WO2020045408A1 - Resin material, layered structure, and multi-layer printed wiring board - Google Patents

Abstract

Provided is a resin material that can (1) increase the homogeneity of surface roughness after etching, (2) increase the dimensional stability under heat when in a cured form, (3) increase plating peel strength, (4) increase embeddability in a contoured surface, and (5) suppress excessive protrusion from a substrate periphery during lamination. This resin material includes a maleimide compound with a framework derived from a dimer diamine or a framework derived from a trimer triamine, and the glass transition temperature of the maleimide compound is 80°C or higher.

Description

Resin material, laminated structure and multilayer printed wiring board

The present invention relates to a resin material containing a maleimide compound. The present invention also relates to a laminated structure and a multilayer printed wiring board using the above resin material.

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

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

Patent Document 2 below discloses a resin composition for an electronic material, including a bismaleimide compound, wherein the bismaleimide compound has two maleimide groups and one or more polyimide groups having a specific structure. . In the bismaleimide compound, the two maleimide groups are independently bonded to both ends of the polyimide group via at least a first linking group in which eight or more atoms are linked in a linear manner. .

WO2016 / 114286A1 JP 2018-90728 A

When an insulating layer is formed using a conventional resin material as described in Patent Documents 1 and 2, the thermal dimensional stability may not be sufficiently high, or the surface roughness after etching may vary. . When the surface roughness after etching varies, the strength of the insulating layer is not sufficiently increased because the resin contributing to the anchor effect is partially thinned. The plating peel strength with the metal layer laminated on the surface of the layer by plating may not be sufficiently high.

Further, when an insulating layer is formed using a conventional resin material as described in Patent Document 1, or when an insulating layer is formed using a conventional resin material including an epoxy resin, a resin for unevenness of a substrate or the like is formed. The embedding property of the material may not be sufficiently high, or the resin material may excessively protrude from the periphery of the substrate during lamination, making it difficult to control the film thickness.

It is an object of the present invention to 1) enhance the uniformity of the surface roughness after etching, 2) increase the thermal dimensional stability of the cured product, 3) increase the plating peel strength, and 4) enhance the embedding property on uneven surfaces. 5) To provide a resin material capable of suppressing excessive protrusion from the periphery of the substrate during lamination. Another object of the present invention is to provide a laminated structure and a multilayer printed wiring board using the above resin material.

According to a broad aspect of the present invention, there is provided a resin material containing a maleimide compound having a skeleton derived from dimerdiamine or a skeleton derived from trimertriamine, wherein the glass transition temperature of the maleimide compound is 80 ° C or higher.

で は In a specific aspect of the resin material according to the present invention, the maleimide compound has a weight average molecular weight of 1,000 or more and 50,000 or less.

で は In a specific aspect of the resin material according to the present invention, the maleimide compound has a weight average molecular weight of 3,000 to 30,000.

で は In a specific aspect of the resin material according to the present invention, the maleimide compound is a citraconic imide compound.

In a specific aspect of the resin material according to the present invention, the maleimide compound has a skeleton derived from the dimer diamine or a skeleton derived from trimer triamine at both ends of the main chain.

In a specific aspect of the resin material according to the present invention, the maleimide compound has a skeleton derived from the dimer diamine or a skeleton derived from the trimer triamine only at both ends of the main chain.

In a specific aspect of the resin material according to the present invention, the maleimide compound has a skeleton derived from a reaction product of a diamine compound other than dimer diamine and an acid dianhydride at a portion other than both ends of the main chain.

で は In a specific aspect of the resin material according to the present invention, the resin material includes a maleimide compound having no skeleton derived from dimer diamine.

で は In a specific aspect of the resin material according to the present invention, the maleimide compound having no skeleton derived from the dimer diamine includes an N-phenylmaleimide compound.

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

で は In a specific aspect of the resin material according to the present invention, the inorganic filler has an average particle size of 1 μm or less.

で は In a specific aspect of the resin material according to the present invention, the inorganic filler is silica.

In a specific aspect of the resin material according to the present invention, the resin material is an epoxy compound and at least one of a phenol compound, a cyanate ester compound, an acid anhydride, an active ester compound, a carbodiimide compound, and a benzoxazine compound. And a curing agent containing the following components:

In one specific aspect of the resin material according to the present invention, the curing agent includes the benzoxazine compound, and the benzoxazine compound has a skeleton derived from dimer diamine.

In one specific aspect of the resin material according to the present invention, the resin material contains a curing accelerator, and the curing accelerator contains an anionic curing accelerator.

で は In a specific aspect of the resin material according to the present invention, the content of the anionic curing accelerator is 20% by weight or more based on 100% by weight of the curing accelerator.

で は In a specific aspect of the resin material according to the present invention, the resin material is a resin film.

According to a broad aspect of the present invention, there is provided a laminated structure including: a member to be laminated having a metal layer on the surface; and a resin film laminated on the surface of the metal layer, wherein the resin film is the resin material described above. A body is provided.

で は In a specific aspect of the laminated structure according to the present invention, the material of the metal layer is copper.

According to a broad aspect of the present invention, a circuit board includes a plurality of insulating layers disposed on a surface of the circuit board, and a metal layer disposed between the plurality of insulating layers. Wherein at least one of the layers is a cured product of the resin material described above.

The resin material according to the present invention contains a maleimide compound having a skeleton derived from dimer diamine or a skeleton derived from trimer triamine, and the glass transition temperature of the maleimide compound is 80 ° C. or higher. Since the resin material according to the present invention has the above-described configuration, 1) enhances the uniformity of the surface roughness after etching, 2) enhances the thermal dimensional stability of the cured product, and 3) increases the plating peel strength. 4) The embedding property to the uneven surface is enhanced, and 5) Excessive protrusion from the periphery of the substrate during lamination can be suppressed. The resin material according to the present invention can exhibit all of the above effects 1) to 5).

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

Hereinafter, the present invention will be described in detail.

The resin material according to the present invention contains a maleimide compound having a skeleton derived from dimer diamine or a skeleton derived from trimer triamine, and the glass transition temperature of the maleimide compound is 80 ° C. or higher.

Since the resin material according to the present invention has the above-described configuration, 1) enhances the uniformity of the surface roughness after etching, 2) enhances the thermal dimensional stability of the cured product, and 3) increases the plating peel strength. 4) The embedding property to the uneven surface is enhanced, and 5) Excessive protrusion from the periphery of the substrate during lamination can be suppressed. The resin material according to the present invention can exhibit all of the above effects 1) to 5).

In a conventional resin material containing a maleimide compound and an inorganic filler, in a cured product of the resin material, phase separation occurs excessively, and a component derived from the maleimide compound and the inorganic filler are locally present. As a result, the surface roughness of the cured product surface after the roughening step may vary. Furthermore, when the maleimide compound has a skeleton derived from dimer diamine, the resin material is more easily etched in the roughening step due to a double bond that the skeleton derived from dimer diamine may have. . Further, for example, in a resin material containing a maleimide compound having a skeleton derived from a conventional dimer diamine and having a glass transition temperature of less than 80 ° C., a skeleton portion derived from a dimer diamine having a high etching property is excessively aggregated. Therefore, the surface roughness after etching may vary. In particular, when a maleimide compound having a skeleton derived from dimer diamine and having a glass transition temperature of less than 80 ° C. and an epoxy compound are used in combination, the protrusion to the periphery after lamination may be excessively large. In addition, when excessive phase separation occurs in the cured product of the resin material, the compatibility between the maleimide compound and other resin components such as an epoxy compound is reduced, and the fluidity of the inorganic filler is also reduced. The embedding property to the uneven surface may decrease.

従 来 In the case of a conventional resin material containing only a compound having a glass transition temperature of less than 80 ° C as a resin component, the thermal dimensional stability of a cured product may be reduced.

On the other hand, since the resin material according to the present invention contains a maleimide compound having a specific skeleton and a specific glass transition temperature, the effects of the present invention described in 1) to 5) above can be exhibited.

Further, in the resin material according to the present invention, the surface roughness can be reduced, and in a laminated substrate such as a multilayer printed wiring board obtained by using a cured product of the resin material, the conductor loss due to the skin effect can be reduced. Can be.

