JP6805338B2 - Resin material, laminated structure and multi-layer printed wiring board - Google Patents

Description

The present invention relates to a resin material containing a maleimide compound or a benzoxazine compound and an inorganic filler. 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 in order to obtain electronic components such as semiconductor devices, laminated boards and printed wiring boards. For example, in a multilayer printed wiring board, a resin material is used to form an insulating layer for insulating the inner layers and to form an insulating layer located on a surface layer portion. Wiring, which is generally metal, is laminated on the surface of the insulating layer. Further, in order to form the insulating layer, a resin film obtained by forming the resin material into a film may be used. The resin material and the resin film are used as an insulating material for a multilayer printed wiring board including a build-up film.

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

Patent Document 2 below discloses a resin composition for an electronic material containing 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 8 or more atoms are linearly linked. ..

WO2016 / 114286A1 JP-A-2018-90728

In order to enhance the electrical characteristics of the cured product (insulating layer), a compound having a small polarity may be added to the resin material (resin composition). However, when a cured product (insulating layer) is formed using a resin material containing a compound having a low polarity, the adhesion between the insulating layer and the metal layer is not sufficiently high, or the cured product is thermally dimensionally stable. The sex may not be high enough. Therefore, the wiring (metal layer) may be peeled off from the insulating layer.

Further, when the insulating layer is formed by using the conventional resin material as described in Patent Documents 1 and 2, the thermal dimensional stability is not sufficiently high, or the surface roughness after etching is sufficiently small. It may not be there. If the surface roughness after etching is not sufficiently small, the strength of the insulating layer will not be sufficiently high because the resin that contributes to the anchor effect will be partially thinned, and the cured product (insulating layer) after etching The plating peel strength with the metal layer laminated on the surface of the insulating layer by plating may not be sufficiently high.

Further, in the conventional resin material containing an epoxy resin, the adhesion between the insulating layer and the metal layer (particularly, the adhesion at high temperature) may not be sufficiently high. As a result, reflow resistance may decrease.

In this way, 1) the dielectric loss tangent of the cured product is lowered, 2) the thermal dimensional stability of the cured product is improved, 3) the adhesion between the insulating layer and the metal layer is improved, and 4) the surface roughness after etching is improved. At present, it is extremely difficult to obtain a resin material that can exhibit all the effects of 1) -5) that can be made smaller and 5) the plating peel strength can be increased.

The object of the present invention is 1) to lower the dielectric loss tangent of the cured product, 2) to improve the thermal dimensional stability of the cured product, 3) to improve the adhesion between the insulating layer and the metal layer, and 4) to roughen the surface after etching. It is to provide a resin material which can reduce the degree and 5) increase the plating peel strength. 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, a bismaleimide compound having a skeleton derived from dimerdiamine and a skeleton derived from a diamine compound other than diaminediamine and a skeleton derived from dimerdiamine, and a diamine Provided is a resin material containing at least one compound A of a benzoxazine compound having a skeleton derived from a diamine compound other than diamine and an inorganic filler.

In certain aspects of the resin material according to the present invention, the distance between amino groups in the skeleton derived from the diamine compound other than the dimer diamine is shorter than the distance between the amino groups in the skeleton derived from the dimer diamine.

In certain aspects of the resin material according to the present invention, the compound A has a skeleton derived from the dimer diamine at both ends of the main chain.

In certain aspects of the resin material according to the present invention, the compound A has a skeleton derived from the dimer diamine only at both ends of the main chain.

In certain aspects of the resin material according to the invention, the compound A has a molecular weight of less than 20000.

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

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

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

In certain aspects of the resin material according to the invention, the resin material comprises a skeletonless maleimide compound derived from a dimer diamine.

In certain aspects of the resin material according to the present invention, the compound A comprises a bismaleimide compound having a skeleton derived from the diamine diamine and having a skeleton derived from a diamine compound other than diamine diamine. A bismaleimide compound having a skeleton derived from dimerdiamine and having a skeleton derived from a diamine compound other than diaminediamine is a first bismaleimide compound having a skeleton derived from dimerdiamine only at both ends of the main chain. And a second bismaleimide compound having a skeleton derived from dimerdiamine in the skeleton other than both ends of the main chain and having two or more imide skeletons.

In certain aspects of the resin material according to the invention, epoxy compounds and phenolic compounds, cyanate ester compounds, acid anhydrides, active ester compounds, carbodiimide compounds, and skeletonless benzoxazine compounds derived from dimerdiamine. Includes a hardener containing at least one of these components.

In certain aspects of the resin material according to the present invention, a curing accelerator is included, and the curing accelerator contains an anionic curing accelerator.

In certain aspects of the resin material according to the present invention, the anionic curing accelerator is an imidazole compound.

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 in 100% by weight of the curing accelerator.

In certain aspects 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, a laminated structure comprising a member to be laminated having a metal layer on its surface and a resin film laminated on the surface of the metal layer, wherein the resin film is the resin material described above. The body is provided.

In certain aspects 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, the plurality of insulating layers include a circuit board, a plurality of insulating layers arranged on the surface of the circuit board, and a metal layer arranged between the plurality of insulating layers. A multilayer printed wiring board is provided in which at least one of the layers is a cured product of the resin material described above.

The resin material according to the present invention has a bismaleimide compound having a skeleton derived from dimerdiamine and a skeleton derived from a diamine compound other than diaminediamine, and a skeleton derived from dimerdiamine, and diaminediamine. It contains at least one compound A of the benzoxazine compounds having a skeleton derived from a diamine compound other than the above. The resin material according to the present invention includes an inorganic filler. Since the resin material according to the present invention has the above-mentioned structure, 1) the dielectric loss tangent of the cured product is lowered, 2) the thermal dimensional stability of the cured product is improved, and 3) the insulating layer and the metal layer are separated from each other. All of the effects of 1) -5) can be exhibited, such as improving the adhesion, 4) reducing the surface roughness after etching, and 5) increasing the plating peel strength.

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

Hereinafter, the present invention will be described in detail.

The resin material according to the present invention has a bismaleimide compound having a skeleton derived from dimerdiamine and a skeleton derived from a diamine compound other than diaminediamine, and a skeleton derived from dimerdiamine, and diaminediamine. It contains at least one compound A of the benzoxazine compounds having a skeleton derived from a diamine compound other than the above. The resin material according to the present invention includes an inorganic filler. The skeleton derived from dimerdiamine and the skeleton derived from a diamine compound other than dimerdiamine exist as partial skeletons in the above compound A.

Since the resin material according to the present invention has the above-mentioned structure, 1) the dielectric loss tangent of the cured product is lowered, 2) the thermal dimensional stability of the cured product is improved, and 3) the insulating layer and the metal layer are separated from each other. All of the effects of 1) -5) can be exhibited, such as improving the adhesion, 4) reducing the surface roughness after etching, and 5) increasing the plating peel strength. Further, for example, 2) the coefficient of linear expansion (CTE) of the cured product can be reduced as the thermal dimensional stability of the cured product. Further, for example, 3) as the adhesion between the insulating layer and the metal layer, the peel strength between the insulating layer and the metal layer in the temperature range of room temperature to high temperature (for example, 260 ° C.) can be increased.

