CN111836857A - Resin material, laminated structure, and multilayer printed wiring board - Google Patents

Abstract

The invention provides a resin material which can 1) reduce the dielectric loss tangent of a cured product, 2) improve the thermal dimensional stability of the cured product, 3) improve the adhesion between an insulating layer and a metal layer, 4) reduce the surface roughness after etching, and 5) improve the glass strength of a coating layer. The resin material of the present invention comprises: the filler contains a compound A and an inorganic filler, wherein the compound A is a bismaleimide compound having a skeleton derived from dimer diamine and having a skeleton derived from a diamine compound other than dimer diamine, and a benzo compound having a skeleton derived from dimer diamine and having a skeleton derived from a diamine compound other than dimer diamine

At least one of oxazine compounds.

Description

Resin material, laminated structure, and multilayer printed wiring board

Technical Field

The invention relates to a composition comprising a maleimide compound or a benzo

An oxazine compound and an inorganic filler. The present invention also relates to a multilayer structure and a multilayer printed wiring board using the resin material.

Background

Conventionally, various resin materials have been used for obtaining electronic components such as semiconductor devices, laminated boards, and printed wiring boards. For example, in a multilayer printed wiring board, a resin material is used to form an insulating layer for insulating internal layers or an insulating layer located in a surface layer portion. On the surface of the insulating layer, a wiring as a metal is generally stacked. In order to form the insulating layer, a resin film formed by forming a film of the resin material 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 (build-up film) and the like.

Patent document 1 below discloses a resin composition containing a compound having a maleimide group, a 2-valent group having at least 2 imide bonds, and a saturated or unsaturated 2-valent hydrocarbon group. Patent document 1 describes that a cured product of the 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 electronic materials, which contains a bismaleimide compound having 2 maleimide groups and 1 or more polyimide groups having a specific structure. In the bismaleimide compound, 2 maleimide groups are independently bonded to both ends of the polyimide group via a1 st linking group in which at least 8 or more atoms are linearly linked.

Documents of the prior art

Patent document

Patent document 1: WO2016/114286A1

Patent document 2: japanese patent laid-open publication No. 2018-90728

Technical problem to be solved by the invention

In order to improve the electrical characteristics of a cured product (insulating layer), a less polar compound may be mixed in a resin material (resin composition). However, when a cured product (insulating layer) is formed using a resin material mixed with a compound having a relatively low polarity, the adhesion between the insulating layer and the metal layer is not sufficiently high, or the thermal dimensional stability of the cured product is not sufficiently high. Therefore, the wiring (metal layer) may be peeled off from the insulating layer.

In addition, when the insulating layer is formed using a conventional resin material as described in patent documents 1 and 2, thermal dimensional stability may not be sufficiently increased, or surface roughness after etching may not be sufficiently reduced. When the surface roughness after etching is not sufficiently reduced, the strength of the insulating layer is not sufficiently increased because the resin contributing to the anchor effect is locally reduced, and the peeling strength between the cured product (insulating layer) after etching and the metal layer laminated on the surface of the insulating layer by plating is not sufficiently increased in some cases.

In addition, 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 be reduced.

Thus, the following situation exists: it is extremely difficult to obtain a resin material that exhibits all the effects of 1) reducing the dielectric loss tangent of a cured product, 2) improving the thermal dimensional stability of a cured product, 3) improving the adhesion of an insulating layer to a metal layer, 4) reducing the surface roughness after etching, and 5) improving the peel strength of a plating layer.

The purpose of the present invention is to provide a resin material which can 1) reduce the dielectric loss tangent of a cured product, 2) improve the thermal dimensional stability of the cured product, 3) improve the adhesion between an insulating layer and a metal layer, 4) reduce the surface roughness after etching, and 5) improve the peel strength of a plating layer. Further, the present invention aims to provide a multilayer structure and a multilayer printed wiring board using the resin material.

Means for solving the problems

According to a broad aspect of the present invention, there is provided a resin material comprising a compound a and an inorganic filler, wherein the compound a is a bismaleimide compound having a skeleton derived from a dimer diamine and having a skeleton derived from a diamine compound other than the dimer diamine, and a benzo compound having a skeleton derived from a dimer diamine and having a skeleton derived from a diamine compound other than the dimer diamine

At least one of oxazine compounds.

In a specific aspect of the resin material of the present invention, the distance between the amino groups in the skeleton of the diamine compound other than the dimer diamine is smaller than the distance between the amino groups in the skeleton of the dimer diamine.

In a specific aspect of the resin material of the present invention, the compound a has the dimer diamine-derived skeleton at both ends of the main chain.

In a specific aspect of the resin material of the present invention, the compound a has the dimer diamine-derived skeleton only at both ends of the main chain.