(4) In the resin material according to the present invention, the dielectric loss tangent of the cured product at room temperature (for example, 23 ° C.) and high temperature (for example, 110 ° C.) can be reduced.

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

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

詳細 Hereinafter, details of each component used in the resin material according to the present invention and uses of the resin material according to the present invention will be described.

[Maleimide compound having a skeleton derived from dimer diamine or a skeleton derived from trimer triamine (maleimide compound A)]
The resin material according to the present invention includes a maleimide compound having a skeleton derived from dimerdiamine or a skeleton derived from trimertriamine (hereinafter, may be referred to as “maleimide compound A”). The maleimide compound A may have a skeleton derived from dimer diamine, may have a skeleton derived from trimer triamine, and has a skeleton derived from dimer diamine and a skeleton derived from trimer triamine. It may be. The maleimide compound A need not have an aromatic skeleton. As the maleimide compound A, only one type may be used, or two or more types may be used in combination.

The skeleton derived from the dimer diamine and the skeleton derived from the trimer triamine are preferably present as a partial skeleton in the maleimide compound A.

The maleimide compound A is preferably a bismaleimide compound.

Note that the maleimide compound includes a citraconic imide compound. The citraconimide compound is a compound in which a methyl group is bonded to one of carbon atoms constituting a double bond between carbon atoms in a maleimide group. The maleimide compound A may be a citraconic imide compound. Since the citraconimide compound has lower reactivity than the maleimide compound, the storage stability of the resin material can be improved. The maleimide compound may be a citraconic imide compound or a maleimide compound other than the citraconic imide compound.

The maleimide compound A preferably has a skeleton derived from the dimer diamine or a skeleton derived from the trimer triamine at both ends of the main chain. In this case, the maleimide compound A may have a skeleton derived from the dimer diamine at both ends of the main chain, or may have a skeleton derived from the trimer triamine at both ends of the main chain. And a skeleton derived from the dimer diamine at one end of the main chain, and a skeleton derived from the trimer triamine at the other end of the main chain. In this case, the maleimide compound A may have a skeleton derived from the dimer diamine or a skeleton derived from a trimer triamine in a skeleton other than both ends of the main chain and both ends of the main chain. A skeleton derived from the dimer diamine or a skeleton derived from the trimer triamine may be present only at both ends of the chain. When the maleimide compound A has a skeleton derived from the dimer diamine or a skeleton derived from the trimer triamine at both ends of the main chain, a maleimide group is bonded to the aliphatic and highly flexible dimer diamine skeleton. Therefore, the reactivity of the maleimide compound A can be increased. Therefore, the thermal dimensional stability of the cured product can be further enhanced, and the adhesion between the insulating layer and the metal layer can be further enhanced.

減 ら す By reducing the content of the skeleton derived from dimer diamine in the main chain skeleton of the maleimide compound A, the compatibility between the maleimide compound A and components other than the maleimide compound A is improved. As a result, compared with the case where the phase separation is strong (for example, the domain size is 1 μm or more), the fluidity of the resin material can be increased, and the embedding property on the uneven surface can be enhanced.

The maleimide compound A more preferably has a skeleton derived from the dimer diamine or a skeleton derived from the trimer triamine only at both ends of the main chain. When the maleimide compound A has a skeleton derived from the dimer diamine or a skeleton derived from the trimer triamine only at both ends of the main chain, the main chain skeleton can be made relatively rigid. The glass transition temperature of the maleimide compound A can be more effectively increased. Therefore, the thermal dimensional stability of the cured product can be further improved, and the adhesion between the insulating layer and the metal layer can be further improved.

The maleimide compound A preferably has a skeleton derived from a diamine compound other than dimer diamine, and more preferably has both a skeleton derived from dimer diamine and a skeleton derived from a diamine compound other than dimer diamine. In this case, the above-described effects 1) to 5) of the present invention can be effectively exhibited. Further, when the maleimide compound A has both a skeleton derived from dimer diamine and a skeleton derived from a diamine compound other than dimer diamine, the thermal dimensional stability is maintained, and the dielectric loss tangent at a high temperature is reduced. can do. The skeleton derived from the diamine compound other than the dimer diamine may be present at both ends of the main chain, or may be present at a portion other than both ends of the main chain.

The maleimide compound A preferably has a skeleton derived from a reaction product of a diamine compound other than dimer diamine and an acid dianhydride, a skeleton derived from dimer diamine, and a diamine compound other than dimer diamine and an acid dianhydride. It is more preferred to have both the skeleton derived from the reactant with In this case, the above-described effects 1) to 5) of the present invention can be effectively exhibited. When the maleimide compound A has both a skeleton derived from dimer diamine and a skeleton derived from a reaction product of a diamine compound other than dimer diamine and an acid dianhydride, the dielectric loss tangent at a high temperature is obtained. Can be lowered. The skeleton derived from the reaction product of the diamine compound other than the dimer diamine and the acid dianhydride may be present at both ends of the main chain, or may be present at a portion other than both ends of the main chain. .

From the viewpoint of effectively exhibiting the effects of the present invention described in 1) to 5) above, the maleimide compound A contains a diamine compound other than dimer diamine and an acid dianhydride at a portion other than both ends of the main chain. It is preferable to have a skeleton derived from the reaction product of

The maleimide compound A has a skeleton derived from the dimer diamine or a skeleton derived from trimer triamine only at both ends of the main chain, and a diamine compound other than the dimer diamine and an acid at a portion other than both ends of the main chain. It preferably has a skeleton derived from a reaction product with a dianhydride. In this case, the effects of the present invention described in 1) to 5) above can be more effectively exhibited, and the dielectric loss tangent at a high temperature can be reduced.

The maleimide compound A is obtained by reacting an acid dianhydride such as a tetracarboxylic dianhydride with a dimer diamine or a trimer triamine, and, if necessary, a diamine compound other than the dimer diamine or a triamine compound other than the trimer triamine. After the reaction product is obtained, it can be obtained by reacting the reaction product with maleic anhydride.

The maleimide compound A having a skeleton derived from the dimer diamine or a skeleton derived from the trimer triamine only at both ends of the main chain can be obtained, for example, as follows. An acid dianhydride such as tetracarboxylic dianhydride is reacted with a diamine compound other than dimer diamine or a triamine compound other than trimer triamine to obtain a first reactant. The obtained first reactant is reacted with dimerdiamine or trimertriamine to obtain a second reactant. The resulting second reactant is reacted with maleic anhydride.

At both ends of the main chain or at one end of the main chain, a skeleton derived from the dimer diamine or a skeleton derived from the trimer triamine, derived from a reaction product of a diamine compound other than dimer diamine and an acid dianhydride The maleimide compound A having a skeleton at random can be obtained, for example, as follows. An acid dianhydride such as tetracarboxylic dianhydride, a diamine compound other than dimer diamine, and dimer diamine or trimer triamine are reacted to obtain a first reactant having an amine skeleton at both ends. The resulting first reactant is reacted with maleic anhydride.

Examples of the above tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetraanhydride Carboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether Tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2 , 3,4-furantetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4'-bis (3,4-dicarboxy Xy) diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane 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′-diphenyl ether dianhydride, and bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride .

Examples of the dimer diamine include Versamine 551 (trade name, 3,4-bis (1-aminoheptyl) -6-hexyl-5- (1-octenyl) cyclohexene, manufactured by BASF Japan), Versamine 552 (trade name) And PRIAMINE 1075 and PRIAMINE 1074 (trade names, both manufactured by Crowda Japan), manufactured by Cognix Japan KK, and the like. Since PRIAMINE 1074 has a larger number of unsaturated bonds than PRIAMINE 1075, PRIAMINE 1074 is more excellent in desmearing property than PRIAMINE 1075.

と し て Examples of the above trimmer triamine include PRIAMINE 1071 (trade name, manufactured by Croda Japan). Since PRIAMINE 1071 has a larger number of unsaturated bonds than PRIAMINE 1075, PRIAMINE 1074 is more excellent in desmearing property than PRIAMINE 1075. However, since PRIAMINE 1071 contains a triamine component at about 20% by mass to 25% by mass, it is necessary to use it in the reaction in consideration of the ratio.