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

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

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

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

[Compound A having a skeleton derived from a dimer diamine and having a skeleton derived from a diamine compound other than dimer diamine]
The resin material according to the present invention has a bismaleimide compound having a skeleton derived from dimerdiamine and a skeleton derived from a diamine compound other than diaminediamine, and a skeleton derived from dimerdiamine, and diaminediamine. It contains at least one compound A of the benzoxazine compounds having a skeleton derived from a diamine compound other than the above. The resin material according to the present invention may contain only the bismaleimide compound or only the benzoxazine compound as the compound A, and may contain both the bismaleimide compound and the benzoxazine compound. It may be included.

By using the above-mentioned compound A, the effects of the above-mentioned 1) -5) of the present invention can be exhibited. By using the above compound A, the surface roughness (surface roughness) of the cured product can be appropriately reduced, and the plating peel strength can be increased. The surface roughness depends on the amount of resin to be etched. Etching tends to occur at the double bond site of the compound contained in the resin material. Therefore, compounds having a skeleton derived from an imide bond and a dimer diamine are easily etched. In the compound A, the imide bond and the content of the skeleton derived from the diamine diamine can be controlled by controlling the molecular weight of the diamine compound other than the diamine diamine, so that the surface roughness after etching can be reduced. Moreover, the plating peel strength can be increased. The compound A may or may not have an aromatic skeleton. As the compound A, only one kind may be used, or two or more kinds may be used in combination.

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.

The skeleton derived from the diamine compound has or does not have an aromatic ring. The skeleton derived from the diamine compound may or may not have an aromatic ring.

The skeleton derived from the diamine compound has or does not have an aliphatic ring. The skeleton derived from the diamine compound may or may not have an aliphatic 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 a dicyclopentadiene.

From the viewpoint of effectively exerting the effects of the present invention of 1) -5) described above, in the compound A, the distance between amino groups in the skeleton derived from a diamine compound other than the dimer diamine is set to the dimer diamine. It is preferably shorter than the distance between the amino groups in the skeleton from which it is derived. That is, it is preferable that the total of B1, B2, and B3 shown below is smaller than the total of A1 and A2 shown below.

Let A1 be the number of aliphatic rings contained in the dimer diamine skeleton. A1 represents an integer of 0 or more. The aliphatic ring means a ring other than the aromatic ring. The aliphatic ring may have a double bond in a part of the ring.

Among the carbon atoms existing between the nitrogen atom constituting one amino group and the nitrogen atom constituting the other amino group in the skeleton derived from the dimerdiamine, the aromatic ring and the aliphatic ring are formed. Let A2 be the number of carbon atoms that are not composed. A2 represents an integer of 1 or more.

Since the dimer diamine is a natural product (mixture), it is difficult to define the structure of the dimer diamine as one structure. Therefore, in order to calculate the above A1 and A2, the skeleton of the formula (3) used in the item of Examples described later may be used as the representative skeleton of the dimer diamine (dimer diamine skeleton). When the skeleton of the formula (3) is used as the dimer diamine skeleton to calculate the above A1 and A2, the total of A1 and A2 is 17. Even if the total of A1 and A2 is 17, the effect of the present invention is not impaired. The dimer diamine skeleton may or may not have an unsaturated bond.

The number of aromatic rings contained in the skeleton derived from the diamine compound other than the diamine diamine is defined as B1, and the number of aliphatic rings contained in the skeleton derived from the diamine compound other than the diamine diamine is defined as B2. B1 and B2 each represent an integer of 0 or more. The aliphatic ring means a ring other than the aromatic ring. The aliphatic ring may have a double bond in a part of the ring. Further, the fused ring is counted as one aromatic ring.

Carbon atom, nitrogen atom and oxygen atom existing between the nitrogen atom constituting one amino group and the nitrogen atom constituting the other amino group in the skeleton derived from the diamine compound other than the dimerdiamine. Of these, the number of carbon atoms, nitrogen atoms, and oxygen atoms that do not constitute an aromatic ring and an aliphatic ring is defined as B3. B3 represents an integer of 1 or more. When determining B3, it is preferable that the one amino group and the other amino group are primary amino groups, respectively. When three or more primary amino groups are present in the skeleton derived from a diamine compound other than the dimer diamine, the larger value of B3 is adopted.

From the viewpoint of effectively exerting the effects of the present invention of 1) -5) described above, it is preferable that the total of B1, B2 and B3 is smaller than the total of A1 and A2. As described above, when the total of A1 and A2 is 17, the total of B1, B2 and B3 is preferably less than 17.

From the viewpoint of exerting the effects of the present invention of 1) -5) described above even more effectively, the absolute value of the difference between the total of A1 and A2 and the total of B1 and B2 and B3 is preferable. Is 5 or more, more preferably 7 or more, preferably 14 or less, and more preferably 10 or less.

<Bismaleimide compound having a skeleton derived from dimerdiamine and having a skeleton derived from a diamine compound other than dimerdiamine (bismaleimide compound A)>
In the resin material according to the present invention, as the compound A, a bismaleimide compound having a skeleton derived from a dimerdiamine and having a skeleton derived from a diamine compound other than dimerdiamine (hereinafter, referred to as “bismaleimide compound A”). It may be described). Only one kind of the bismaleimide compound A may be used, or two or more kinds may be used in combination.

The bismaleimide compound A may be a citraconimide compound. The citraconimide compound is a compound in which a methyl group is bonded to one of the carbon atoms constituting the double bond between the carbon atoms in the maleimide group. Since the citraconimide compound has slightly lower reactivity than the maleimide compound, storage stability can be improved.

The bismaleimide compound A preferably has a skeleton derived from the dimer diamine at both ends of the main chain. In this case, the bismaleimide compound A may have a skeleton derived from the dimer diamine in a skeleton other than both ends of the main chain and both ends of the main chain, and the dimer only at both ends of the main chain. It may have a skeleton derived from diamine. The skeleton derived from the dimer diamine is a flexible skeleton. Therefore, when the bismaleimide compound A has a skeleton derived from the dimer diamine at both ends of the main chain, the reactivity of the maleimide group can be enhanced and the curing reaction can be sufficiently advanced. .. As a result, 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.

It is more preferable that the bismaleimide compound A has a skeleton derived from the dimer diamine only at both ends of the main chain. When the bismaleimide compound A has a skeleton derived from the dimer diamine only at both ends of the main chain, the softening point of the bismaleimide compound A can be made higher, so that the cured product of the resin material can be made higher. The glass transition temperature can be increased even more effectively. 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. When the bismaleimide compound A has a skeleton derived from the dimer diamine only at both ends of the main chain, the skeleton other than the skeleton derived from the dimer diamine of the main chain of the bismaleimide compound A is other. The compatibility with thermosetting resins (epoxy compounds, curing agents, etc.) can be enhanced, and the viscosity of the film, especially when cut at a low temperature, can be reduced.

The bismaleimide compound A has a first bismaleimide compound having a skeleton derived from dimerdiamine only at both ends of the main chain, and a skeleton derived from dimerdiamine in a skeleton other than both ends of the main chain. Moreover, it is preferable to contain a second bismaleimide compound having two or more imide skeletons. In this case, the effects of the present invention described in 1) -5) can be effectively exerted.

The bismaleimide compound A is obtained by reacting a tetracarboxylic dianhydride, a dimer diamine, and a diamine compound other than dimer diamine to obtain a reaction product, and then reacting the reaction product with maleic anhydride. be able to. The reaction product of the tetracarboxylic dianhydride and the dimer diamine is preferably a compound having amino groups at both ends.

