C) have a hollow and a shell surrounding the hollow. The number of the hollows surrounded by the shell is usually one.

[0127] The hollow inorganic particles (C) are formed of an inorganic substance. More specifically, the shell of the hollow inorganic particles (C) is formed of an inorganic substance.

[0128] Examples of the inorganic substance for forming the hollow inorganic particles (C) include silica, aluminosilicate, silsesquioxane, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium phosphotungstate. Only one kind of the inorganic substance may be used, or two or more kinds may be used in combination.

[0129] The inorganic substance for forming the hollow inorganic particles (C) preferably contains silica, aluminosilicate or silsesquioxane, and preferably contains silica or aluminosilicate. The hollow inorganic particles (C) preferably contain hollow silica particles, hollow aluminosilicate particles or hollow silsesquioxane particles, and preferably contain hollow silica particles or hollow aluminosilicate particles. In this case, the dielectric constant and the dielectric loss tangent of the cured product of the resin material can be further reduced.

[0130] The average particle diameter of the hollow inorganic particles (C) is preferably 50 nm or more, more preferably 75 nm or more, still more preferably 100 nm or more, preferably 10 μm or less, more preferably 5 μm or less, and still more preferably 2 μm or less. If the average particle diameter is within the range from the lower limit to the upper limit, the surface roughness after etching can be reduced, the plating peeling strength can be improved, and in addition, the adhesion between the insulating layer and the metal layer can be further improved.

[0131] As the average particle diameter of the hollow inorganic particles (C), the value of the median diameter (d50) that becomes 50% is adopted. The average particle diameter can be measured using a particle size distribution measuring device by the laser diffraction scattering method. It should be noted that when the hollow inorganic particles (C) are aggregated particles, the average particle diameter of the hollow inorganic particles (C) refers to the primary particle diameter.

[0132] The shape of the hollow inorganic particles (C) is not particularly limited, and the hollow inorganic particles (C) are preferably spherical. In this case, the surface roughness of the surface of the cured product is effectively reduced, and further, the adhesion strength between the cured product and the metal layer is effectively improved. When the hollow inorganic particles (C) are spherical, the aspect ratio of the hollow inorganic particles (C) is preferably 2 or less, more preferably 1.5 or less.

[0133] The number of pores (the number of hollows) contained in the hollow inorganic particles (C) is not particularly limited, and is preferably 1.

[0134] The porosity of the hollow inorganic particles (C) is preferably 20% by volume or more, more preferably 30% by volume or more, still more preferably 50% by volume or more, preferably 90% by volume or less, more preferably 85% by volume or less, still more preferably 80% by volume or less. When the porosity is above the lower limit and below the upper limit, the dielectric constant and the dielectric loss tangent of the cured product of the resin material can be further reduced.

[0135] When the number of pores (the number of hollows) contained in the hollow inorganic particles (C) is 1, the porosity can be calculated as follows. Take a photograph of the hollow inorganic particles (C) using a transmission electron microscope (TEM). Measure the particle diameters of 50 arbitrary hollow inorganic particles (C) from the obtained micrograph, and take the average value thereof as the average particle diameter (X). In addition, cut the hollow inorganic particles (C) in half, and take a photograph of the cut hollow inorganic particles (C) using a transmission electron microscope (TEM). From the obtained micrograph, measure the diameters of the hollow portions of the cut surfaces of 50 arbitrarily cut hollow inorganic particles (C), and take the average value thereof as the average diameter (Y) of the hollow portions. Calculate the porosity by the following formula.

[0136] Porosity (% by volume) = (Y 3 / X 3 ) × 100

[0137] X: Average particle diameter (X)

[0138] Y: Average diameter (Y) of the hollow portions

[0139] When the number of pores (the number of hollows) contained in the hollow inorganic particles (C) is 2 or more, the porosity can also be obtained using a transmission electron microscope (TEM) based on the volume of the hollow inorganic particles (C) obtained from the particle diameter of the hollow inorganic particles (C) and the volume of the hollow portions obtained from the diameters of the hollow portions.

[0140] The hollow inorganic particles (C) are preferably surface-treated hollow inorganic particles, more preferably hollow inorganic particles surface-treated with a coupling agent. By surface-treating the hollow inorganic particles (C), the surface roughness of the surface of the cured product becomes further smaller, and the adhesive strength between the cured product and the metal layer becomes further higher. In addition, by surface-treating the hollow inorganic particles (C), finer circuits can be formed on the surface of the cured product, and better insulation reliability between circuits and interlayer insulation reliability can be imparted to the cured product.

[0141] Examples of the coupling agent include silane coupling agents, titanium coupling agents, and aluminum coupling agents. Examples of the silane coupling agent include methacrylic acid-based silanes, acrylic acid-based silanes, phenylamino silanes, phenyl silanes, imidazole silanes, vinyl silanes, alkylamino silanes, and epoxy silanes.

[0142] The hollow inorganic particles (C) are preferably hollow inorganic particles surface-treated with a silane coupling agent, more preferably hollow inorganic particles surface-treated with a vinylsilane, a phenylaminosilane, or a phenylsilane. In this case, the laminating property can be made better. Further, since the laminating property can be made good, the plating peel strength of the cured product can be further improved.

[0143] The hollow inorganic particles (C) can be produced by a conventionally known method. The hollow inorganic particles (C) can be produced, for example, by the methods described in Japanese Unexamined Patent Application Publication No. 2015-155373 and Japanese Unexamined Patent Application Publication No. 2016-121026.

[0144] In 100% by weight of the components other than the solvent in the resin material, the content of the hollow inorganic particles (C) is preferably 10% by weight or more, more preferably 15% by weight or more, preferably 60% by weight or less, more preferably 55% by weight or less, and still more preferably 50% by weight or less. When the content of the hollow inorganic particles (C) is at least the lower limit, the dielectric constant and the dielectric loss tangent of the cured product of the resin material can be further reduced. When the content of the hollow inorganic particles (C) is at least the lower limit, the thermal dimensional stability can be improved, and the warpage of the cured product can be effectively suppressed. When the content of the hollow inorganic particles (C) is at least the lower limit and at most the upper limit, the surface roughness of the surface of the cured product can be further reduced, and finer circuits can be formed on the surface of the cured product. Further, when the content of the hollow inorganic particles (C) is such, the thermal expansion rate of the cured product can be reduced, and the smear removal property can also be made good.