Examples of diamine compounds other than the dimer diamine include 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, bis (aminomethyl) norbornane, and 3 (4), 8 (9) -bis (Aminomethyl) tricyclo [5.2.1.02,6] decane, 1,1-bis (4-aminophenyl) cyclohexane, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 2,7-diamino Fluorene, 4,4'-ethylenedianiline, isophoronediamine, 4,4'-methylenebis (cyclohexylamine), 4,4'-methylenebis (2,6-diethylaniline), 4,4'-methylenebis (2-ethyl -6-methylaniline), 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 and the like.

From the viewpoint of effectively exhibiting the effects of the present invention of 1) to 5), the diamine compound other than the dimer diamine is preferably a diamine compound having 36 or less carbon atoms.

From the viewpoint of effectively exhibiting the effects of the present invention described in 1) to 5) above, the diamine compound other than the dimer diamine is preferably a diamine compound having a cyclohexane ring skeleton.

ト リ Examples of triamine compounds other than the above-mentioned trimeric triamine include 1,2,4-triaminobenzene.

骨 格 The skeleton derived from the dimer diamine has or does not have an aliphatic ring. The skeleton derived from the dimer diamine may or may not have an aliphatic ring.

骨 格 The skeleton derived from the trimer triamine may or may not have an aliphatic ring. The skeleton derived from the trimer triamine may or may not have an aliphatic ring.

骨 格 A skeleton derived from a diamine compound other than the above dimer diamine may or may not have an aliphatic ring. The skeleton derived from a diamine compound other than the dimer diamine preferably has an aliphatic ring. The aliphatic ring preferably has a cyclohexane ring skeleton.

骨 格 The skeleton derived from a diamine compound other than the above dimer diamine may or may not have an aromatic ring. The skeleton derived from a diamine compound other than the dimer diamine may or may not have an aromatic ring.

骨 格 The skeleton derived from the above triamine compound has or does not have an aromatic ring. The skeleton derived from the triamine compound may or may not have an aromatic ring.

Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a tetracene ring, a chrysene ring, a triphenylene ring, a tetraphen ring, a pyrene ring, a pentacene ring, a picene ring and a perylene ring.

Examples of the aliphatic ring include a monocycloalkane ring, a bicycloalkane ring, a tricycloalkane ring, a tetracycloalkane ring, and dicyclopentadiene.

(4) The glass transition temperature of the maleimide compound A is 80 ° C. or higher from the viewpoint of improving the thermal dimensional stability of the cured product and the adhesiveness between the insulating layer and the metal layer. When the glass transition temperature of the maleimide compound A is less than 80 ° C., the thermal dimensional stability of the cured product may decrease.

From the viewpoint of further increasing the thermal dimensional stability of the cured product and further enhancing the adhesion between the insulating layer and the metal layer, the glass transition temperature of the maleimide compound A is preferably 95 ° C or higher, more preferably 100 ° C. The temperature is more preferably 110 ° C. or higher, further preferably 120 ° C. or higher, and particularly preferably 125 ° C. or higher. The upper limit of the glass transition temperature of the maleimide compound A is not particularly limited. From the viewpoint of ease of synthesis of the maleimide compound, the glass transition temperature of the maleimide compound A may be 190 ° C. or lower.

The above glass transition temperature is determined by heating from −30 ° C. to 200 ° C. in a nitrogen atmosphere at a rate of 3 ° C./min using a differential scanning calorimeter (eg, “Q2000” manufactured by TA Instruments). From the inflection point of the reverse heat flow.

From the viewpoint of further increasing the embedding property on the uneven surface, the molecular weight of the maleimide compound A is preferably 1,000 or more, more preferably 3,000 or more, still more preferably 4,000 or more, preferably 50,000 or less, more preferably 30,000 or less, and still more preferably. Is 20,000 or less, particularly preferably 15,000 or less. When the molecular weight of the maleimide compound A is equal to or more than the lower limit, the coefficient of linear expansion of the resin material can be reduced. Further, when the molecular weight of the maleimide compound exceeds 50,000, the melt viscosity of the resin material becomes higher than in the case where the molecular weight of the maleimide compound A is 50,000 or less, and the embedding property on the uneven surface may be reduced.

分子 The molecular weight of the maleimide compound A means a molecular weight that can be calculated from the structural formula when the maleimide compound A is not a polymer or when the structural formula of the maleimide compound A can be specified. When the maleimide compound A is a polymer, the molecular weight of the maleimide compound A indicates a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC). Therefore, it is preferable that the weight average molecular weight of the maleimide compound A satisfies the preferable range described above.

The weight ratio of the content of the maleimide compound A to the total content of the epoxy compound and the component X described later (content of the maleimide compound A / total content of the epoxy compound and the component X) is , Preferably 0.03 or more, more preferably 0.1 or more, still more preferably 0.5 or more, preferably 0.9 or less, more preferably 0.75 or less. When the weight ratio is at least the lower limit, the dielectric loss tangent at room temperature and high temperature can be further reduced, the thermal dimensional stability can be further improved, and the desmear property can be improved. When the weight ratio is equal to or less than the upper limit, the thermal dimensional stability can be further improved, the surface roughness after etching can be further reduced, and the plating peel strength can be further increased.

The content of the maleimide compound A is preferably 3% by weight or more, more preferably 5% by weight or more, and still more preferably 10% by weight or more in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material. It is preferably at most 80% by weight, more preferably at most 70% by weight, even more preferably at most 50% by weight. When the content of the maleimide compound A is equal to or more than the lower limit, the dielectric loss tangent at room temperature and high temperature can be further reduced, the adhesion between the insulating layer and the metal layer can be further increased, and the desmear property can be increased. Can be. When the content of the maleimide compound A is equal to or less than the upper limit, the thermal dimensional stability can be further improved, and the surface roughness after etching can be further reduced.

[Epoxy compound]
The resin material preferably contains an epoxy compound. As the epoxy compound, a conventionally known epoxy compound can be used. The epoxy compound refers to an organic compound having at least one epoxy group. One of the above epoxy compounds may be used alone, or two or more thereof may be used in combination.

Examples of the epoxy compound include a bisphenol A epoxy compound, a bisphenol F epoxy compound, a bisphenol S epoxy compound, a phenol novolak epoxy compound, a biphenyl epoxy compound, a biphenyl novolak epoxy compound, a biphenol epoxy compound, and a naphthalene 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 An epoxy compound and an epoxy compound having a triazine nucleus in a skeleton are exemplified.

From the viewpoint of further lowering the dielectric loss tangent of the cured product, and enhancing the thermal dimensional stability and flame retardancy of the cured product, the epoxy compound preferably contains an epoxy compound having an aromatic skeleton, and a naphthalene skeleton or An epoxy compound having a phenyl skeleton is preferably included, and an epoxy compound having an aromatic skeleton is more preferable.

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

The viscosity at 25 ° C. of the liquid epoxy compound at 25 ° C. is preferably 1,000 mPa · s or less, more preferably 500 mPa · s or less.

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

エ ポ キ シ It is more preferable that the molecular weight of the epoxy compound is 1,000 or less. In this case, even if the content of the inorganic filler is 50% by weight or more based on 100% by weight of the components excluding the solvent in the resin material, a resin material having high fluidity at the time of forming the insulating layer can be obtained. Therefore, when the uncured resin material or the B-staged resin material is laminated on the circuit board, the inorganic filler can be uniformly present.

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

From the viewpoint of further increasing the thermal dimensional stability of the cured product, the content of the epoxy compound is preferably 15% by weight or more, more preferably 25% by weight or more, in 100% by weight of the components excluding the solvent in the resin material. , Preferably 50% by weight or less, more preferably 40% by weight or less.

The weight ratio of the content of the epoxy compound to the total content of the maleimide compound A and the component X described below (content of the epoxy compound / total content of the maleimide compound A and the component X) is: , Preferably 0.2 or more, more preferably 0.3 or more, preferably 0.9 or less, more preferably 0.8 or less. When the weight ratio is equal to or more than the lower limit and equal to or less than the upper limit, the dielectric loss tangent can be further reduced, and the thermal dimensional stability can be further increased.