The bismaleimide compound A having a skeleton derived from the dimer diamine only at both ends of the main chain can be obtained, for example, as follows. The tetracarboxylic dianhydride is reacted with a diamine compound other than dimerdiamine to obtain a first reaction product. The obtained first reaction product is reacted with a dimer diamine to obtain a second reaction product having amino groups at both ends. The second reaction product obtained is reacted with maleic anhydride.

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

Examples of commercially available products 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. (Product name, hydrogenated product of Versamine 551, manufactured by Cognix Japan), PRIAMINE 1075, and PRIAMINE 1074 (trade name, both manufactured by Croda Japan) and the like.

Examples of diamine compounds other than the above diamine diamines include 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, bis (aminomethyl) norbornane, 3 (4), 8 (9) -bis. (Aminomethyl) tricyclo [5.2.1.02,6] decane, 1,1-bis (4-aminophenyl) cyclohexane, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 2,7-diamino Fluorene, 4,4'-ethylenedianiline, isophorone diamine, 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.

Weight ratio of the content of the bismaleimide compound A to the total content of the epoxy compound and the component X described later (content of the bismaleimide compound A / total content of the epoxy compound and the component X) ) Is preferably 0.05 or more, more preferably 0.1 or more, still more preferably 0.15 or more. Weight ratio of the content of the bismaleimide compound A to the total content of the epoxy compound and the component X described later (content of the bismaleimide compound A / total content of the epoxy compound and the component X) ) Is preferably 0.9 or less, more preferably 0.75 or less. When the weight ratio is at least the above lower limit and at least the above upper limit, the dielectric loss tangent can be further lowered and the thermal dimensional stability can be further improved. Further, when the weight ratio is at least the above lower limit and at least the above upper limit, the surface roughness after etching can be further reduced, and the plating peel strength can be further increased.

The content of the bismaleimide compound A is preferably 5% by weight or more, more preferably 10% by weight or more, still more preferably 15% by weight or more in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material. , Preferably 80% by weight or less, more preferably 70% by weight or less. When the content of the bismaleimide compound A is not more than the above lower limit, the dielectric loss tangent can be further lowered, the adhesion between the insulating layer and the metal layer can be further improved, and the surface roughness after etching can be further improved. It can be made smaller. When the content of the bismaleimide compound A is not more than the above upper limit, the thermal dimensional stability can be further improved.

From the viewpoint of effectively exerting the effects of the present invention of 1) -5) described above, the molecular weight of the bismaleimide compound A is preferably 500 or more, more preferably 1000 or more, preferably less than 20000, and more preferably. It is less than 15,000, more preferably less than 7,500, and particularly preferably less than 5,000. When the molecular weight is at least the above upper limit, the melt viscosity of the resin material may be higher than when the molecular weight is less than the above upper limit, and the embedding property in holes or irregularities of the circuit board may be deteriorated. ..

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

In a bismaleimide compound having a skeleton derived from dimerdiamine and not having a skeleton derived from a diamine compound other than diaminediamine, when the molecular weight of the bismaleimide compound is large (for example, the number average molecular weight is 1500 or more). In the case of), the bismaleimide compound tends to agglomerate excessively, and the viscosity of the resin material may become too high. As a commercially available product of the bismaleimide compound having a skeleton derived from the above dimer diamine and not having a skeleton derived from a diamine compound other than dimer diamine, for example, Designer Molecules Inc. Examples thereof include "BMI 3000J" and "BMI 5000" manufactured by the same company.

From the viewpoint of further enhancing the thermal dimensional stability of the cured product and further enhancing the adhesion between the insulating layer and the metal layer, the softening point of the bismaleimide compound A is preferably 75 ° C. or higher, more preferably 90 ° C. or higher. That is all.

The inflection point is heated from −30 ° C. to 200 ° C. in a nitrogen atmosphere at a heating rate of 3 ° C./min using a differential scanning calorimetry device (for example, “Q2000” manufactured by TA Instruments). It can be obtained from the inflection point of the reverse heat flow.

<A benzoxazine compound having a skeleton derived from diamine diamine and having a skeleton derived from a diamine compound other than diamine diamine (benzoxazine compound A)>
The resin material according to the present invention refers to the above-mentioned compound A as a benzoxazine compound having a skeleton derived from a dimer diamine and having a skeleton derived from a diamine compound other than dimer diamine (hereinafter, referred to as "benzoxazine compound A"). May be described). As the benzoxazine compound A, only one kind may be used, or two or more kinds may be used in combination.

The benzoxazine compound A preferably has a skeleton derived from the dimer diamine at both ends of the main chain. In this case, the benzoxazine compound A may have a skeleton derived from the dimer diamine in a skeleton other than both ends of the main chain and both ends of the main chain, and the dimer only at both ends of the main chain. It may have a skeleton derived from diamine. The skeleton derived from the dimer diamine is a flexible skeleton. Therefore, when the benzoxazine compound A has a skeleton derived from the dimer diamine at both ends of the main chain, the reactivity of the benzoxazine group can be enhanced and the curing reaction can be sufficiently advanced. it can. As a result, 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.

It is more preferable that the benzoxazine compound A has a skeleton derived from the dimer diamine only at both ends of the main chain. When the benzoxazine compound A has a skeleton derived from the diamine diamine only at both ends of the main chain, the softening point of the benzoxazine compound A can be made higher, so that the cured product of the resin material can be made higher. The glass transition temperature can be increased even more effectively. 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. When the benzoxazine compound A has a skeleton derived from the diamine diamine only at both ends of the main chain, the skeleton other than the skeleton derived from the diamine diamine of the main chain of the benzoxazine compound A is other. The compatibility with thermosetting resins (epoxy compounds, curing agents, etc.) can be enhanced, and the viscosity of the film, especially when cut at a low temperature, can be reduced.

The benzoxazine compound A is obtained by reacting a tetracarboxylic acid dianhydride, a dimer diamine, and a diamine compound other than dimer diamine to obtain a reaction product, and then reacting the reaction product with phenol and paraformaldehyde. Obtainable. The reaction product of the tetracarboxylic dianhydride and the dimer diamine is preferably a compound having amino groups at both ends.

The benzoxazine compound A having a skeleton derived from the dimer diamine only at both ends of the main chain can be obtained, for example, as follows. The tetracarboxylic dianhydride is reacted with a diamine compound other than dimerdiamine to obtain a first reaction product. The obtained first reaction product is reacted with a dimer diamine to obtain a second reaction product having amino groups at both ends. The second reaction product obtained is reacted with phenol and paraformaldehyde.

Examples of the tetracarboxylic dianhydride include the above-mentioned tetracarboxylic dianhydride.

Examples of the commercially available product of the dimer diamine include the above-mentioned commercially available products.

Examples of the diamine compound other than the above-mentioned diamine diamine include the above-mentioned diamine compounds.

Weight ratio of the content of the benzoxazine compound A to the total content of the epoxy compound and the component X described later (content of the benzoxazine compound A / total content of the epoxy compound and the component X) ) Is preferably 0.05 or more, more preferably 0.1 or more, still more preferably 0.15 or more. Weight ratio of the content of the benzoxazine compound A to the total content of the epoxy compound and the component X described later (content of the benzoxazine compound A / total content of the epoxy compound and the component X) ) Is preferably 0.9 or less, more preferably 0.75 or less. When the weight ratio is at least the above lower limit and at least the above upper limit, the dielectric loss tangent can be further lowered and the thermal dimensional stability can be further improved. Further, when the weight ratio is at least the above lower limit and at least the above upper limit, the surface roughness after etching can be further reduced, and the plating peel strength can be further increased.