[0145] In the resin material, the weight ratio of the content of the hollow inorganic particles (C) to the content of the maleimide compound (A) (content of the hollow inorganic particles (C) / content of the maleimide compound (A)) is preferably 0.1 or more, more preferably 0.2 or more, preferably 3 or less, and more preferably 2.5 or less. When the weight ratio (content of the hollow inorganic particles (C) / content of the maleimide compound (A)) is at least the lower limit and at most the upper limit, the effects of the present invention can be more effectively exhibited.

[0146] In the resin material, the weight ratio of the content of the hollow inorganic particles (C) to the total content of the maleimide compound (A) and the thermosetting compound (B) (content of the hollow inorganic particles (C) / total content of the maleimide compound (A) and the thermosetting compound (B)) is preferably 0.05 or more, more preferably 0.1 or more, preferably 2 or less, and more preferably 1.5 or less. When the weight ratio (content of the hollow inorganic particles (C) / total content of the maleimide compound (A) and the thermosetting compound (B)) is at or above the lower limit and at or below the upper limit, the effects of the present invention can be more effectively exerted.

[0147] [Curing accelerator (D)]

[0148] The resin material contains a curing accelerator (curing accelerator (D)). By using the curing accelerator (D), the curing speed becomes faster. By rapidly curing the resin material, the crosslinked structure in the cured product becomes uniform, and the number of unreacted functional groups decreases, resulting in a higher crosslinking density. In addition, by using the curing accelerator (D), the resin material can be well cured even at a lower temperature. The curing accelerator (D) can be used alone or in combination of two or more.

[0149] Examples of the curing accelerator (D) include anionic curing accelerators such as imidazole compounds; cationic curing accelerators such as amine compounds; curing accelerators other than anionic and cationic curing accelerators such as organic phosphorus compounds and organometallic compounds; and free radical curing accelerators such as peroxides.

[0150] 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-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole Trimellitate, 1-cyanoethyl-2-phenylimidazole Trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-dihydroxymethylimidazole, etc.

[0151] Examples of the amine compound include diethylamine, triethylamine, diethylenetetramine, triethylenetetramine, diethylenetriamine, ethylenediamine, tris(dimethylaminomethyl)phenol, benzyldimethylamine, m-xylenedi(dimethylamine), N,N'-dimethylpiperazine, N-methylpyrrolidine, N-methylhydroxypiperidine, m-xylylenediamine, isophoronediamine, N-aminoethylpiperazine, polyoxypropylene polyamine, 4,4-dimethylaminopyridine, etc. In addition, the amine compound may also be a modified product of these amine compounds.

[0152] Examples of the organic phosphorus compound include triphenylphosphine, tricyclohexylphosphine, tribenzylphosphine, diphenyl(alkylphenyl)phosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, tris(alkylalkoxyphenyl)phosphine, tris(dialkylphenyl)phosphine, tris(trialkylphenyl)phosphine, tris(tetraalkylphenyl)phosphine, tris(dialkoxyphenyl)phosphine, tris(trialkoxyphenyl)phosphine, tris(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkylarylphosphine, alkyl diarylphosphine and other organophosphorus compounds, and tetraphenyl · Tetraphenyl borate, etc. Salt compounds, etc.

[0153] Examples of the organometallic compound include zinc naphthenate, cobalt naphthenate, tin octoate, cobalt octoate, cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, etc.

[0154] Examples of the peroxide include diacyl peroxide, peroxide ester, diperoxycarbonate, monoperoxycarbonate, peroxide ketal, dialkyl peroxide, dibenzyl peroxide, diisopropylbenzene peroxide, hydroperoxide and ketone peroxide, etc.

[0155] The curing accelerator (D) preferably contains an amine compound, an imidazole compound, a peroxide or an organic phosphorus compound, and more preferably contains an imidazole compound or a peroxide. In this case, the effects of the present invention can be more effectively exerted.

[0156] In the resin material, relative to 100 parts by weight of the total content of the maleimide compound (A) and the thermosetting compound (B), the content of the curing accelerator (D) is preferably 0.01 part by weight or more, more preferably 0.05 part by weight or more, preferably 10 parts by weight or less, and more preferably 5 parts by weight or less. When the content of the curing accelerator (D) is within the above lower limit and the above upper limit, the effects of the present invention can be more effectively exerted.

[0157] [Solvent]

[0158] The resin material does not contain a solvent or contains a solvent. The resin material optionally contains a solvent. The resin material may contain a solvent or may not contain a solvent. By using the solvent, the viscosity of the resin material can be controlled within an appropriate range, and the coatability of the resin material can be improved. In addition, the solvent can be used to obtain a slurry containing the hollow inorganic particles (C). The solvent can be used alone or in combination of two or more.

[0159] 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, N,N-dimethylformamide, methyl isobutyl ketone, N-methylpyrrolidone, n-hexane, cyclohexane, cyclohexanone, and naphtha as a mixture.

[0160] 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, and 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 according to the coatability of the resin composition and the like.

[0161] In the case where the resin material is a B-stage film, in 100% by weight of the B-stage film, the content of the solvent is preferably 1% by weight or more, more preferably 2% by weight or more, preferably 10% by weight or less, and more preferably 5% by weight or less.

[0162] [Other components]

[0163] For the purpose of improving impact resistance, heat resistance, resin compatibility, operability, etc., the resin material may contain other components in addition to the above components (maleimide compound (A), thermosetting compound (B), hollow inorganic particles (C), curing accelerator (D), and solvent). Examples of the other components include thermoplastic resins; organic fillers; inorganic fillers; leveling agents; flame retardants; coupling agents; colorants; antioxidants; anti-ultraviolet degradation agents; defoaming agents; thickeners; thixotropy imparting agents, etc. The other components may be used alone or in combination of two or more kinds.

[0164] Examples of the thermoplastic resin include polyimide resin, phenoxy resin, and polyvinyl acetal resin, etc.

[0165] Examples of the coupling agent include silane coupling agents, titanium coupling agents, and aluminum coupling agents, etc. Examples of the silane coupling agent include vinyl silane, amino silane, imidazole silane, and epoxy silane, etc.

[0166] The resin material may contain glass cloth or may not contain glass cloth. The resin material preferably does not contain glass cloth. The resin material is preferably not a prepreg.

[0167] (Resin film)

[0168] By forming the resin composition into a film shape, a resin film (B-stage product / B-stage film) is obtained. The resin material is preferably a resin film. The resin film is preferably a B-stage film.