[Inorganic filler]
The resin material preferably contains an inorganic filler. By using the inorganic filler, the dielectric loss tangent of the cured product can be further reduced. In addition, the use of the inorganic filler further reduces the dimensional change of the cured product due to heat. As the inorganic filler, only one kind may be used, or two or more kinds may be used in combination.

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

Reduces the surface roughness of the surface of the cured product, further increases the adhesive strength between the cured product and the metal layer, forms finer wiring on the surface of the cured product, and provides better insulation reliability with the cured product From the viewpoint of imparting the following, the inorganic filler is preferably silica or alumina, more preferably silica, and further preferably fused silica. By using silica, the coefficient of thermal expansion of the cured product is further reduced, and the dielectric loss tangent of the cured product is further reduced. In addition, by using silica, the surface roughness of the surface of the cured product is effectively reduced, and the adhesive strength between the cured product and the metal layer is effectively increased. The shape of the silica is preferably spherical.

Regardless of the curing environment, advance the curing of the resin, effectively increase the glass transition temperature of the cured product, from the viewpoint of effectively reducing the coefficient of linear thermal expansion of the cured product, the inorganic filler is spherical silica Is preferred.

The average particle size of the inorganic filler is preferably 50 nm or more, more preferably 100 nm or more, further preferably 500 nm or more, preferably 5 μm or less, more preferably 3 μm or less, and further preferably 1 μm or less. When the average particle size of the inorganic filler is equal to or greater than the lower limit and equal to or less than the upper limit, the surface roughness after etching can be reduced, and the plating peel strength can be increased. Adhesion can be further improved.

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

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

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

The inorganic filler is preferably surface-treated, more preferably a surface-treated product with a coupling agent, and even more preferably a surface-treated product with a silane coupling agent. By the surface treatment of the inorganic filler, the surface roughness of the surface of the roughened and cured product is further reduced, and the adhesive strength between the cured product and the metal layer is further increased. Further, since the inorganic filler is subjected to the surface treatment, finer wiring can be formed on the surface of the cured product, and more favorable inter-wiring insulation reliability and interlayer insulation reliability can be obtained in the cured product. Can be granted.

Examples of the coupling agent include a silane coupling agent, a titanium coupling agent, and an aluminum coupling agent. Examples of the silane coupling agent include methacryl silane, acryl silane, amino silane, imidazole silane, vinyl silane, and epoxy silane.

The content of the inorganic filler is preferably 50% by weight or more, more preferably 60% by weight or more, still more preferably 65% by weight or more, and particularly preferably 68% by weight, based on 100% by weight of the components excluding the solvent in the resin material. % Or less, preferably 90% by weight or less, more preferably 85% by weight or less, still more preferably 80% by weight or less, and particularly preferably 75% by weight or less. When the content of the inorganic filler is equal to or more than the lower limit, the dielectric loss tangent is effectively reduced. When the content of the inorganic filler is equal to or less than the upper limit, the thermal dimensional stability can be enhanced, and the warpage of the cured product can be effectively suppressed. When the content of the inorganic filler is equal to or greater than the lower limit and equal to or less than the upper limit, the surface roughness of the surface of the cured product can be further reduced, and finer wiring can be formed on the surface of the cured product. Can be. Further, with the content of the inorganic filler, it is possible to lower the coefficient of thermal expansion of the cured product and at the same time to improve the smear removal property.

[A maleimide compound having no skeleton derived from dimerdiamine or a maleimide compound having a skeleton derived from dimerdiamine and having a molecular weight of 1,000 or less (maleimide compound B)]
The resin material is a maleimide compound having no skeleton derived from dimer diamine or a maleimide compound having a skeleton derived from dimer diamine and having a molecular weight of 1,000 or less (hereinafter, may be referred to as “maleimide compound B”. ) Is preferable. The maleimide compound B may be a maleimide compound having no skeleton derived from dimerdiamine, or may be a maleimide compound having a skeleton derived from dimerdiamine and having a molecular weight of 1,000 or less. The maleimide compound B may be both a maleimide compound having no skeleton derived from dimerdiamine and a maleimide compound having a skeleton derived from dimerdiamine and having a molecular weight of 1,000 or less. The maleimide compound B is different from the maleimide compound A. By using the maleimide compound A and the maleimide compound B in combination, the effects of the present invention can be exhibited more effectively. It is preferable that the maleimide compound B does not have a skeleton derived from a trimer triamine. The maleimide compound B preferably has a skeleton derived from a diamine compound other than dimer diamine, but does not have to have a skeleton derived from a diamine compound. The maleimide compound B preferably has an aromatic skeleton. The glass transition temperature of the maleimide compound B may be less than 80 ° C. The maleimide compound B may be a polymaleimide compound having three or more maleimide skeletons. The maleimide compound B may be a citraconimide compound. As the maleimide compound B, only one type may be used, or two or more types may be used in combination.

In the maleimide compound B, the nitrogen atom in the maleimide skeleton and the aromatic ring are preferably bonded.

と し て Examples of the maleimide compound B include N-phenylmaleimide compounds.

From the viewpoint of effectively exhibiting the effects 1) to 5) described above, the maleimide compound B preferably contains an N-phenylmaleimide compound, and more preferably is an N-phenylmaleimide compound.

The content of the maleimide compound B is preferably 2.5% by weight or more, more preferably 5% by weight or more, and further preferably 7.5% in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material. % By weight, preferably 50% by weight or less, more preferably 35% by weight or less. When the content of the maleimide compound B is equal to or greater than the lower limit and equal to or less than the upper limit, the effects of the present invention described in 1) to 5) above can be further exhibited, and in particular, the thermal dimensional stability of the cured product can be further improved. Can be further enhanced.

From the viewpoint of effectively exhibiting the effects of the present invention described in 1) to 5) above, the molecular weight of the maleimide compound B is preferably 100 or more, more preferably 1,000 or more, preferably less than 30,000, more preferably 20,000. Is less than.

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

Commercially available maleimide compounds having no skeleton derived from the dimer diamine (maleimide compound B) include, for example, “MIR-3000” manufactured by Nippon Kayaku Co., Ltd., “BMI4000” and “BMI5100” manufactured by Daiwa Kasei Kogyo Co., Ltd. Is mentioned. Commercially available maleimide compounds having a skeleton derived from dimerdiamine and having a molecular weight of 1,000 or less (maleimide compound B) include, for example, Designer @ Molecules @ Inc. "BMI-689". Further, commercially available maleimide compounds (maleimide compounds B), which are citraconimide compounds, include, for example, Designer {Molecules} Inc. "BCI-737".

[Curing agent]
The resin material preferably contains a curing agent. The curing agent is not particularly limited. As the curing agent, a conventionally known curing agent can be used. One of the above curing agents may be used alone, or two or more thereof may be used in combination.

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

From the viewpoint of further increasing the thermal dimensional stability, the curing agent may include at least one component of a phenol compound, a cyanate ester compound, an acid anhydride, an active ester compound, a carbodiimide compound, and a benzoxazine compound. preferable. That is, the resin material preferably contains a curing agent containing at least one component of a phenol compound, a cyanate ester compound, an acid anhydride, an active ester compound, a carbodiimide compound, and a benzoxazine compound.

に お い て In the present specification, “at least one component among phenol compounds, cyanate ester compounds, acid anhydrides, active ester compounds, carbodiimide compounds, and benzoxazine compounds” may be referred to as “component X”.

From the viewpoint of effectively exhibiting the effects of the present invention of 1) to 5) and improving the desmear property, the benzoxazine compound may be a benzoxazine compound having a skeleton derived from dimerdiamine. preferable.

Therefore, it is preferable that the resin material contains a curing agent containing the component X. As the component X, only one type may be used, or two or more types may be used in combination.