The content of the benzoxazine compound A in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material is preferably 5% by weight or more, more preferably 10% by weight or more, still more preferably 15% by weight or more. , Preferably 80% by weight or less, more preferably 70% by weight or less. When the content of the benzoxazine compound A is at least the above lower limit, the dielectric loss tangent can be further lowered, the adhesion between the insulating layer and the metal layer can be further improved, and the surface roughness after etching can be further improved. It can be made smaller. When the content of the benzoxazine compound A is not more than the above upper limit, the thermal dimensional stability can be further enhanced.

From the viewpoint of effectively exerting the effects of the present invention of 1) -5) described above, the molecular weight of the benzoxazine compound A is preferably 500 or more, more preferably 1000 or more, preferably less than 20000, and more preferably. It is less than 15,000, more preferably less than 7,500, and particularly preferably less than 5,000. When the molecular weight is at least the above upper limit, the melt viscosity of the resin material may be higher than when the molecular weight is less than the above upper limit, and the embedding property in holes or irregularities of the circuit board may be deteriorated. ..

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

From the viewpoint of further enhancing the thermal dimensional stability of the cured product and further enhancing the adhesion between the insulating layer and the metal layer, the softening point of the benzoxazine compound A is preferably 75 ° C. or higher, more preferably 90 ° C. or higher. That is all.

The inflection point is heated from −30 ° C. to 200 ° C. in a nitrogen atmosphere at a heating rate of 3 ° C./min using a differential scanning calorimetry device (for example, “Q2000” manufactured by TA Instruments). It can be obtained from the inflection point of the reverse heat flow.

[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. Only one type of the epoxy compound may be used, or two or more types may be used in combination.

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

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

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

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

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

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

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

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

Weight ratio of the content of the epoxy compound to the total content of the bismaleimide compound A and the component X described later (content of the epoxy compound / total content of the bismaleimide compound A and the component X) ) Is preferably 0.1 or more, more preferably 0.2 or more, preferably 0.9 or less, and more preferably 0.8 or less. When the weight ratio is at least the above lower limit and at least the above upper limit, the dielectric loss tangent can be further lowered and the thermal dimensional stability can be further improved.

Weight ratio of the content of the epoxy compound to the total content of the benzoxazine compound A and the component X described later (content of the epoxy compound / total content of the benzoxazine compound A and the component X) ) Is preferably 0.1 or more, more preferably 0.2 or more, preferably 0.9 or less, and more preferably 0.8 or less. When the weight ratio is at least the above lower limit and at least the above upper limit, the dielectric loss tangent can be further lowered and the thermal dimensional stability can be further improved.

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

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

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

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

The average particle size of the inorganic filler is preferably 50 nm or more, more preferably 100 nm or more, still more preferably 500 nm or more, preferably 5 μm or less, more preferably 3 μm or less, still more preferably 1 μm or less. When the average particle size of the inorganic filler is not less than the above lower limit and not more than the above upper limit, the surface roughness after etching can be reduced and the plating peel strength can be increased, and the insulating layer and the metal layer can be combined. Adhesion can be further improved.

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

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

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

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

The content of the inorganic filler in 100% by weight of the component excluding the solvent in the resin material 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. % Or more, preferably 90% by weight or less, more preferably 85% by weight or less, still more preferably 80% by weight or less, and particularly preferably 75% by weight or less. When the content of the inorganic filler is at least the above lower limit, the dielectric loss tangent is effectively lowered. When the content of the inorganic filler is not more than the above upper limit, the thermal dimensional stability can be improved and the warpage of the cured product can be effectively suppressed. When the content of the inorganic filler is at least the above lower limit and at least the above upper limit, the surface roughness of the surface of the cured product can be further reduced, and finer wiring can be formed on the surface of the cured product. Can be done. Further, with this amount of inorganic filler, it is possible to reduce the coefficient of thermal expansion of the cured product and at the same time improve the smear removability.

[Maleimide compound without skeleton derived from dimer diamine]
The resin material preferably contains a maleimide compound having no skeleton derived from a dimer diamine. The maleimide compound having no skeleton derived from the dimer diamine is different from the bismaleimide compound A. By using the bismaleimide compound A in combination with the maleimide compound having no skeleton derived from the dimer diamine, the effect of the present invention can be further exhibited, and in particular, the thermal dimensional stability of the cured product can be improved. Can be enhanced. The maleimide compound having no skeleton derived from the dimer diamine preferably has a skeleton derived from a diamine compound other than the dimer diamine. The maleimide compound having no skeleton derived from the dimer diamine preferably has an aromatic skeleton. As the maleimide compound having the above aromatic skeleton, only one kind may be used, or two or more kinds may be used in combination.

In the maleimide compound having no skeleton derived from the dimerdiamine, it is preferable that the nitrogen atom in the maleimide skeleton and the aromatic ring are bonded.

Examples of the maleimide compound having no skeleton derived from the dimer diamine include N-phenylmaleimide and the like.

The content of the skeleton-free maleimide compound derived from the dimerdiamine is preferably 2.5% by weight or more, more preferably 5% by weight, out of 100% by weight of the components excluding the inorganic filler and the solvent in the resin material. % Or more, more preferably 7.5% by weight or more, preferably 50% by weight or less, and more preferably 35% by weight or less. When the content of the maleimide compound having no skeleton derived from the dimer diamine is not less than the above lower limit and not more than the above upper limit, the effect of the present invention described in 1) -5) can be further exhibited.

From the viewpoint of effectively exerting the effects of the present invention of 1) -5) described above, the molecular weight of the skeleton-free maleimide compound derived from the dimer diamine is preferably 500 or more, more preferably 1000 or more. It is preferably less than 50,000, more preferably less than 20,000.

The molecular weight of the skeleton-free maleimide compound derived from the dimer diamine is that the maleimide compound having no skeleton derived from the dimer diamine is not a polymer and the maleimide compound having no skeleton derived from the dimer diamine. When the structural formula of the compound can be specified, it means the molecular weight that can be calculated from the structural formula. The molecular weight of the skeleton-free maleimide compound derived from the dimerdiamine is measured by gel permeation chromatography (GPC) when the skeleton-free maleimide compound derived from the dimerdiamine is a polymer. The weight average molecular weight in terms of polystyrene is shown.

Examples of commercially available maleimide compounds having no skeleton derived from the dimer diamine include "BMI 4000" and "BMI 5100" manufactured by Daiwa Kasei Kogyo Co., Ltd.

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

Examples of the curing agent include cyanate ester compound (cyanate ester curing agent), amine compound (amine curing agent), thiol compound (thiol curing agent), imidazole compound, phosphine compound, dicyandiamide, phenol compound (phenol curing agent), and acid anhydride. Examples thereof include substances, active ester compounds, carbodiimide compounds (carbodiimide curing agents), and benzoxazine compounds (benzoxazine curing agents) having no skeleton derived from dimerdiamine. The curing agent preferably has a functional group capable of reacting with the epoxy group of the epoxy compound.

The curing agent preferably contains at least one component of a phenol compound, a cyanate ester compound, an acid anhydride, an active ester compound, a carbodiimide compound, and a skeletonless benzoxazine compound derived from dimerdiamine. .. By using these preferred curing agents, thermal dimensional stability can be further enhanced.