[0169] Examples of the method for forming a resin film by forming the resin composition into a film shape include the following methods. An extrusion molding method in which the resin composition is melt-kneaded using an extruder, and after extrusion, it is formed into a film shape through a T-die or a circular die, etc. A casting molding method in which the resin composition containing a solvent is cast and formed into a film shape. Other conventionally known film forming methods. From the viewpoint of being able to cope with thinning, the extrusion molding method or the casting molding method is preferred. A film includes a sheet.

[0170] By forming the resin composition into a film shape and heating and drying it at 50 °C to 150 °C for 1 minute to 10 minutes to such an extent that curing by heat does not proceed excessively, a resin film as a B-stage film can be obtained.

[0171] The film-shaped resin composition obtained through the above drying process is called 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.

[0172] The resin film may not be a prepreg. In the case where the resin film is not a prepreg, movement along a glass cloth or the like does not occur. Further, in the case of laminating or pre-curing the resin film, unevenness caused by the glass cloth does not occur on the surface.

[0173] 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.

[0174] 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 film. The surface of the base film may be subjected to a release treatment as needed.

[0175] From the viewpoint of further uniformly controlling the degree of curing of the resin film, the thickness of the resin film is preferably 5 μm or more and preferably 200 μm or less. In the case where the resin film is used as an insulating layer of a circuit, the thickness of the insulating layer formed by the resin film is preferably equal to or greater 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.

[0176] (Other details of the resin material)

[0177] In 100% by weight of the components other than the solvent in the resin material, the total content of the maleimide compound (A), the thermosetting compound (B), and the hollow inorganic particles (C) is preferably 80% by weight or more, more preferably 85% by weight or more, still more preferably 90% by weight or more, preferably less than 100% by weight, and more preferably 99% by weight or less. When the total content is equal to or greater than the lower limit and equal to or less than (or less than) the upper limit, the effects of the present invention can be more effectively exhibited.

[0178] When a cured product of the resin material is obtained by heating the resin material at 180 °C for 30 minutes and then heating at 200 °C for 60 minutes, the dielectric constant (Dk) of the obtained cured product at 10 GHz is preferably 3.0 or less, more preferably 2.5 or less, still more preferably 2.0 or less. The dielectric constant (Dk) of the cured product at 10 GHz can be 1.5 or more.

[0179] The dielectric constant (Dk) of the cured product at 10 GHz can be measured as follows. After heating the resin material at 180 °C for 30 minutes, it is heated at 200 °C for 60 minutes to obtain a cured product of the resin material. Using a dielectric constant measuring device (for example, "Resonant Cavity Perturbation Method Dielectric Constant Measuring Device CP521" manufactured by Kanto Electronics Application Development Co., Ltd.), the dielectric constant (Dk) of the cured product obtained is measured by the resonant cavity method under the conditions of normal temperature (23 °C) and a frequency of 10 GHz.

[0180] When obtaining a cured product of the resin material by heating the resin material at 180 °C for 30 minutes and then at 200 °C for 60 minutes, the average coefficient of thermal expansion (CTE) of the obtained cured product at 25 °C or higher and 150 °C or lower is preferably 40 ppm / °C or lower, more preferably 35 ppm / °C or lower, and further preferably 30 ppm / °C or lower. The average coefficient of thermal expansion (CTE) of the cured product at 25 °C or higher and 150 °C or lower can be 0 ppm / °C, or can be 0 ppm / °C or higher.

[0181] The average coefficient of thermal expansion (CTE) of the cured product at 25 °C or higher and 150 °C or lower can be measured as follows. After heating the resin material at 180 °C for 30 minutes, it is heated at 200 °C for 60 minutes to obtain a cured product of the resin material. Using a thermomechanical analysis device (for example, "EXSTAR TMA / SS6100" manufactured by SII NanoTechnology Inc.), the average coefficient of thermal expansion (CTE) of the obtained cured product at 25 °C or higher and 150 °C or lower is measured under the conditions of a tensile load of 33 mN and a heating rate of 5 °C / minute.

[0182] It should be noted that when manufacturing components such as a multilayer substrate using the resin material, a cured product can be obtained by heating at 180 °C for 30 minutes and then at 200 °C for 60 minutes, or a cured product can be obtained by heating the resin material under heating conditions other than these heating conditions.

[0183] The resin material can be used for various purposes. The resin material is, for example, suitable for use as a molding resin for embedding a semiconductor chip in a semiconductor device. In addition, the resin material is suitable for alternative uses of liquid crystal polymer (LCP), millimeter-wave antenna uses, and redistribution layer uses. The resin material is not limited to the above uses and is suitable for the overall use of circuit formation.

[0184] The resin material is suitable as an adhesive material. The resin material is, for example, suitable as an adhesive material for power cover packaging, an adhesive material for printed circuit boards, an adhesive material for the cover layer of flexible printed circuit boards, and an adhesive material for semiconductor bonding. The resin material is preferably an adhesive material.

[0185] The resin material is suitable for use as an insulating material. The resin material is suitable for forming an insulating layer in a printed circuit board, and is more suitable for forming an insulating layer in a multi-layer printed circuit board. The resin material is preferably an insulating material, and more preferably an interlayer insulating material. The insulating material may also function as an adhesive material.

[0186] The cured product of the present invention is a cured product of the resin material cured from the resin material. The cured product of the present invention is a cured product of a resin material, and the resin material is the above-mentioned resin material. The cured product of the present invention can be obtained by curing the resin material. The heating conditions of the resin material when obtaining the cured product of the present invention are not particularly limited as long as the resin material is cured.

[0187] Using the resin material, a laminate having a cured product of the resin material and a metal layer can be manufactured. In the laminate, a metal layer is disposed on the surface of the cured product. The manufacturing method of the laminate preferably includes a step of forming a metal layer on the surface of the cured product of the resin material (the above-mentioned resin material) by a sputtering method. The metal layer formed by the sputtering method can be a seed layer. The metal layer formed by the sputtering is preferably a copper layer.

[0188] (Laminate Structure and Copper Clad Laminate)

[0189] By laminating the resin film on one or both sides of a laminate object member having a metal layer on the surface, a laminate structure can be obtained. The laminate structure includes a laminate object member having a metal layer on the surface and a resin film laminated on the surface of the metal layer, and the resin film is the resin material. The method of laminating the resin film and the laminate object member is not particularly limited, and a known method can be used. For example, a device such as a parallel plate press or a roll laminator can be used to apply pressure with or without heating to laminate the resin film on the laminate object member.

[0190] The material of the metal layer is preferably copper.

[0191] The laminate object member having a metal layer on the surface can be a metal foil such as a copper foil.