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

Commercially available phenol compounds include novolak phenol ("TD-2091" manufactured by DIC), biphenyl novolak phenol ("MEH-7851" manufactured by Meiwa Kasei Co., Ltd.), and aralkyl phenol compounds ("MEH manufactured by Meiwa Kasei Co., Ltd."). -7800 "), and a phenol having an aminotriazine skeleton (" LA1356 "and" LA3018-50P "manufactured by DIC).

Examples of the cyanate ester compound include a novolak-type cyanate ester resin, a bisphenol-type cyanate ester resin, and a prepolymer partially trimerized. Examples of the novolak type cyanate ester resin include a phenol novolak type cyanate ester resin and an alkylphenol type cyanate ester resin. Examples of the bisphenol type cyanate ester resin include a bisphenol A type cyanate ester resin, a bisphenol E type cyanate ester resin, and a tetramethyl bisphenol F type cyanate ester resin.

Commercially available cyanate ester compounds include phenol novolak type cyanate ester resins (“PT-30” and “PT-60” manufactured by Lonza Japan) and prepolymers obtained by trimerizing bisphenol type cyanate ester resins (Lonza Japan). “BA-230S”, “BA-3000S”, “BTP-1000S” and “BTP-6020S”).

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

市 販 Commercially available acid anhydrides include “Likacid TDA-100” manufactured by Nippon Rika Co., Ltd.

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

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

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

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

Commercially available active ester compounds include “HPC-8000-65T”, “EXB-9416-70BK”, “EXB-8100-65T”, “EXB-8”, and “HPC-8150-62T” manufactured by DIC. And "HPC-8150-60T".

The carbodiimide compound has a structural unit represented by the following formula (2). In the following formula (2), the right end and the left end are binding sites to other groups. One kind of the carbodiimide compound may be used alone, or two or more kinds may be used in combination.

In the above formula (2), X is an alkylene group, a group having a substituent bonded to an alkylene group, a cycloalkylene group, a group having a substituent bonded to a cycloalkylene group, an arylene group, or a substituent having been bonded to an arylene group. Represents a group, and p represents an integer of 1 to 5. When there are a plurality of Xs, the plurality of Xs may be the same or different.

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

Commercially available carbodiimide compounds include Nisshinbo Chemical's "Carbodilite @ V-02B", "Carbodilite @ V-03", "Carbodilite @ V-04K", "Carbodilite @ V-07", "Carbodilite @ V-09", and "Carbodilite". 10M-SP "and" Carbodilite @ 10M-SP (revised) ", as well as" STABAXOL P "," STABAKSOL P400 ", and" HIKAZIL 510 "manufactured by Rhein Chemie.

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

市 販 Commercially available benzoxazine compounds include "Pd type" manufactured by Shikoku Chemicals.

含有 The content of the component X with respect to 100 parts by weight of the epoxy compound is preferably 70 parts by weight or more, more preferably 85 parts by weight or more, preferably 150 parts by weight or less, more preferably 120 parts by weight or less. When the content of the component X is equal to or higher than the lower limit and equal to or lower than the upper limit, the curability is further improved, the thermal dimensional stability is further increased, and the volatilization of the remaining unreacted component can be further suppressed.

In 100% by weight of the components excluding the inorganic filler and the solvent in the resin material, the total content of the epoxy compound and the component X is preferably 50% by weight or more, more preferably 60% by weight or more, and preferably It is at most 90% by weight, more preferably at most 85% by weight. When the total content of the epoxy compound and the component X is not less than the lower limit and not more than the upper limit, the curability is more excellent, and the thermal dimensional stability can be further increased.

[Curing accelerator]
The resin material preferably contains a curing accelerator. The use of the curing accelerator further increases the curing speed. 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 an increase in the crosslink density. The curing accelerator is not particularly limited, and a conventionally known curing accelerator can be used. One type of the above-mentioned curing accelerator may be used alone, or two or more types may be used in combination.

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

Examples of the imidazole compound include 2-undecylimidazole, 2-heptadecylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 1-benzyl-imidazole. 2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-un Decylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2 ′ －Met Imidazolyl- (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 and the like No.

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

リ ン Examples of the phosphorus compound include a triphenylphosphine compound.

{Examples of the organometallic compound include zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, bisacetylacetonatocobalt (II), and trisacetylacetonatocobalt (III).

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

When the peroxide is used as the curing accelerator, a one-minute half-life temperature can be provided between the preliminary curing temperature and the final curing temperature, so that the surface roughness can be improved, The plating peel strength and desmear property can be further improved.

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

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

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

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

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

フ ェ The phenoxy resin contained in the resin material is not particularly limited. As the phenoxy resin, a conventionally known phenoxy resin can be used. The phenoxy resin may be used alone or in combination of two or more.

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

Commercially available phenoxy resins include, for example, "YP50", "YP55" and "YP70" manufactured by Nippon Steel & Sumitomo Metal Corporation, and "1256B40", "4250", "4256H40", and "4256H40" manufactured by Mitsubishi Chemical Corporation. 4275 "," YX6954BH30 "and" YX8100BH30 ".

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

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

Examples of the above tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetraanhydride Carboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether Tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2 , 3,4-furantetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4'-bis (3,4-dicarboxy Xy) diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane 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′-diphenyl ether dianhydride, and bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride .

Examples of the dimer diamine include Versamine 551 (trade name, manufactured by BASF Japan Ltd., 3,4-bis (1-aminoheptyl) -6-hexyl-5- (1-octenyl) cyclohexene), Versamine 552 (trade name, Cognix Japan Co., Ltd., hydrogenated product of Versamine 551), PRIAMINE 1075, PRIAMINE 1074 (trade names, all manufactured by Croda Japan KK) and the like.

The above-mentioned polyimide compound may have an acid anhydride structure, a maleimide structure, or a citraconic imide structure at a terminal. In this case, the polyimide compound can react with the epoxy resin. The thermal dimensional stability of the cured product can be increased by reacting the polyimide compound with the epoxy resin.

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

The weight average molecular weight of the thermoplastic resin, the polyimide resin, and the phenoxy resin indicates a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

含有 The contents of the thermoplastic resin, the polyimide resin and the phenoxy resin are not particularly limited. The content of the thermoplastic resin in 100% by weight of the resin material excluding the inorganic filler and the solvent (in the case where the thermoplastic resin is a polyimide resin or a phenoxy resin, the content of the polyimide resin or the phenoxy resin ) Is preferably at least 1% by weight, more preferably at least 2% by weight, preferably at most 30% by weight, more preferably at most 20% by weight. When the content of the thermoplastic resin is equal to or more than the lower limit and equal to or less than the upper limit, the embedding property of the resin material into holes or irregularities of the circuit board is improved. When the content of the thermoplastic resin is equal to or more than the above lower limit, formation of a resin film is further facilitated, and a better insulating layer is obtained. When the content of the thermoplastic resin is equal to or less than the upper limit, the coefficient of thermal expansion of the cured product is further reduced. When the content of the thermoplastic resin is equal to or less than the upper limit, the surface roughness of the surface of the cured product is further reduced, and the adhesive strength between the cured product and the metal layer is further increased.

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

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, Examples include N, N-dimethylformamide, methyl isobutyl ketone, N-methyl-pyrrolidone, n-hexane, cyclohexane, cyclohexanone, and naphtha which is a mixture.

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

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

[Other components]
For the purpose of improving impact resistance, heat resistance, resin compatibility, workability, etc., the above resin materials are used as leveling agents, flame retardants, coupling agents, coloring agents, antioxidants, ultraviolet deterioration inhibitors, defoamers. It may contain a thermosetting resin other than an agent, a thickener, a thixotropic agent and an epoxy compound.

Examples of the coupling agent include a silane coupling agent, a titanium coupling agent, and an aluminum coupling agent. Examples of the silane coupling agent include vinyl silane, amino silane, imidazole silane and epoxy silane.

Other thermosetting resins include polyphenylene ether resin, divinyl benzyl ether resin, polyarylate resin, diallyl phthalate resin, benzoxazole resin, and acrylate resin.

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

方法 As a method of forming the resin composition into a film to obtain a resin film, the following method can be mentioned. An extrusion molding method in which a resin composition is melt-kneaded using an extruder, extruded, and then formed into a film by a T-die or a circular die. A casting method in which a resin composition containing a solvent is cast to form a film. Other known film forming methods. The extrusion molding method or the casting molding method is preferable because it can cope with thinning. The film includes a sheet.