Hereinafter, "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 having no skeleton derived from dimerdiamine" is referred to as "component X". May be described.

Therefore, the resin material preferably contains a curing agent containing the component X. It is more preferable that the component X contains at least a phenol compound. As the component X, only one kind may be used, or two or more kinds may be used in combination.

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

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

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

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

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

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

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, a naphthalene ring which may have a substituent, and the like. Examples of the substituent include a hydrocarbon group. The hydrocarbon group has preferably 12 or less carbon atoms, more preferably 6 or less carbon atoms, and even more preferably 4 or less carbon atoms.

The combination of X1 and X2 includes a combination of a benzene ring which may have a substituent and a benzene ring which may have a substituent, a benzene ring which may have a substituent, and a substitution. Examples thereof include a combination with a naphthalene ring which may have a group. Further, as a combination of X1 and X2, a combination of an aliphatic ring which may have a substituent and a benzene ring which may have a substituent, and a naphthalene ring which may have a substituent may be used. And a combination with 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 lowering the dielectric loss tangent of the cured product and increasing the thermal dimensional stability of the cured product, it is more preferable to have a naphthalene ring in the main chain skeleton of the active ester.

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

The carbodiimide compound 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 for other groups. Only one kind of the carbodiimide compound may be used, or two or more kinds may be used in combination.

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

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

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

Examples of the skeleton-free benzoxazine compound derived from the dimer diamine include P-d-type benzoxazine and Fa-type benzoxazine.

Examples of commercially available products of the skeleton-free benzoxazine compound derived from the dimer diamine include "P-d type" manufactured by Shikoku Chemicals Corporation.

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, and more preferably 120 parts by weight or less. When the content of the component X is not less than the above lower limit and not more than the above upper limit, the curability is further improved, the thermal dimensional stability is further enhanced, and the volatilization of the residual unreacted component can be further suppressed.

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

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

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

Examples of the imidazole compound include 2-undecyl imidazole, 2-heptadecyl imidazole, 2-methyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 2-phenyl-4-methyl imidazole and 1-benzyl-. 2-Methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-un Decylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimerite, 1-cyanoethyl-2-phenylimidazolium trimerite, 2,4-diamino-6- [2' -Methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino- 6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s -Triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-dihydroxymethylimidazole And so on.

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

Examples of the phosphorus compound include triphenylphosphine compounds.

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

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

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

From the viewpoint of further suppressing the curing temperature and effectively suppressing the warp of the cured product, the content of the anionic curing accelerator is preferably 20% by weight or more, more preferably 20% by weight or more, based on 100% by weight of the curing accelerator. Is 50% by weight or more, more preferably 70% by weight or more, and most preferably 100% by weight (total amount). Therefore, the curing accelerator is most preferably the anionic curing accelerator. By using the anionic curing accelerator and the radical curing accelerator in combination, the curing behavior may be controlled more precisely. Further, when the epoxy compound and the active ester compound are used, the curing behavior can be controlled more precisely by using dimethylaminopyridine as a cationic curing accelerator in order to control the curing temperature.

The content of the curing accelerator is not particularly limited. The content of the curing accelerator is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, and preferably 5% by weight in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material. Hereinafter, it is more preferably 3% by weight or less. When the content of the curing accelerator is at least the above lower limit and at least the above upper limit, the resin material is efficiently cured. If the content of the curing accelerator is in a more preferable range, the storage stability of the resin material becomes even higher, and a better cured product can be obtained.

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

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

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

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

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

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

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

Examples of the tetracarboxylic dianhydride include the above-mentioned tetracarboxylic dianhydride.

Examples of the commercially available product of the dimer diamine include the above-mentioned commercially available products.

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

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

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

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

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

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

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

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

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

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

Examples of the other thermosetting resin include polyphenylene ether resin, divinylbenzyl ether resin, polyarylate resin, diallylphthalate resin, polyimide resin, benzoxazine resin, benzoxazole resin, bismaleimide resin and acrylate resin.

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

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

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

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

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

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 mold release treatment, if necessary.

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

From the viewpoint of further enhancing 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 resin material or the resin film is preferably 150 ° C. or higher, more preferably. Is 170 ° C. or higher.

The glass transition temperature is measured as follows.

When the resin material is not a resin film, it is molded into a film to obtain a resin film. The resin film is press-molded to obtain an object to be measured. The obtained measurement object is measured using a viscoelasticity measuring device (for example, "ARES-G2" manufactured by TAINSTRUMENTS), and the peak temperature of the loss tangent of the obtained measurement result is defined as the glass transition temperature Tg. In the above measurement, a parallel plate having a diameter of 8 mm was used as a jig, and the temperature was lowered from 100 ° C. to -10 ° C. at a temperature lowering rate of 3 ° C./min, and the frequency was 1 Hz and the strain was 1%. Make a measurement.

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

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

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

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

The material of the metal layer is preferably copper.

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

The resin material is preferably used to obtain a copper-clad laminate. An example of the copper-clad laminate is a copper-clad laminate comprising a copper foil and a resin film laminated on one surface of the copper foil.

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

The resin material is preferably used to obtain a multilayer substrate.

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

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

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

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

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

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

Among the multilayer boards, the multilayer printed wiring board is required to have low dielectric loss tangent and high insulation reliability due to the insulating layer. In the resin material according to the present invention, the insulation reliability can be effectively improved by lowering the dielectric loss tangent and improving the adhesion and etching performance between the insulating layer and the metal layer. Therefore, the resin material according to the present invention is suitably used for forming an insulating layer in a multilayer printed wiring board.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The following materials were prepared.

(Compound A)
Bismaleimide compound A1 (synthesized according to Synthesis Example 1 below)
Bismaleimide compound A2 (synthesized according to Synthesis Example 2 below)
Bismaleimide compound A3 (synthesized according to Synthesis Example 3 below)
Benzoxazine compound A1 (synthesized according to Synthesis Example 4 below)

(Synthesis Example 1)
135.0 g of tetracarboxylic dianhydride (“BisDA-1000” manufactured by SABIC Japan GK) and 400 g of cyclohexanone were placed in a reaction vessel equipped with a stirrer, a water divider, a thermometer and a nitrogen gas introduction tube. The solution in the reaction vessel was heated to 60 ° C. Next, 17.5 g of 1,3-bisaminomethylcyclohexane (manufactured by Mitsubishi Gas Chemical Company, molecular weight 142.25) was added dropwise to the reaction vessel to cause a reaction, and the reaction product had acid anhydrides at both ends. Got Next, 148 g of dimer diamine (“PRIAMINE 1075” manufactured by Croda Japan) was slowly added to the reaction vessel, and then 60.0 g of methylcyclohexane was 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 to obtain an imide compound having an amine structure at both ends. Then, 28 g of maleic anhydride was added, and the obtained mixture was refluxed for another 12 hours to perform maleimideization. After completion of the reaction, isopropanol was added and reprecipitated, and then the precipitate was collected and dried. In this way, an N-alkylbismaleimide compound (weight average molecular weight 10000) having a skeleton derived from dimerdiamine and having a skeleton derived from a diamine compound other than diaminediamine was obtained. The recovery rate of the obtained N-alkylbismaleimide compound was 83%.