[0192] The resin material is suitable for obtaining a copper clad laminate. As an example of the copper clad laminate, a copper clad laminate having a copper foil and a resin film laminated on one surface of the copper foil, and the resin film is the resin material can be cited.

[0193] The thickness of the copper foil of the copper-clad laminate is not particularly limited. The thickness of the copper foil is preferably 1 μm or more and 100 μm or less. In addition, in order to improve the adhesion strength between the cured product of the resin material and the copper foil, the copper foil preferably has fine irregularities on its surface. The method for forming the irregularities is not particularly limited. Examples of the method for forming the irregularities include a method based on treatment with a known chemical solution, a method based on known plasma treatment, and a method based on known UV treatment, etc.

[0194] (Circuit board with insulating layer)

[0195] The resin material is suitable for obtaining a circuit board with an insulating layer. As an example of the circuit board with an insulating layer, there can be cited a circuit board with an insulating layer that includes a circuit board and an insulating layer disposed on the surface of the circuit board, and the insulating layer is a cured product of the resin material.

[0196] In the circuit board with an insulating layer, the insulating layer is preferably laminated on the surface of the circuit board where the circuit is provided. In the circuit board with an insulating layer, a part of the insulating layer is preferably buried between the circuits.

[0197] The circuit board with an insulating layer can be obtained by a conventionally known method.

[0198] (Multilayer substrate and multilayer printed wiring board)

[0199] The resin material is applicable to obtaining a multilayer substrate. As an example of the multilayer substrate, there can be cited a multilayer substrate that includes a circuit board and an insulating layer laminated on the circuit board. The insulating layer of the multilayer substrate is a cured product of the resin material. The insulating layer is preferably laminated on the surface of the circuit board where the circuit (metal layer) is provided. A part of the insulating layer is preferably buried between the circuits.

[0200] In the multilayer substrate, it is preferred that the surface of the insulating layer on the side opposite to the surface on which the circuit board is laminated has been roughened.

[0201] The roughening treatment method can use a conventionally known roughening treatment method and is not particularly limited. The surface of the insulating layer can be subjected to a swelling treatment before the roughening treatment.

[0202] In addition, the multilayer substrate preferably further includes: a copper plating layer laminated on the roughened surface of the insulating layer.

[0203] The multi-layer substrate preferably includes: a seed layer (first metal layer) disposed on the roughened surface of the insulating layer, and a metal layer (second metal layer) laminated on the surface of the seed layer opposite to the insulating layer side. The multi-layer substrate may have an adhesion layer (third metal layer) between the seed layer and the insulating layer.

[0204] The seed layer (first metal layer) is preferably a copper layer. The seed layer can be formed, for example, by sputtering treatment and electroless plating treatment. As the electroless plating treatment, electroless copper plating, etc. can be cited. From the viewpoint of further improving the adhesion between the insulating layer and the metal layer, the seed layer is preferably formed by sputtering treatment. The seed layer is preferably a sputtered layer.

[0205] The metal layer (second metal layer) is preferably a copper-plated layer.

[0206] As the adhesion layer (third metal layer), a titanium layer, etc. can be cited.

[0207] A multi-layer substrate including an insulating layer, a seed layer (first metal layer), and a metal layer (second metal layer) can be manufactured, for example, in the following manner. After heating the resin material at 180°C for 30 minutes, the surface of the cured product is roughened. Then, a seed layer (first metal layer) is formed by sputtering treatment and electroless plating treatment. Then, electroplating is performed to form a metal layer (second metal layer). Then, the cured product is heated at 200°C for 60 minutes to further cure the cured product. It should be noted that by forming an adhesion layer (third metal layer) by sputtering or the like before forming the seed layer (first metal layer), a multi-layer substrate including an insulating layer, an adhesion layer (third metal layer), a seed layer (first metal layer), and a metal layer (second metal layer) can be obtained. It should be noted that the curing conditions of the resin material are an example. When manufacturing the multi-layer substrate, as described above, it may be the condition of heating the resin material at 180°C for 30 minutes and then at 200°C for 60 minutes, or it may be conditions other than this condition.

[0208] The peel strength (coating peel strength) of the metal layer (the laminated metal layer of the first metal layer, the second metal layer, and the third metal layer) with respect to the insulating layer is preferably 0.2 kgf / cm or more, more preferably 0.3 kgf / cm or more, and further preferably 0.4 kgf / cm or more.

[0209] The peel strength can be measured in the following manner. Strip-shaped incisions each 10 mm wide are formed at 5-mm intervals on the surface side of the second metal layer, for a total of six locations. In a 90° peel tester (e.g., "TE-3001" manufactured by TESTER SANGYO Co., Ltd.), a cured product having the metal layer (the first to third metal layers) disposed on its upper surface is set. The end portions of the metal layer (the first to third metal layers) where the incisions are made are pinched with a jig, and the metal layer (the first to third metal layers) is peeled by 20 mm, and the peel strength is measured. The peel strength is measured for each of the six incision sites, and the average value thereof is taken as the peel strength of the metal layer (the first to third metal layers).

[0210] As other examples of the multilayer substrate, there can be mentioned: a multilayer substrate including a circuit board, an insulating layer laminated on the surface of the circuit board, and a copper foil laminated on the surface of the insulating layer on the side opposite to the surface on which the circuit board is laminated. The insulating layer is preferably formed by the following method: using a copper-clad laminate including a copper foil and a resin film laminated on one surface of the copper foil, and curing the resin film. Further, the copper foil is preferably a copper circuit that has been subjected to an etching process.

[0211] As other examples of the multilayer substrate, there can be mentioned: a multilayer substrate 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 disposed on the circuit board is formed using the resin material. The multilayer substrate preferably further includes: a circuit laminated on at least one surface of the insulating layer formed using the resin film.

[0212] The resin material is suitable for forming an insulating layer in a multilayer printed wiring board.

[0213] The multilayer printed wiring board includes, for example: a circuit board, a plurality of insulating layers disposed on the surface of the circuit board, and a metal layer disposed between the plurality of insulating layers. In the multilayer printed wiring board, at least one of the insulating layers is a cured product of the resin material.

[0214] Figure 1 It is a cross-sectional view schematically showing a multilayer printed wiring board using the resin material of one embodiment of the present invention.