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

フ ィ ル ム The film-shaped resin composition obtained by the above-mentioned drying step is referred to as a B-stage film. The B stage film is in a semi-cured state. The semi-cured product is not completely cured, and curing may proceed further.

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

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

From the viewpoint of controlling the degree of curing of the resin film more uniformly, the thickness of the resin film is preferably 5 μm or more, and more preferably 200 μm or less. When 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 a conductor layer (metal layer) forming the circuit. The thickness of the insulating layer is preferably 5 μm or more, and more preferably 200 μm or less.

(Semiconductor devices, printed wiring boards, copper-clad laminates and multilayer printed wiring boards)
The resin material is suitably used for forming a mold resin for embedding a semiconductor chip in a semiconductor device.

The above resin material is suitably used for forming an insulating layer in a printed wiring board.

The printed wiring board is obtained, for example, by heating and pressing the resin material.

部 材 A member to be laminated having a metal layer on one surface or both surfaces can be laminated on the resin film. A laminated structure comprising a member to be laminated having a metal layer on the surface and a resin film laminated on the surface of the metal layer, wherein the resin film is the resin material described above, can be suitably obtained. The method of laminating the resin film and the member to be laminated having the metal layer on the surface is not particularly limited, and a known method can be used. For example, using a device such as a parallel plate press or a roll laminator, the resin film can be laminated on a member to be laminated having a metal layer on the surface while heating or pressing without heating.

材料 The material of the metal layer is preferably copper.

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

The above resin material is suitably used for obtaining a copper-clad laminate. An example of the copper-clad laminate is a copper-clad laminate including a copper foil and a resin film laminated on one surface of the copper foil.

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

The above resin material is suitably used for obtaining a multilayer substrate.

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

In the multilayer substrate, it is preferable that a surface of the insulating layer opposite to a surface on which the circuit board is laminated is subjected to a roughening treatment.

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

Preferably, the multilayer substrate further includes a copper plating layer laminated on the roughened surface of the insulating layer.

Further, as another example of the multilayer substrate, a circuit board, an insulating layer stacked on the surface of the circuit board, and a surface of the insulating layer opposite to the surface on which the circuit board is stacked are stacked on a surface opposite to the surface on which the circuit board is stacked. And a multi-layer substrate provided with a copper foil. It is preferable that the insulating layer is formed by curing the resin film using a copper-clad laminate including a copper foil and a resin film laminated on one surface of the copper foil. Further, the copper foil has been subjected to an etching treatment, and is preferably a copper circuit.

Another example of the multilayer board is a multilayer board including a circuit board and a plurality of insulating layers stacked 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. It is preferable that the multilayer substrate further includes a circuit laminated on at least one surface of the insulating layer formed using the resin film.

の う ち In a multilayer printed wiring board of a multilayer substrate, a low dielectric loss tangent is required, and high insulation reliability by an insulating layer is required. Therefore, the resin material according to the present invention is suitably used for forming an insulating layer in a multilayer printed wiring board.

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

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

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

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

(Roughening and swelling)
The resin material is preferably used to obtain a cured product that is subjected to a roughening treatment or a desmear treatment. The cured product also includes a pre-cured product that can be further cured.

硬化 In order to form fine irregularities on the surface of the cured product obtained by pre-curing the resin material, the cured product is preferably subjected to a roughening treatment. Before the roughening treatment, the cured product is preferably subjected to a swelling treatment. The cured product is preferably subjected to a swelling treatment after the preliminary curing and before the roughening treatment, and is preferably cured after the roughening treatment. However, the cured product does not necessarily have to be subjected to a swelling treatment.

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

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

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

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

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

表面 In order to remove the smear, the surface of the cured product is preferably desmeared. Desmear processing may also serve as roughening processing.

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

使用 By using the above resin material, the surface roughness of the surface of the desmeared cured product becomes sufficiently small.

本 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited to the following examples.

The following materials were prepared.

(Maleimide compound)
<Maleimide compound A>
Maleimide compound A1 (molecular weight 9000) synthesized according to Synthesis Example 1 below
Maleimide compound A2 (molecular weight 4500) synthesized according to Synthesis Example 2 below
<Maleimide compound B>
N-alkyl bismaleimide compound 1 (“BMI-3000” manufactured by Designer Molecular Inc., having a molecular weight of more than 3000)
N-alkyl bismaleimide compound 2 (“BMI-689” manufactured by Designer Molecular Inc., molecular weight less than 1000)
N-phenylmaleimide compound (“MIR-3000” manufactured by Nippon Kayaku Co., Ltd., molecular weight less than 1000)

(Synthesis example 1)
In a reaction vessel equipped with a stirrer, a water separator, a thermometer and a nitrogen gas inlet tube, 55 g of pyromellitic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 254.15) and 300 g of toluene are put, and the reaction vessel Was heated to 60 ° C. Next, a solution in which 26.7 g of bis (aminomethyl) norbornane (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight: 154.26) was dissolved in toluene was dropped into the reaction vessel, and the reaction product having acid anhydrides at both ends was added. I got something. Next, 46.0 g of dimer diamine ("PRIAMINE 1075" manufactured by Croda Japan) was slowly added to the reaction vessel, a Dean Stark trap and a condenser were attached to the flask, and the mixture was heated to reflux for 2 hours. An imide compound having a structure was obtained. Next, 8.7 g of maleic anhydride was added, and the resulting mixture was refluxed for another 12 hours to perform maleimidation. Subsequently, isopropanol was poured, the product was precipitated, collected, and dried in a vacuum oven to obtain a maleimide compound A1 having a skeleton derived from dimer diamine only at both ends of the main chain. The yield of the maleimide compound A1 was 83%.

(Synthesis example 2)
250 mL of toluene was placed in a 500 mL eggplant flask, and 13.2 g (32 mmol) of dimer diamine ("PRIAMINE 1075" manufactured by Crowda Japan) and 24.9 g (128 mmol) of tricyclodecanediamine were added. Then, 35.3 g (120 mmol) of biphenyl dianhydride was added little by little. The eggplant flask was attached to a Dean-Stark apparatus, and heated and refluxed for 2 hours. Thus, a compound having an amine at both terminals and having a plurality of imide skeletons was obtained. After removing the water discharged at the time of the condensation and returning the temperature to room temperature, 8.83 g (90 mmol) of maleic anhydride was added, and the mixture was stirred and reacted by heating in the same manner. Thus, a compound having a maleimide skeleton at both terminals was obtained. The product was reprecipitated with isopropanol. Thereafter, the resultant was dried in a vacuum oven to obtain a maleimide compound A2 having a skeleton derived from dimer diamine. The maleimide compound A2 has a structure represented by the following formula (A2).

分子 The molecular weights of the maleimide compounds A1 and A2 synthesized in Synthesis Examples 1 and 2 were determined as follows.

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

(Epoxy compound)
Biphenyl type epoxy compound ("NC-3000" manufactured by Nippon Kayaku Co., Ltd.)
Resorcinol diglycidyl ether ("EX-201" manufactured by Nagase ChemteX Corporation)
Hyperbranched aliphatic epoxy compound (“FoldiE101” manufactured by Nissan Chemical Industries, Ltd.)
Naphthalene type epoxy compound (“HP-4032D” manufactured by DIC)
Naphthol aralkyl epoxy compound (“ESN-475V” manufactured by Nippon Steel & Sumitomo Metal Corporation)

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

(Curing agent)
Component X:
Liquid containing cyanate ester compound (“BA-3000S” manufactured by Lonza Japan, solid content 75% by weight)
Liquid containing active ester compound 1 (“EXB-9416-70BK” manufactured by DIC, solid content 70% by weight)
Active ester compound 2 (“EXB-8” manufactured by DIC, solid content 100% by weight)
Liquid containing active ester compound 3 (“HPC-8150-62T” manufactured by DIC, solid content 62% by weight)
Phenol compound-containing liquid ("LA-1356" manufactured by DIC, solid content 60% by weight)
Liquid containing carbodiimide compound (“V-03” manufactured by Nisshinbo Chemical Inc., solid content 50% by weight)
Benzoxazine compound (benzoxazine compound having a skeleton derived from dimer diamine) synthesized according to Synthesis Example 3 below

(Synthesis example 3)
100 mL of toluene was placed in a 250 mL reaction vessel, and 10.25 g (25 mmol) of dimer diamine ("PRIAMINE 1075" manufactured by Croda Japan) was sufficiently dissolved. Next, 11.25 g (130 mmol to 140 mmol) of formaldehyde solution and 7.06 g (75 mmol) of phenol were added little by little, and the mixture was heated to 120 ° C. with stirring, and reacted for 3 hours while removing generated water. Thereafter, the reaction solution was cooled to room temperature. The cooled reaction solution was washed with methanol and then dried to obtain 8.3 g of a viscous liquid benzoxazine compound.