(Synthesis Example 2)
55 g of pyromellitic dianhydride (manufactured by Tokyo Kasei Co., Ltd., molecular weight 254.15) and 300 g of cyclohexanone were placed in a reaction vessel equipped with a stirrer, a water divider, a thermometer and a nitrogen gas introduction tube, and the mixture was contained in the reaction vessel. The solution was heated to 60 ° C. Next, a solution prepared by dissolving 26.7 g of bis (aminomethyl) norbornane (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 154.26) in cyclohexanone was added dropwise to the reaction vessel to react, and both ends were acid anhydrides. The reaction product was obtained. Then, isopropanol was added, and an imide compound having an acid anhydride at both ends was recovered. Then, the precipitate was dissolved in cyclohexanone again, 46.0 g of dimer diamine (“PRIAMINE 1075” manufactured by Claude Japan Co., Ltd.) was slowly added to the reaction vessel, and then 45.0 g of methylcyclohexane was added to the reaction vessel. A Dean-Stark trap and a condenser were attached to a flask, and the mixture was refluxed for 2 hours and heated to obtain an imide compound having a dimer diamine structure at both ends. Then, 8.7 g of maleic anhydride was added, and the obtained mixture was refluxed for another 12 hours to perform maleimideization. Then, after completion of the reaction, isopropanol was added and reprecipitated, and then the precipitate was collected and dried. In this way, a bismaleimide compound (weight average molecular weight 8700) having a skeleton derived from dimerdiamine and having a skeleton derived from a diamine compound other than diaminediamine was obtained. The obtained bismaleimide compound has a skeleton derived from dimer diamine only at both ends of the main chain. The yield of the obtained bismaleimide compound was 70%.

(Synthesis Example 3)
55 g of pyromellitic dianhydride (manufactured by Tokyo Kasei Co., Ltd., molecular weight 254.15) and 300 g of cyclohexanone were placed in a reaction vessel equipped with a stirrer, a water divider, a thermometer and a nitrogen gas introduction tube, and the mixture was contained in the reaction vessel. The solution was heated to 60 ° C. Next, a solution prepared by dissolving 39.1 g of 4,4'-methylenebis (2-methylcyclohexylamine) (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 238.42) in cyclohexanone was added dropwise to the reaction vessel to react. , A reaction product was obtained in which both ends were acid anhydrides. Then, isopropanol was added, and an imide compound having an acid anhydride at both ends was recovered. Then, the precipitate was dissolved in cyclohexanone again, 46.0 g of dimer diamine (“PRIAMINE 1075” manufactured by Claude Japan Co., Ltd.) was slowly added to the reaction vessel, and then 45.0 g of methylcyclohexane was added to the reaction vessel. A Dean-Stark trap and a condenser were attached to a flask, and the mixture was heated to reflux for 2 hours to obtain an imide compound having a dimer diamine structure at both ends. Then, 8.9 g of maleic anhydride was added, and the obtained mixture was refluxed for another 12 hours to perform maleimideization. Then, after completion of the reaction, isopropanol was added and reprecipitated, and then the precipitate was collected and dried. In this way, a bismaleimide compound (weight average molecular weight 9800) having a skeleton derived from dimerdiamine and having a skeleton derived from a diamine compound other than diaminediamine was obtained. The obtained bismaleimide compound has a skeleton derived from dimer diamine only at both ends of the main chain. The yield of the obtained bismaleimide compound was 65%.

(Synthesis Example 4)
135.0 g of tetracarboxylic dianhydride (“BisDA-1000” manufactured by SABIC Japan GK) and 400 g of cyclohexanone were placed in a reaction vessel equipped with a stirrer, a water divider, a thermometer and a nitrogen gas introduction tube. The solution in the reaction vessel was heated to 60 ° C. Next, 17.5 g of 1,3-bisaminomethylcyclohexane (manufactured by Mitsubishi Gas Chemical Company, molecular weight 142.25) was added dropwise to the reaction vessel to cause a reaction, and the reaction product had acid anhydrides at both ends. Got Next, 148 g of dimer diamine (“PRIAMINE 1075” manufactured by Croda Japan) was slowly added to the reaction vessel, and then 60.0 g of methylcyclohexane was 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 to obtain an imide compound having an amine structure at both ends. Phenol and paraformaldehyde were then added and the resulting mixture was refluxed for an additional 12 hours for benzoxazine formation. After completion of the reaction, isopropanol was added and reprecipitated, and then the precipitate was collected and dried. In this way, a benzoxazine compound (weight average molecular weight 11000) having a skeleton derived from dimerdiamine and having a skeleton derived from a diamine compound other than diaminediamine was obtained. The yield of the obtained benzoxazine compound was 83%.

The weight average molecular weights of the bismaleimide compounds A1, A2 and A3 synthesized in Synthesis Example 1-3 and the benzoxazine compound A1 synthesized in Synthesis Example 4 were determined as follows.

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

In the obtained bismaleimide compounds A1, A2 and A3 and the benzoxazine compound A1, the number A1 of the aliphatic rings of the dimerdiamine skeleton was 1. In the dimerdiamine skeleton of the obtained bismaleimide compound A1, A2, A3 and benzoxazine compound A1, it exists between the nitrogen atom constituting one amino group and the nitrogen atom constituting the other amino group. The number A2 of carbon atoms not constituting the aromatic ring and the aliphatic ring was 16. The following formula (3) shows an example of the structure of maleimide in the skeleton derived from dimer diamine. Since the dimer diamine is a natural product (mixture), not all of the dimer diamines used have the structure of the following formula (3), but 17 which is the total of A1 and A2 and B1 which will be described later Even if the sum of B2 and B3 is compared, the effect of the present invention is not affected due to the properties of the bismaleimide compound.

In the obtained bismaleimide compound A1, the number B1 of aromatic rings contained in the skeleton derived from a diamine compound other than dimerdiamine was 0, and the number B2 of aliphatic rings was 1. In the skeleton derived from a diamine compound other than dimerdiamine in the obtained bismaleimide compound A1, carbon existing between the nitrogen atom constituting one amino group and the nitrogen atom constituting the other amino group. Among the atoms, nitrogen atoms and oxygen atoms, the number B3 of carbon atoms, nitrogen atoms and oxygen atoms that do not constitute an aromatic ring and an aliphatic ring was 2. The following formula (4) shows an example of a skeleton derived from a diamine compound other than dimer diamine.

In the obtained bismaleimide compound A2, the number B1 of aromatic rings possessed by the skeleton derived from a diamine compound other than dimerdiamine was 0, and the number B2 of aliphatic rings was 1. In the skeleton derived from a diamine compound other than dimerdiamine in the obtained bismaleimide compound A2, carbon existing between the nitrogen atom constituting one amino group and the nitrogen atom constituting the other amino group. Among the atoms, nitrogen atoms and oxygen atoms, the number B3 of carbon atoms, nitrogen atoms and oxygen atoms which do not constitute an aromatic ring and an aliphatic ring was 2.

In the obtained bismaleimide compound A3, the number B1 of aromatic rings contained in the skeleton derived from a diamine compound other than dimerdiamine was 0, and the number B2 of aliphatic rings was 2. In the skeleton derived from a diamine compound other than dimerdiamine in the obtained bismaleimide compound A3, carbon existing between the nitrogen atom constituting one amino group and the nitrogen atom constituting the other amino group. Among the atoms, nitrogen atoms and oxygen atoms, the number B3 of carbon atoms, nitrogen atoms and oxygen atoms that do not constitute an aromatic ring and an aliphatic ring was 1.