[0215] Figure 1In the multi-layer printed circuit board 11 shown, 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 layers. A metal layer 17 is formed in a part of the region of the upper surface 12a of the circuit board 12. Among the plurality of insulating layers 13 to 16, in the insulating layers 13 to 15 other than the insulating layer 16 on the surface on the outer side opposite to the circuit board 12 side, a metal layer 17 is formed in a part of the upper surface region. The metal layer 17 is a circuit. The metal layers 17 are respectively provided between the circuit board 12 and the insulating layer 13 and between the respective layers of the laminated insulating layers 13 to 16. 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).

[0216] In the multi-layer printed circuit 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, micropores (not shown) are formed on the surfaces of the insulating layers 13 to 16. In addition, the metal layer 17 extends into the interior of the micropores. In addition, in the multi-layer printed circuit 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. In addition, in the multi-layer printed circuit board 11, good insulation reliability is imparted between the upper metal layer and the lower metal layer that are not connected by a via-hole connection and a through-hole connection (not shown).

[0217] Hereinafter, the present invention will be specifically described by giving examples and comparative examples. The present invention is not limited to the following examples.

[0218] Prepare the following materials.

[0219] (Maleimide compound (A))

[0220] Maleimide compound (A1) ("BMI3000J" manufactured by Designer Molecules Inc., a maleimide compound having an aliphatic skeleton, number of maleimide groups: 2, weight average molecular weight: 3000)

[0221] Maleimide compound (A2) ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., a maleimide compound having an aromatic skeleton)

[0222] Maleimide compound (A3) (synthesized according to Synthesis Example A3 below, number of maleimide groups: 2, weight average molecular weight: 10,000)

[0223] Maleimide compound (A4) (synthesized according to Synthesis Example A4 below, number of maleimide groups: 2, weight average molecular weight: 8,700)

[0224] <Synthesis Example A3>

[0225] In a reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen inlet tube, 135.0 g of a tetracarboxylic dianhydride (“BisDA-1000” manufactured by SABIC JAPAN Co., Ltd.) and 400 g of cyclohexanone were added, and the solution in the reaction vessel was heated to 60°C. Then, 17.5 g of 1,3-bis(aminomethyl)cyclohexane (manufactured by MITSUBISHI GAS CHEMICAL COMPANY, molecular weight 142.25) was added dropwise to the reaction vessel and reacted to obtain a reaction product with acid anhydride groups at both ends. Then, 148 g of a dimer diamine (“PRIAMINE 1075” manufactured by CRODA JAPAN Co., Ltd.) was slowly added to the reaction vessel, and then 60.0 g of methylcyclohexane was added to the reaction vessel. A Dean-Stark separator and a condenser were installed on the flask, and the mixture was heated to reflux for 2 hours to obtain an imide compound having an amine structure at both ends. Then, 28 g of maleic anhydride was added, and the resulting mixture was further refluxed for 12 hours for maleimidation. After the reaction was completed, isopropyl alcohol was added, and after reprecipitation, the precipitate was recovered and dried. Thus, an N-alkylbismaleimide compound having a skeleton derived from a dimer diamine and a skeleton derived from a diamine compound other than the dimer diamine (weight average molecular weight: 10,000) was obtained. The recovery rate of the obtained N-alkylbismaleimide compound was 83%.

[0226] <Synthesis Example A4>

[0227] In a reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen inlet tube, 55 g of pyromellitic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 254.15) and 300 g of cyclohexanone were added, and the solution in the reaction vessel was heated to 60°C. Then, a solution prepared by dissolving 26.7 g of bis(aminomethyl)norbornane (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 154.26) in cyclohexanone was added dropwise to the reaction vessel to cause a reaction, and a reaction product with acid anhydride groups at both ends was obtained. Then, isopropanol was added to recover the imide compound with acid anhydride groups at both ends. Next, the precipitate was dissolved in cyclohexanone again, and after slowly adding 46.0 g of a dimer diamine (“PRIAMINE 1075” manufactured by CRODA JAPAN Co., Ltd.) to the reaction vessel, 45.0 g of methylcyclohexane was added to the reaction vessel. A Dean-Stark separator and a condenser were installed on the flask, and the mixture was heated to reflux for 2 hours to obtain an imide compound having a dimer diamine structure at both ends. Then, 8.7 g of maleic anhydride was added, and the resulting mixture was further refluxed for 12 hours for maleimidation. Then, after the reaction was completed, isopropanol was added, and after reprecipitation, the precipitate was recovered and dried. Thus, a bismaleimide compound (weight-average molecular weight: 8700) having a skeleton derived from a dimer diamine and a skeleton derived from a diamine compound other than the dimer diamine was obtained. The obtained bismaleimide compound has a skeleton derived from a dimer diamine only at both ends of the main chain. The yield of the obtained bismaleimide compound was 70%.

[0228] (Thermosetting compound (B))

[0229] Low molecular weight polyphenylene ether·styrene compound (“OPE-2St” manufactured by Mitsubishi Gas Chemical Company, Inc.)

[0230] Polyphenylene ether·methacrylic acid compound (“SA9000-111” manufactured by SABIC, solid at 25°C)

[0231] Biphenyl type epoxy compound (“NC3000” manufactured by Nippon Kayaku Co., Ltd., solid at 25°C)

[0232] N-Phenylmaleimide (solid at 25°C)

[0233] Cyanate ester compound-containing liquid (“BA-3000S” manufactured by Lonza Japan Co., Ltd., solid content 75% by weight)

[0234] P-d type benz oxazine (“P-d” manufactured by Shikoku Chemicals Corporation, solid at 25°C)

[0235] Divinylbenzene (viscosity at 25°C: 1 mPa·s)

[0236] Bisphenol A cyanate resin (“P-201” manufactured by MITSUBISHI GAS CHEMICAL COMPANY, viscosity at 25°C: 100 mPa·s)

[0237] Epoxy compound having an amino group (“630” manufactured by MITSUBISHI CHEMICAL COMPANY, viscosity at 25°C: 750 mPa·s)

[0238] (Hollow inorganic particles (C))

[0239] Hollow silica particles 1 (particles obtained by subjecting the particles prepared according to the following production method C1 to surface treatment according to the following surface treatment method C1, surface treatment product based on vinylsilane, average particle diameter: 1 μm, porosity: 50 vol%)

[0240] Hollow silica particles 2 (particles prepared according to the following production method C1, not subjected to surface treatment, average particle diameter: 1 μm, porosity: 50 vol%)

[0241] Hollow aluminosilicate particles (particles obtained by subjecting commercially available hollow aluminosilicate particles (“CellSpheres NF” manufactured by TAIHEIYO CEMENT CORPORATION) to surface treatment according to the following surface treatment method C1, surface treatment product based on vinylsilane, average particle diameter: 1 μm, porosity: 75 vol%)