(Curing accelerator)
Dimethylaminopyridine (“DMAP” manufactured by Wako Pure Chemical Industries, Ltd.)
2-phenyl-4-methylimidazole (“2P4MZ”, manufactured by Shikoku Chemicals, anionic curing accelerator)
Dicumyl peroxide (Tokyo Chemical Industry Co., Ltd.)

(Thermoplastic resin)
Polyimide compound (polyimide resin):
A polyimide compound-containing solution (non-volatile content: 26.8% by weight), which is a reaction product of tetracarboxylic dianhydride and dimer diamine, was synthesized according to Synthesis Example 4 below.

(Synthesis example 4)
In a reaction vessel equipped with a stirrer, a water separator, a thermometer and a nitrogen gas inlet tube, 300.0 g of tetracarboxylic dianhydride (“BisDA-1000” manufactured by SABIC Japan GK) and 665.5 g of cyclohexanone were placed. And the solution in the reaction vessel was heated to 60 ° C. Next, 89.0 g of dimer diamine ("PRIAMINE 1075", manufactured by Croda Japan) and 54.7 g of 1,3-bisaminomethylcyclohexane (manufactured by Mitsubishi Gas Chemical Company) were added dropwise to the reaction vessel. Next, 121.0 g of methylcyclohexane and 423.5 g of ethylene glycol dimethyl ether were added to the reaction vessel, and an imidization reaction was performed at 140 ° C. for 10 hours. Thus, a polyimide compound-containing solution (non-volatile content: 26.8% by weight) was obtained. The molecular weight (weight average molecular weight) of the obtained polyimide compound was 20,000. The molar ratio of the acid component / amine component was 1.04.

分子 The molecular weight of the polyimide compound synthesized in Synthesis Example 4 was determined as follows.

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

(Examples 1 to 14 and Comparative Examples 1 and 2)
The components shown in the following Tables 1 to 4 were blended in the amounts shown in the following Tables 1 to 4 (unit: parts by weight of solid content), and stirred at room temperature until a uniform solution was obtained, to obtain a resin material.

Preparation of resin film:
Using an applicator, the obtained resin material was coated on the release-treated surface of a release-treated PET film (“XG284” manufactured by Toray Industries, Inc., thickness: 25 μm), and the coating was performed in a gear oven at 100 ° C. for 2 minutes. After drying for 30 seconds, the solvent was evaporated. Thus, a laminated film (a laminated film of a PET film and a resin film) in which a resin film (B-stage film) having a thickness of 40 μm was laminated on the PET film was obtained.

(Evaluation)
(1) Glass transition temperature of maleimide compound Heating from −30 ° C. to 200 ° C. in a nitrogen atmosphere at a rate of 3 ° C./min using a differential scanning calorimeter (TA Instruments “Q2000”). The glass transition temperature was determined from the inflection point of the reverse heat flow. In the tables, the glass transition temperatures of the maleimide compound A are described in Examples 7 to 9, and 14.

(2) Embedding property on uneven surface and prevention of protrusion (prevention of excessive wetting and spreading)
Only the copper foil of a 100 mm square copper-clad laminate (a laminate of a glass epoxy substrate having a thickness of 400 μm and a copper foil having a thickness of 25 μm) was etched to form a depression (opening) having a diameter of 100 μm and a depth of 25 μm, The substrate was opened so that an interval of the center between adjacent holes was 900 μm on a straight line with respect to a 30 mm square area of the center of the substrate. Thus, an evaluation substrate having a total of 900 holes was prepared.

The resin film side of the obtained laminated film is superimposed on the evaluation substrate, and using a “batch type vacuum laminator MVLP-500-IIA” manufactured by Meiki Seisakusho, a laminating pressure of 0.4 MPa for 20 seconds and a pressing pressure of 0.8 MPa. For 20 seconds at 90 ° C. for laminating and pressing. After cooling at room temperature, the PET film was peeled off. Thus, an evaluation sample in which the resin film was laminated on the evaluation substrate was obtained.

に つ い て Voids in the depressions were observed for the obtained evaluation sample using an optical microscope. By evaluating the ratio of the dents in which voids were observed, the embedding property on the uneven surface was determined according to the following criteria.

[Evaluation criteria for embedding property on uneven surface]
：: 0% of pits where voids were observed
Δ: The percentage of dents where voids were observed was more than 0% and less than 5% ×: The percentage of dents where voids were observed was 5% or more

に つ い て The obtained evaluation sample was observed using an optical microscope to determine whether or not the resin film had protruded from a predetermined region on the substrate, and the anti-protrusion property was determined based on the following criteria.

[Criteria for preventing protrusion]
：: The protrusion of the resin film from the periphery of the evaluation substrate after lamination is 2 mm or less. Δ: The protrusion of the resin film from the periphery of the evaluation substrate after lamination exceeds 2 mm and 3 mm or less. Overhang of resin film exceeds 3mm

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

[Criteria for determining average linear expansion coefficient]
○: Average linear expansion coefficient is 25 ppm / ° C. or less ○: Average linear expansion coefficient is more than 25 ppm / ° C. and 30 ppm / ° C. or less ×: Average linear expansion coefficient is more than 30 ppm / ° C.

(4) Surface roughness (surface roughness) and uniformity of surface roughness after etching Laminating step and semi-curing treatment:
A double-sided copper-clad laminate (CCL substrate) (“E679FG” manufactured by Hitachi Chemical Co., Ltd.) was prepared. Both surfaces of the copper foil surface of this double-sided copper-clad laminate were immersed in “Cz8101” manufactured by MEC to roughen the surface of the copper foil. On both sides of the roughened copper-clad laminate, the resin film (B-stage film) side of the laminated film is placed on the copper-clad laminate using “Machine Seisakusho Co., Ltd.“ batch type vacuum laminator MVLP-500-IIA ””. And laminated to obtain a laminated structure. The laminating conditions were such that the pressure was reduced to 13 hPa or less by reducing the pressure for 30 seconds, and then the pressing was performed at 100 ° C. and a pressure of 0.4 MPa for 30 seconds. Then, it heated at 180 degreeC for 30 minutes, and the resin film was semi-hardened. Thus, a laminate in which the semi-cured resin film was laminated on the CCL substrate was obtained.

Roughening treatment:
(A) Swelling treatment:
The obtained laminate was put into a swelling liquid at 60 ° C. (“Swelling Dip Securiganto P” manufactured by Atotech Japan) and rocked for 10 minutes. Thereafter, the substrate was washed with pure water.

(B) Permanganate treatment (roughening treatment and desmear treatment):
The laminated body after the swelling treatment was put into a roughened aqueous solution of potassium permanganate (“Concentrate Compact CP” manufactured by Atotech Japan) at 80 ° C. and rocked for 30 minutes. Next, the sample was treated for 2 minutes using a washing liquid at 25 ° C. (“Reduction Securiganto P” manufactured by Atotech Japan), and then washed with pure water to obtain an evaluation sample.