In the obtained benzoxazine compound A1, the number B1 of aromatic rings contained in the skeleton derived from a diamine compound other than dimerdiamine was 0, and the number B2 of aliphatic rings was 1. In the skeleton derived from a diamine compound other than dimerdiamine in the obtained benzoxazine compound A1, carbon existing between the nitrogen atom constituting one amino group and the nitrogen atom constituting the other amino group. Among the atoms, nitrogen atoms and oxygen atoms, the number B3 of carbon atoms, nitrogen atoms and oxygen atoms which do not constitute an aromatic ring and an aliphatic ring was 2.

Details of the obtained bismaleimide compounds A1, A2, A3 and benzoxazine compound A1 are shown in Table 1.

(Other)
N-alkylbismaleimide compound 1 (“BMI-1700” manufactured by Designer Moleculars Inc., softening point 60 ° C.)
N-alkylbismaleimide compound 2 (“BMI-1500” manufactured by Designer Molecules Inc.)
N-Phenylmaleimide compound ("BMI-4000" manufactured by Daiwa Kasei Kogyo Co., Ltd.)

(Epoxy compound)
Biphenyl type epoxy compound ("NC-3000" manufactured by Nippon Kayaku Co., Ltd.)
Naphthalene type epoxy compound ("HP-4032D" manufactured by DIC Corporation)
Resorcinol diglycidyl ether (“EX-201” manufactured by Nagase ChemteX Corporation)
Dicyclopentadiene type epoxy compound ("EP4088S" manufactured by ADEKA CORPORATION)
Naphthol aralkyl type epoxy compound ("ESN-475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)

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

(Hardener)
Ingredient X:
Cyanate ester compound-containing liquid (Lonza Japan's "BA-3000S", solid content 75% by weight)
Liquid containing 1 active ester compound ("EXB-9416-70BK" manufactured by DIC Corporation, solid content 70% by weight)
Active ester compound 2 containing liquid (DIC Corporation "HPC-8000L", solid content 65% by weight)
Active ester compound 3 containing liquid (“HPC-8150” manufactured by DIC Corporation, solid content 62% by weight)
Phenol compound-containing liquid ("LA-1356" manufactured by DIC Corporation, solid content 60% by weight)
Carbodiimide compound-containing liquid ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., solid content 50% by weight)

(Curing accelerator)
Dimethylaminopyridine ("DMAP" manufactured by Wako Pure Chemical Industries, Ltd.)
2-Phenyl-4-methylimidazole ("2P4MZ" manufactured by Shikoku Chemicals Corporation)
2-Ethyl-4-methylimidazole ("2E4MZ" manufactured by Shikoku Chemicals Corporation)
Dikmyl peroxide (manufactured by Tokyo Chemical Industry Co., Ltd.)

(Thermoplastic resin)
Polyimide compound (polyimide resin):
A polyimide compound-containing solution (nonvolatile content 26.8% by weight), which is a reaction product of tetracarboxylic dianhydride and dimer diamine, was synthesized according to the following Synthesis Example 5.

(Synthesis Example 5)
300.0 g of tetracarboxylic dianhydride (“BisDA-1000” manufactured by SABIC Japan GK) and 665.5 g of cyclohexanone were placed in a reaction vessel equipped with a stirrer, a water divider, a thermometer and a nitrogen gas introduction tube. And the solution in the reaction vessel was heated to 60 ° C. Next, 89.0 g of dimer diamine (“PRIAMINE 1075” manufactured by Croda Japan) and 54.7 g of 1,3-bisaminomethylcyclohexane (manufactured by Mitsubishi Gas Chemical Company) were added dropwise to the reaction vessel. Next, 121.0 g of methylcyclohexane and 423.5 g of ethylene glycol dimethyl ether were added to the reaction vessel, and an imidization reaction was carried out at 140 ° C. for 10 hours. In this way, a polyimide compound-containing solution (nonvolatile content 26.8% by weight) was obtained. The molecular weight (weight average molecular weight) of the obtained polyimide compound was 20000. The molar ratio of the acid component / amine component was 1.04.

The molecular weight of the polyimide compound synthesized in Synthesis Example 5 was determined as follows.

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

(Examples 1 to 17 and Comparative Examples 1 to 3)
The components shown in Tables 2 to 4 below were blended in the blending amounts (unit: parts by weight of solid content) shown in Tables 2 to 4 below, and stirred at room temperature until a uniform solution was obtained to obtain a resin material.

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

(Evaluation)
(1) Dielectric Dissipation Factor The obtained resin film was cut into a size of 2 mm in width and 80 mm in length, and five sheets were laminated to obtain a laminated body 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 brought to room temperature (23 ° C) by the cavity resonance method using "Cavity Resonance Permittivity Measuring Device CP521" manufactured by Kanto Electronics Application Development Co., Ltd. and "Network Analyzer N5224A PNA" manufactured by Keysight Technology Co., Ltd. The dielectric loss tangent was measured at a frequency of 1.0 GHz.

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

[Criteria for determining the coefficient of linear expansion]
○ ○: Average coefficient of linear expansion is 25 ppm / ° C or less ○: Average coefficient of linear expansion exceeds 25 ppm / ° C and is 30 ppm / ° C or less ×: Average coefficient of linear expansion exceeds 30 ppm / ° C

(3) Adhesion between the insulating layer and the metal layer (peeling strength)
Laminating process:
A double-sided copper-clad laminate (copper foil thickness 18 μm on each side, substrate thickness 0.7 mm, substrate size 100 mm × 100 mm, “MCL-E679FG” manufactured by Hitachi Kasei Co., Ltd.) was prepared. Both sides of the copper foil surface of this double-sided copper-clad laminate were immersed in "Cz8101" manufactured by MEC to roughen the surface of the copper foil. Using "Batch type vacuum laminator MVLP-500-IIA" manufactured by Meiki Co., Ltd. on both sides of the roughened copper-clad laminate, the resin film (B stage film) side of the laminate is placed on the copper-clad laminate. It was laminated on top of each other to obtain a laminated structure. The laminating conditions were such that the pressure was reduced for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then the pressure was pressed at 100 ° C. and a pressure of 0.4 MPa for 30 seconds.

Film peeling process:
In the obtained laminated structure, the PET films on both sides were peeled off.

Copper foil pasting process:
The shiny surface of the copper foil (thickness 35 μm, manufactured by Mitsui Mining & Smelting Co., Ltd.) was subjected to Cz treatment (“Cz8101” manufactured by MEC), and the surface of the copper foil was etched by about 1 μm. An etched copper foil was bonded to the laminated structure from which the PET film had been peeled off to obtain a substrate with a copper foil. The obtained substrate with copper foil was heat-treated in a gear oven at 190 ° C. for 90 minutes to obtain an evaluation sample.

(3-1) Measurement of peel strength in room temperature environment (adhesion):
A strip-shaped notch with a width of 1 cm was made on the surface of the copper foil of the evaluation sample. Set the evaluation sample on a 90 ° peeling tester (“TE-3001” manufactured by Tester Sangyo Co., Ltd.), pick up the end of the notched copper foil with a grasper, peel the copper foil by 20 mm, and peel strength (peel). Strength) was measured.