[0242] <Production method C1>

[0243] Add 4.5 g of an EO-PO-EO block copolymer (EO80-PO30-EO80, “PLURONIC (registered trademark) F68” manufactured by ADEKA CORPORATION) to 965.5 g of pure water and stir until dissolved. After adding 30 g of n-dodecane to the resulting aqueous solution, pre-emulsify using a shaft generator (“T50 digital ULTRA TURRAX” manufactured by IKA WORKS, INC.). Then, perform three emulsification operations at a pressure of 40 MPa using a high-pressure emulsifier (“LAB2000” manufactured by SMT Co., Ltd.) to obtain a fine emulsion. To the resulting fine emulsion, slowly add 30 g of a diluted sodium silicate aqueous solution (SiO2 concentration: 10 mass%, Na2O concentration: 3.6 mass%) and 2M hydrochloric acid so that the pH becomes 2, maintain at 25°C and stir well. Then, slowly dropwise add 1M sodium hydroxide aqueous solution so that the pH becomes 6 to obtain an oil core-silica shell particle dispersion liquid.

[0244] The obtained oil core-silica shell particle dispersion was heated to 70 °C, and 1 M aqueous sodium hydroxide solution was slowly added while stirring to adjust the pH to 9. Subsequently, a diluted sodium silicate aqueous solution and 0.5 M hydrochloric acid were slowly added in such a manner that the pH was maintained around 9. Then, after maintaining at 70 °C for 2 days, it was slowly cooled to room temperature to obtain a hollow silica precursor dispersion.

[0245] The obtained hollow silica precursor dispersion was pressure-filtered (pressure: 0.28 MPa) using a hydrophilic polytetrafluoroethylene (PTFE) membrane filter with a pore size of 0.45 μm. The filtered hollow silica cake was calcined in a nitrogen atmosphere at 60 °C for 1 hour and at 400 °C for 4 hours (heating rate: 5 °C / minute) to remove organic components, thereby obtaining a hollow silica precursor. The obtained hollow silica precursor was fired at 800 °C for 4 hours (heating rate: 5 °C / minute) to obtain hollow silica particles.

[0246] <Surface treatment method C1>

[0247] 100 parts by weight of the hollow inorganic particles obtained by Preparation method C1 or 100 parts by weight of the hollow inorganic particles of a commercially available product (“CellSpheres NF” manufactured by TAIHEIYO CEMENT Corporation) were put into a Henschel mixer and heated to 100 °C while stirring. 1 part by weight of vinyltrimethoxysilane (“KBM-1003” manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed onto the stirring hollow inorganic particles. Ten minutes after the spraying was completed, the surface-treated hollow inorganic particles were recovered.

[0248] (Inorganic particles not equivalent to hollow inorganic particles)

[0249] Solid silica particles (“SFP-30M” manufactured by Denka Company, no surface treatment, average particle size: 0.6 μm)

[0250] (Curing accelerator (D))

[0251] Peroxide (“PERBUTYL P” manufactured by NOF Corporation)

[0252] Imidazole compound (2-phenyl-4-methylimidazole, “2P4MZ” manufactured by Shikoku Kasei Kogyo Co., Ltd., anionic curing accelerator)

[0253] (Examples 1 to 19 and Comparative Examples 1 to 4)

[0254] The components shown in Tables 1, 3, 5, 7, and 9 below were formulated in the formulation amounts (in parts by weight of solid components) shown in Tables 1, 3, 5, 7, and 9 below, and stirred at room temperature until a uniform solution was obtained to obtain a resin material.

[0255] Preparation of Resin Film:

[0256] After applying the obtained resin material onto the release-treated surface of a polyethylene terephthalate film (PET film, "XG284" manufactured by TORAY, thickness 25 μm) using a coater, it was dried in a gear oven at 100 °C for 2 minutes and 30 seconds to evaporate the solvent. Thus, a laminated film (a laminated film of a PET film and a resin film) in which a resin film (B-stage film) with a thickness of 40 μm was laminated on the PET film was obtained.

[0257] (Evaluation)

[0258] (1) Dielectric Constant (Dk) and Dissipation Factor (Df) of the Cured Product

[0259] The obtained resin film (B-stage film) with a thickness of 40 μm was heated at 180 °C for 30 minutes and then at 200 °C for 60 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 pieces were overlapped as a measurement sample. Using a "Resonant Cavity Perturbation Dielectric Constant Measuring Device CP521" manufactured by Kanto Electronic Application Development Co., Ltd. and a "Network Analyzer N5224A PNA" manufactured by Keysight Technologies, Inc., the dielectric constant (Dk) and dissipation factor (Df) of the cured product were measured at room temperature (23 °C) and a frequency of 10 GHz using the resonant cavity method.

[0260] [Judgment Criteria for Dielectric Constant (Dk) of the Cured Product]

[0261] ○○: Dielectric constant is 2.0 or less

[0262] ○: Dielectric constant exceeds 2.0 and is 2.5 or less

[0263] △: Dielectric constant exceeds 2.5 and is 3.0 or less

[0264] ×: Dielectric constant exceeds 3.0

[0265] [Judgment Criteria for Dissipation Factor (Df) of the Cured Product]

[0266] ○○: Dissipation factor is 0.002 or less

[0267] ○: Dissipation factor exceeds 0.002 and is 0.003 or less

[0268] △: Dissipation factor exceeds 0.003 and is 0.005 or less

[0269] ×: Dissipation factor exceeds 0.005

[0270] (2) Coefficient of Thermal Expansion (CTE) of the cured product

[0271] The obtained resin film (B-stage film) with a thickness of 40 μm was heated at 180 °C for 30 minutes and then at 200 °C for 60 minutes. The obtained cured product was cut into a size of 3 mm × 25 mm. Using a thermomechanical analysis device (for example, "EXSTAR TMA / SS6100" manufactured by SIINanoTechnology), under the conditions of a tensile load of 33 mN and a heating rate of 5 °C / minute, the average coefficient of thermal expansion (ppm / °C) of the cut cured product was calculated at temperatures above 25 °C and below 150 °C.