Measurement of surface roughness:
Ten areas of 94 μm × 123 μm were arbitrarily selected on the surface of the evaluation sample (cured material subjected to the roughening treatment). The arithmetic average roughness Ra was measured for each of these 10 regions using a non-contact three-dimensional surface shape measuring device (“WYKO NT1100” manufactured by Veeco). The following surface roughness was evaluated from the average value of the arithmetic mean roughness Ra measured at 10 points, and the following value was calculated from the absolute value of the difference between the maximum value and the minimum value of the measured arithmetic average roughness Ra at 10 points. The uniformity of the surface roughness was evaluated. The arithmetic average roughness Ra was measured in accordance with JIS B0601: 1994.

[Criteria for surface roughness after etching]
○: Average value of arithmetic average roughness Ra is less than 80 nm ○: Average value of arithmetic average roughness Ra is 80 nm or more and less than 120 nm ×: Average value of arithmetic average roughness Ra is 120 nm or more

[Criteria for determining uniformity of surface roughness (surface roughness) after etching]
：: Absolute value of difference between maximum value and minimum value of arithmetic average roughness Ra is less than 20 nm Δ: Absolute value of difference between maximum value and minimum value of arithmetic average roughness Ra is 20 nm or more and less than 30 nm ×: Arithmetic average The absolute value of the difference between the maximum value and the minimum value of the roughness Ra is 30 nm or more

(5) Plating peel strength Electroless plating:
(4) The surface of the roughened cured product obtained by the evaluation of the surface roughness after etching (surface roughness) and the uniformity of the surface roughness was cleaned with a 60 ° C. alkaline cleaner (“Cleaner” manufactured by Atotech Japan KK). (Securigant 902 ") for 5 minutes, and degreased and washed. After washing, the cured product was treated with a pre-dip liquid at 25 ° C. (“Pre-Dip Neo Gant B” manufactured by Atotech Japan) for 2 minutes. Thereafter, the cured product was treated with an activator solution ("Activator Neo Gant 834" manufactured by Atotech Japan) at 40 ° C for 5 minutes to attach a palladium catalyst. Next, the cured product was treated with a reducing solution at 30 ° C. (“Reducer Neogant WA” manufactured by Atotech Japan) for 5 minutes.

Next, the cured product was placed in a chemical copper solution (“Basic Print Gant MSK-DK”, “Copper Print Gant MSK”, “Stabilizer Print Gant MSK”, and “Reducer Cu” manufactured by Atotech Japan), and electroless plating was performed. Was carried out until the plating thickness became about 0.5 μm. After the electroless plating, annealing was performed at a temperature of 120 ° C. for 30 minutes in order to remove the remaining hydrogen gas. In addition, all the processes up to the process of the electroless plating were performed while making the treatment liquid 2 L on a beaker scale and oscillating the cured product.

Electroplating treatment:
Next, electrolytic plating was performed on the cured product subjected to the electroless plating until the plating thickness became 25 μm. Copper sulfate solution ("Copper sulfate pentahydrate" manufactured by Wako Pure Chemical Industries, "Sulfuric acid" manufactured by Wako Pure Chemical Industries, "Basic Leveler Capparaside HL" manufactured by Atotech Japan, "Atotech Japan" A current of 0.6 A / cm ² was passed using a compensating agent Capparaside GS ”) to perform electrolytic plating until the plating thickness became about 25 μm. After the copper plating treatment, the cured product was heated at 190 ° C. for 90 minutes to further cure the cured product. Thus, a cured product having the copper plating layer laminated on the upper surface was obtained.

Measurement of plating peel strength:
A strip of 0.5 cm width was cut into the surface of the cured copper plating layer having the obtained copper plating layer laminated on the upper surface. The cured product having the copper plating layer laminated on the upper surface was set on a 90 ° peel tester (“TE-3001” manufactured by Tester Sangyo Co., Ltd.), and the end of the copper plating layer with the notch was picked up with a gripper, and the copper was lifted. The plating layer was peeled off by 15 mm, and the peel strength (plating peel strength) was measured.

[Criteria for plating peel strength]
○: plating peel strength of 0.5 kgf or more ：: plating peel strength of 0.3 kgf or more and less than 0.5 kgf ×: plating peel strength of less than 0.3 kgf

(6) Dielectric loss tangent The obtained resin film was cut into a size of 2 mm in width and 80 mm in length, and five sheets were overlaid to obtain a laminate having a thickness of 200 µm. The obtained laminate was heated at 190 ° C. for 90 minutes to obtain a cured product. The obtained cured product was subjected to a cavity resonance method at room temperature (23 ° C.) using “Cavity Resonance Perturbation Method Permittivity Measurement Apparatus CP521” manufactured by Kanto Electronics Application Development Co., Ltd. and “Network Analyzer N5224A PNA” manufactured by Keysight Technology, Inc. The dielectric loss tangent was measured at a high temperature (110 ° C.) at a frequency of 1.0 GHz. The dielectric loss tangent at a high temperature (110 ° C.) was measured by placing the measurement site in a thermostat.

The compositions and results are shown in Tables 1 to 4 below.

DESCRIPTION OF SYMBOLS 11 ... Multilayer printed wiring board 12 ... Circuit board 12a ... Upper surface 13-16 ... Insulating layer 17 ... Metal layer

Claims (20)

1. Including a maleimide compound having a skeleton derived from dimer diamine or a skeleton derived from trimer triamine,
   A resin material, wherein the maleimide compound has a glass transition temperature of 80 ° C. or higher.
2. The resin material according to claim 1, wherein the maleimide compound has a weight average molecular weight of 1,000 or more and 50,000 or less.
3. The resin material according to claim 2, wherein the weight average molecular weight of the maleimide compound is 3,000 or more and 30,000 or less.
4. 樹脂 The resin material according to any one of claims 1 to 3, wherein the maleimide compound is a citraconic imide compound.
5. The resin material according to any one of claims 1 to 4, wherein the maleimide compound has a skeleton derived from the dimer diamine or a skeleton derived from trimer triamine at both ends of the main chain.
6. The resin material according to any one of claims 1 to 5, wherein the maleimide compound has a skeleton derived from the dimer diamine or a skeleton derived from a trimer triamine only at both ends of the main chain.
7. The maleimide compound according to any one of claims 1 to 6, wherein the maleimide compound has a skeleton derived from a reaction product of a diamine compound other than dimer diamine and an acid dianhydride at a portion other than both ends of the main chain. Resin material.
8. The resin material according to any one of claims 1 to 7, further comprising a maleimide compound having no skeleton derived from dimer diamine.
9. The resin material according to claim 8, wherein the maleimide compound having no skeleton derived from the dimer diamine includes an N-phenylmaleimide compound.
10. Including inorganic filler,
    The resin material according to any one of claims 1 to 9, wherein the content of the inorganic filler is 50% by weight or more based on 100% by weight of components other than the solvent in the resin material.
11. The resin material according to claim 10, wherein the inorganic filler has an average particle size of 1 µm or less.
12. The resin material according to claim 10 or 11, wherein the inorganic filler is silica.
13. An epoxy compound;
    The curing agent according to any one of claims 1 to 12, comprising a phenol compound, a cyanate ester compound, an acid anhydride, an active ester compound, a carbodiimide compound, and a curing agent containing at least one component among benzoxazine compounds. Resin material.
14. The curing agent contains the benzoxazine compound,
    The resin material according to claim 13, wherein the benzoxazine compound has a skeleton derived from dimer diamine.
15. Contains a curing accelerator,
    The resin material according to any one of claims 1 to 14, wherein the curing accelerator includes an anionic curing accelerator.
16. The resin material according to claim 15, wherein the content of the anionic curing accelerator is 20% by weight or more based on 100% by weight of the curing accelerator.
17. The resin material according to any one of claims 1 to 16, which is a resin film.
18. A member to be laminated having a metal layer on the surface, comprising a resin film laminated on the surface of the metal layer,
    A laminated structure, wherein the resin film is the resin material according to any one of claims 1 to 17.
19. 19. The laminated structure according to claim 18, wherein the material of the metal layer is copper.
20. A circuit board,
    A plurality of insulating layers disposed on the surface of the circuit board,
    A metal layer disposed between the plurality of insulating layers,
    A multilayer printed wiring board, wherein at least one of the plurality of insulating layers is a cured product of the resin material according to any one of claims 1 to 17.

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