[Criteria for peel strength in room temperature environment]
○ ○: Peel strength is 0.6 kgf or more ○: Peel strength is 0.4 kgf or more and less than 0.6 kgf ×: Peel strength is less than 0.4 kgf

(3-2) Measurement of peel strength under high temperature (260 ° C) environment:
A strip-shaped notch with a width of 1 cm was made on the surface of the copper foil of the evaluation sample. After installing the heating unit at the place where the evaluation sample of the 90 ° peeling tester (“TE-3001” manufactured by Tester Sangyo Co., Ltd.) was set, the evaluation sample was set and the heating unit was set to 260 ° C. Then, the end portion of the notched copper foil was picked up with a gripper, the copper foil was peeled off by 20 mm, and the peel strength (peel strength) was measured.

[Criteria for determining peel strength in a high temperature (260 ° C) environment]
○ ○: Peel strength is 0.1 kgf or more ○: Peel strength is 0.05 kgf or more and less than 0.1 kgf ×: Peel strength is less than 0.05 kgf

(4) Surface roughness after etching (surface roughness)
Laminating process and semi-hardening process:
A double-sided copper-clad laminate (CCL substrate) (“E679FG” manufactured by Hitachi Kasei Co., Ltd.) was prepared. Both sides of the copper foil surface of this double-sided copper-clad laminate were immersed in "Cz8101" manufactured by MEC to roughen the surface of the copper foil. Using "Batch type vacuum laminator MVLP-500-IIA" manufactured by Meiki Co., Ltd. on both sides of the roughened copper-clad laminate, the resin film (B stage film) side of the laminate is placed on the copper-clad laminate. It was laminated on top of each other to obtain a laminated structure. The laminating conditions were such that the pressure was reduced for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then the pressure was pressed at 100 ° C. and a pressure of 0.4 MPa for 30 seconds. Then, the resin film was semi-cured by heating at 180 ° C. for 30 minutes. In this way, a laminated body in which a semi-cured resin film was laminated on the CCL substrate was obtained.

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

(B) Permanganate treatment (roughening treatment and desmear treatment):
The swelled laminate was placed in a crude aqueous solution of potassium permanganate (“Concentrate Compact CP” manufactured by Atotech Japan) at 70 ° C. and shaken for 30 minutes. Next, the mixture was treated with a cleaning solution at 25 ° C. (“Reduction Securigant P” manufactured by Atotech Japan) for 2 minutes, and then washed with pure water to obtain an evaluation sample.

Measurement of surface roughness:
Arithmetic mean roughness Ra was measured on the surface of the evaluation sample (roughened cured product) in a measurement area of 94 μm × 123 μm using a non-contact three-dimensional surface shape measuring device (“WYKO NT1100” manufactured by Veeco). did. The arithmetic mean roughness Ra was measured according to JIS B0601: 1994. The surface roughness was judged according to the following criteria.

[Criteria for surface roughness]
○○: Ra is less than 50 nm ○: Ra is 50 nm or more and less than 200 nm ×: Ra is 200 nm or more

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

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

Electroplating:
Next, electroless plating was performed on the cured product that had been electroless plated until the plating thickness became 25 μm. Copper sulfate solution for electrolytic copper plating ("Copper sulfate pentahydrate" manufactured by Wako Pure Chemical Industries, Ltd., "Sulfate" manufactured by Wako Pure Chemical Industries, Ltd., "Basic leveler capallaside HL" manufactured by Atotech Japan, "Basic leveler capallaside HL" manufactured by Atotech Japan. Using the corrective agent Capalacid GS ”), electrolytic plating was carried out by passing a current of 0.6 A / cm ² until the plating thickness became about 25 μm. After the copper plating treatment, the cured product was heated at 190 ° C. for 90 minutes to further cure the cured product. In this way, a cured product in which the copper plating layer was laminated on the upper surface was obtained.

Measurement of plating peel strength:
A strip-shaped notch with a width of 0.5 cm was made on the surface of the copper plating layer of the cured product in which the obtained copper plating layer was laminated on the upper surface. Set the cured product with the copper plating layer laminated on the upper surface in a 90 ° peeling tester ("TE-3001" manufactured by Tester Sangyo Co., Ltd.), pick up the end of the notched copper plating layer with a grip, and copper. The plating layer was peeled off by 15 mm and the peeling strength (plating peel strength) was measured.

[Criteria for plating peel strength]
○ ○: Plating peel strength is 0.5 kgf or more 〇: Plating peel strength is 0.3 kgf or more and less than 0.5 kgf ×: Plating peel strength is less than 0.3 kgf

The composition and results are shown in Tables 2-4 below. In Tables 2 to 4, the content of each component is shown in terms of net content (parts by weight of solid content).

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

Claims (16)

A bismaleimide compound having a skeleton derived from dimerdiamine and a skeleton derived from a diamine compound other than diaminediamine, and a skeleton having a skeleton derived from dimerdiamine and derived from a diamine compound other than diaminediamine. At least one of the benzoxazine compounds having compound A and
Including inorganic fillers (excluding conductive inorganic fillers)
The distance between amino groups in the skeleton derived from a diamine compound other than the dimer diamine is shorter than the distance between amino groups in the skeleton derived from the dimer diamine.
A resin material in which the content of the inorganic filler is 50% by weight or more and 90% by weight or less in 100% by weight of the components excluding the solvent in the resin material. The resin material according to claim 1 , wherein the compound A has a skeleton derived from the dimer diamine at both ends of the main chain. The resin material according to claim 1 or 2 , wherein the compound A has a skeleton derived from the dimer diamine only at both ends of the main chain. The resin material according to any one of claims 1 to 3 , wherein the compound A has a molecular weight of less than 20000. The resin material according to any one of claims 1 to 4 , wherein the average particle size of the inorganic filler is 1 μm or less. The resin material according to any one of claims 1 to 5 , wherein the inorganic filler is silica. The resin material according to any one of claims 1 to 6 , which contains a maleimide compound having no skeleton derived from a dimer diamine. The compound A contains a bismaleimide compound having a skeleton derived from the dimer diamine and having a skeleton derived from a diamine compound other than dimer diamine.
A first bismaleimide compound having a skeleton derived from the diamine diamine and having a skeleton derived from a diamine compound other than the diamine diamine has a skeleton derived from the diamine diamine only at both ends of the main chain. Any 1 of claims 1 to 7 , which comprises a compound and a second bismaleimide compound having a skeleton derived from diamine diamine in a skeleton other than both ends of the main chain and having two or more imide skeletons. The resin material described in the section. Epoxy compounds and
A claim 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 of a skeletonless benzoxazine compound derived from dimerdiamine. The resin material according to any one of 1 to 8 . Contains a curing accelerator,
The resin material according to any one of claims 1 to 9 , wherein the curing accelerator contains an anionic curing accelerator. The resin material according to claim 10 , wherein the anionic curing accelerator is an imidazole compound. The resin material according to claim 10 or 11 , wherein the content of the anionic curing accelerator is 20% by weight or more in 100% by weight of the curing accelerator. The resin material according to any one of claims 1 to 12 , which is a resin film. A member to be laminated having a metal layer on its surface and a resin film laminated on the surface of the metal layer are provided.
A laminated structure in which the resin film is the resin material according to any one of claims 1 to 13 . The laminated structure according to claim 14 , wherein the material of the metal layer is copper. With the circuit board
A plurality of insulating layers arranged on the surface of the circuit board,
With a plurality of metal layers arranged between the insulating layers,
A multilayer printed wiring board in which at least one of the plurality of insulating layers is a cured product of the resin material according to any one of claims 1 to 13 .

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