[0272] [Criteria for Judging the Coefficient of Thermal Expansion (CTE) of the Cured Product]

[0273] ○: The average coefficient of thermal expansion is 30 ppm / °C or less

[0274] △: The average coefficient of thermal expansion exceeds 35 ppm / °C and is 40 ppm / °C or less

[0275] ×: The average coefficient of thermal expansion exceeds 40 ppm / °C

[0276] (3) Laminability

[0277] A mask was attached to a copper layer with a thickness of 18 μm in such a way that the etched area was a rectangle with a length of 1 mm × a width of 2 mm, and the copper was etched to prepare a 100 mm square substrate with a 1 mm × 2 mm rectangular depression. Both sides of the copper foil surface of this substrate were immersed in "Cz8101" manufactured by MEC to roughen the surface of the copper foil. Using a "Batch Vacuum Laminator MVLP-500-IIA" manufactured by Meiki Seisakusho, on both sides of the roughened substrate, the resin film (B-stage film) of the laminated film was laminated on the substrate with emphasis to obtain a laminated structure. The lamination conditions were as follows: The pressure was reduced for 30 seconds to make the air pressure 13 hPa or less, and then lamination was carried out at 30 seconds, 100 °C, and a pressure of 0.7 MPa. Further, it was pressed at a pressing pressure of 0.8 MPa and a pressing temperature of 100 °C for 60 seconds. The PET film was peeled off, heated at 100 °C for 30 minutes, and then further heated at 180 °C for 30 minutes to semi-cure the resin film. The surface of the semi-cured product of the resin film in the part with the copper pattern (the surface on the side opposite to the substrate) and the surface of the semi-cured product of the resin film in the part without the copper pattern (the surface on the side opposite to the substrate) were observed, and the maximum value of the height difference between the adjacent concave and convex parts was obtained using an optical step gauge.

[0278] [Criteria for Judging Laminability]

[0279] ○: The maximum value of the height difference is less than 1.5 μm

[0280] △: The maximum value of the height difference is 1.5 μm or more and less than 2 μm

[0281] ×: The maximum value of the height difference is 2 μm or more

[0282] (4) The surface roughness after roughening treatment

[0283] Lamination process and semi-curing treatment:

[0284] Prepare a double-sided copper-clad laminate (CCL substrate) (manufactured by Showa Denko Materials Co., Ltd., "MCL-E-679FG"). Immerse both sides of the copper foil surface of the double-sided copper-clad laminate in "Cz8101" manufactured by MEC Co., Ltd. to roughen the surface of the copper foil. On both sides of the roughened copper-clad laminate, use a batch-type vacuum laminator "MVLP-500-IIA" manufactured by Meiki Seisakusho Co., Ltd. to laminate and press the resin film (B-stage film) side of the laminate film onto the copper-clad laminate to obtain a laminated structure. The lamination conditions are as follows: reduce the pressure for 30 seconds to make the air pressure 13 hPa or less, then laminate at 30 seconds, 100 °C, and a pressure of 0.7 MPa, and further press at a pressing pressure of 0.8 MPa and a pressing temperature of 100 °C for 60 seconds. Peel off the PET film and heat it at 180 °C for 30 minutes to semi-cure the resin film. In this way, a laminate with a semi-cured product having a resin film laminated on the CCL substrate is obtained.

[0285] Roughening treatment:

[0286] (a) Swelling treatment:

[0287] Place the obtained laminate in a swelling solution (manufactured by ATOTECH JAPAN Co., Ltd., "SWELLING DIP SECURIGANTH P") at 60 °C and shake for 10 minutes. Then, wash it with pure water.

[0288] (b) Permanganate treatment (roughening treatment and desmearing treatment):

[0289] Add the laminate after swelling treatment to a potassium permanganate (manufactured by ATOTECH JAPAN Co., Ltd., "CONCENTRATE COMPACT CP") roughening aqueous solution at 80 °C and shake for 30 minutes. Then, treat it with a cleaning solution (manufactured by ATOTECH JAPAN Co., Ltd., "REDUCTION SECURIGANTH P") at 25 °C for 2 minutes and then wash it with pure water to obtain evaluation sample A.

[0290] Measurement of surface roughness:

[0291] On the surface of the evaluated sample A (the roughened cured product), 10 regions of 94 μm × 123 μm were arbitrarily selected. For each of these 10 regions, the arithmetic mean roughness Ra was measured using a non-contact three-dimensional surface shape measuring device ("WYKO NT1100" manufactured by Veeco). The uniformity of the surface roughness was evaluated based on the measured arithmetic mean roughness Ra at the 10 locations. The surface roughness after the roughening treatment was evaluated based on the absolute value of the difference between the maximum and minimum values of the measured arithmetic mean roughness Ra at the 10 locations. It should be noted that the arithmetic mean roughness Ra was measured in accordance with JIS B0601:1994.

[0292] [Criterion for the surface roughness after roughening treatment]

[0293] ○○: The absolute value of the difference between the maximum and minimum values of the arithmetic mean roughness Ra is less than 25 nm

[0294] ○: The absolute value of the difference between the maximum and minimum values of the arithmetic mean roughness Ra is 25 nm or more and less than 50 nm

[0295] △: The absolute value of the difference between the maximum and minimum values of the arithmetic mean roughness Ra is 50 nm or more and less than 100 nm

[0296] ×: The absolute value of the difference between the maximum and minimum values of the arithmetic mean roughness Ra is 100 nm or more

[0297] (5) Adhesion force with the metal layer

[0298] Using the evaluated sample A obtained in the above-mentioned "(4) Surface roughness after roughening treatment", the following "(5-1A) Sputtering treatment" and the following "(5-2) Electroplating treatment" were carried out to obtain a cured product with a copper plating layer laminated on the upper surface. In addition, using the evaluated sample A obtained in the above-mentioned "(4) Surface roughness after roughening treatment", the following "(5-1B) Electroless plating treatment" and the following "(5-2) Electroplating treatment" were carried out to obtain a cured product with a copper plating layer laminated on the upper surface. Using the obtained cured product with a copper plating layer laminated on the upper surface, the following "(5-3) Measurement of peel strength" was carried out.

[0299] (5-1A) Sputtering treatment:

[0300] On the surface of the roughened cured product in the evaluated sample A, a titanium layer (Ti layer) with a thickness of 150 nm was formed as an adhesion layer using a sputtering device ("SIV-500" manufactured by ULVAC). On the formed Ti layer, a copper layer (Cu layer) with a thickness of 200 nm was formed as a power supply layer (seed layer) using the sputtering device. Then, annealing treatment was carried out at a temperature of 180 °C for 60 minutes.

[0301] (5-1B) Electroless plating treatment:

[0302] The surface of the roughened solidified product in Evaluation Sample A was treated with an alkaline cleaner at 60°C (“CLEANER SECURIGANTH 902” manufactured by ATOTECH JAPAN) for 5 minutes for degreasing and cleaning. After cleaning, the solidified product was treated with a pre-dip solution at 25°C (“PRE DIP NEOGANTH B” manufactured by ATOTECH JAPAN) for 2 minutes. Then, the solidified product was treated with an activation solution at 40°C (“ACTIVATOR NEOGANTH 834” manufactured by ATOTECH JAPAN) for 5 minutes to add a palladium catalyst. Next, the solidified product was treated with a reducing solution at 30°C (“REDUCER NEOGANTH WA” manufactured by ATOTECH JAPAN) for 5 minutes. Next, the solidified product was added to an electroless copper solution (“BASIC PRINTOGANTH MSK-DK”, “COPPER PRINTOGANTH MSK”, “STABILIZER PRINTOGANTH MSK” and “REDUCER Cu” manufactured by ATOTECH JAPAN), and electroless plating was performed until the thickness of the plating layer was about 0.5 μm. After electroless plating, in order to remove residual hydrogen, annealing treatment was performed at a temperature of 120°C for 30 minutes. It should be noted that for all the processes up to the electroless plating process, the treatment solution was set to 2 L according to the beaker scale, and the solidified product was shaken while the treatment was carried out.

[0303] (5-2) Electroplating treatment:

[0304] Then, electroplating was performed on the solidified product having a seed layer formed on its surface until the plating thickness reached 25 μm. As electrolytic copper plating, a copper sulfate solution (“copper sulfate pentahydrate” manufactured by Wako Pure Chemical Industries, Ltd., “sulfuric acid” manufactured by Wako Pure Chemical Industries, Ltd., “BASIC LEVELER CUPRACID HL” manufactured by ATOTECH JAPAN, “Corrector CUPRACID GS” manufactured by ATOTECH JAPAN) was used, and a current of 0.6 A / cm 2 was passed, and electroplating was performed until the plating thickness reached about 25 μm. After the copper plating treatment, the solidified product was heated at 200°C for 60 minutes to further solidify the solidified product. Thus, a solidified product having a copper plating layer laminated on its upper surface was obtained.

[0305] (5-3) Measurement of peel strength:

[0306] On the surface of the copper-plated layer of the obtained cured product with a copper-plated layer laminated on the upper surface, strip-shaped incisions with a width of 10 mm are made at a total of 6 positions at intervals of 5 mm. The cured product with a copper-plated layer laminated on the upper surface is set in a 90° peel tester ("TE-3001" manufactured by TESTER SANGYO Co., Ltd.). The end of the copper-plated layer with the incision is clamped by a jig, and the copper-plated layer is peeled off by 20 mm, and the peel strength (coating peel strength) is measured. The peel strength (coating peel strength) is measured at the incision positions at 6 positions respectively, and the average value of the peel strength is used as the peel strength (coating peel strength) of the copper-plated layer. The adhesion to the metal layer is judged according to the following criteria.

[0307] [Judgment Criteria for Adhesion to Metal Layer]

[0308] ○○: The peel strength of the copper-plated layer is 0.4 kgf / cm or more

[0309] ○: The peel strength of the copper-plated layer is 0.3 kgf / cm or more and less than 0.4 kgf / cm

[0310] △: The peel strength of the copper-plated layer is 0.2 kgf / cm or more and less than 0.3 kgf / cm

[0311] ×: The peel strength of the copper-plated layer is less than 0.2 kgf / cm

[0312] The composition and results are shown in Tables 1 to 10 below.

[0313] [Table 1]

[0314]

[0315] [Table 2]

[0316]

[0317] [Table 3]

[0318]

[0319] [Table 4]

[0320]

[0321] [Table 5]

[0322]

[0323] [Table 6]

[0324]

[0325] [Table 7]

[0326]

[0327] [Table 8]

[0328]

[0329] [Table 9]

[0330]

[0331] [Table 10]

[0332]

[0333] Symbol Explanation

[0334] 11…Multi-layer printed circuit board

[0335] 12…Circuit board

[0336] 12a…Upper surface

[0337] 13~16…Insulating layer

[0338] 17…Metal layer

Claims

1. A resin material, comprising: A maleimide compound (A) having two or more maleimide groups; A thermosetting compound (B), which is a thermosetting compound having one maleimide group or a thermosetting compound having a functional group capable of reacting with a maleimide group and not having a maleimide group; Hollow inorganic particles (C); and A curing accelerator (D), In 100% by weight of the components other than the solvent in the resin material, the content of the maleimide compound (A) is 20% by weight or more and 70% by weight or less.

2. The resin material according to claim 1, wherein The thermosetting compound (B) includes a thermosetting compound that is liquid at 25°C.

3. The resin material according to claim 1 or 2, wherein The inorganic substance forming the hollow inorganic particles (C) includes silica, aluminosilicate, or silsesquioxane.

4. The resin material according to any one of claims 1 to 3, wherein In 100% by weight of the components other than the solvent in the resin material, the content of the hollow inorganic particles (C) is 60% by weight or less.

5. The resin material according to any one of claims 1 to 4, wherein The thermosetting compound (B) includes a thermosetting compound having an epoxy group, vinyl group, styryl group, benzoxazine group, cyanate ester group, allyl group, methacryloyl group, acryloyl group or maleimide group. ​ 6. The resin material according to any one of claims 1 to 5, wherein The hollow inorganic particles (C) are surface-treated hollow inorganic particles.

7. The resin material according to any one of claims 1 to 6, wherein When the resin material is heated at 180°C for 30 minutes and then heated at 200°C for 60 minutes to obtain a cured product of the resin material, the dielectric constant of the obtained cured product at 10 GHz is 2.5 or less, and the average coefficient of linear expansion of the obtained cured product at 25°C or higher and 150°C or lower is 40 ppm / °C or less.

8. The resin material according to any one of claims 1 to 7, which is a resin film.

9. The resin material according to any one of claims 1 to 8, which is used to form an insulating layer in a multilayer printed wiring board.

10. A cured product of a resin material, wherein The resin material is the resin material according to any one of claims 1 to 9.

11. A method for manufacturing a laminate including a cured product of a resin material and a metal layer, comprising: A step of forming a metal layer on the surface of the cured product of the resin material by a sputtering method, The resin material is the resin material according to any one of claims 1 to 9.

12. A multilayer printed wiring board, comprising: A circuit board; A plurality of insulating layers disposed on the surface of the circuit board; and A metal layer disposed between the plurality of insulating layers, At least one layer of the plurality of insulating layers is a cured product of the resin material according to any one of claims 1 to 9.

Images