In a specific aspect of the resin material of the present invention, the molecular weight of the compound a is less than 20000.

In a specific aspect of the resin material of the present invention, the inorganic filler has an average particle diameter of 1 μm or less.

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

In a specific aspect of the resin material of the present invention, the content of the inorganic filler is 50% by weight or more based on 100% by weight of components other than the solvent in the resin material.

In a certain specific aspect of the resin material of the present invention, the resin material contains a maleimide compound having no skeleton derived from a dimer diamine.

In a specific aspect of the resin material of the present invention, the compound a includes the bismaleimide compound having a skeleton derived from dimer diamine and having a skeleton derived from a diamine compound other than dimer diamine, and the bismaleimide compound having a skeleton derived from dimer diamine and having a skeleton derived from a diamine compound other than dimer diamine includes a1 st bismaleimide compound and a2 nd bismaleimide compound, the 1 st bismaleimide compound having a skeleton derived from dimer diamine only at both ends of a main chain, and the 2 nd bismaleimide compound having a skeleton derived from dimer diamine in a skeleton other than both ends of a main chain and having 2 or more imide skeletons.

In a specific aspect of the resin material of the present invention, the resin material comprises: an epoxy compound and a curing agent containing a phenol compound, a cyanate ester compound, an acid anhydride, and an active ingredientEster compound, carbodiimide compound, and benzene having no skeleton derived from dimer diamine

At least 1 component of an oxazine compound.

In a specific aspect of the resin material of the present invention, the resin material contains a curing accelerator that contains an anionic curing accelerator.

In a specific aspect of the resin material of the present invention, the anionic curing accelerator is an imidazole compound.

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

In a specific aspect of the resin material of the present invention, the resin material is a resin film.

According to a broad aspect of the present invention, there is provided a laminated structure comprising: the resin film is made of the resin material.

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

According to a broad aspect of the present invention, there is provided a multilayer printed wiring board comprising: a circuit substrate; a multilayer insulating layer disposed on a surface of the circuit substrate; and a metal layer disposed between the plurality of insulating layers, wherein at least 1 of the plurality of insulating layers is a cured product of the resin material.

ADVANTAGEOUS EFFECTS OF INVENTION

The resin material of the present invention contains a compound A which is a bismaleimide compound having a skeleton derived from dimer diamine and having a skeleton derived from a diamine compound other than dimer diamine, and a benzo compound having a skeleton derived from dimer diamine and having a skeleton derived from a diamine compound other than dimer diamine

At least one of oxazine compounds. The resin material of the present invention contains an inorganic filler. The resin material of the present invention has the above-described technical features, and therefore, can exhibit all of the following effects 1) to 5): 1) reducing the dielectric loss tangent of the cured product, 2) improving the thermal dimensional stability of the cured product, 3) improving the adhesion of the insulating layer to the metal layer, 4) reducing the surface roughness after etching, and 5) improving the peel strength of the plating layer.

Drawings

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

Detailed Description

The present invention will be described in detail below.

The resin material of the present invention contains a compound A which is a bismaleimide compound having a skeleton derived from dimer diamine and having a skeleton derived from a diamine compound other than dimer diamine, and a benzo compound having a skeleton derived from dimer diamine and having a skeleton derived from a diamine compound other than dimer diamine

At least one of oxazine compounds. The resin material of the present invention contains an inorganic filler. The skeleton derived from dimer diamine and the skeleton derived from a diamine compound other than dimer diamine are present as partial skeletons in the compound a.

The resin material of the present invention has the above-described technical features, and therefore, can exhibit all of the following effects 1) to 5): can 1) reduce the dielectric loss tangent of a cured product, 2) improve the thermal dimensional stability of the cured product, 3) improve the adhesion between an insulating layer and a metal layer, 4) reduce the surface roughness after etching, and 5) improve the peel strength of a plating layer. For example, 2) the thermal dimensional stability of the cured product can reduce the coefficient of linear expansion (CTE) of the cured product. For example, 3) the adhesion between the insulating layer and the metal layer can be improved by increasing the peel strength between the insulating layer and the metal layer in a temperature range from room temperature to a high temperature (for example, 260 ℃).

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

The resin material of 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 comprises a liquid state. The resin material of the present invention is preferably a resin film in view of excellent handling properties.

The resin material of 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.

The details of each component used in the resin material of the present invention, the use of the resin material of the present invention, and the like will be described below.

[ 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 of the present invention contains a compound A which is a bismaleimide compound having a skeleton derived from a dimer diamine and having a skeleton derived from a diamine compound other than the dimer diamine, and a benzo compound having a skeleton derived from a dimer diamine and having a skeleton derived from a diamine compound other than the dimer diamine

At least one of oxazine compounds. In the resin material of the present invention, the compound a may contain only the bismaleimide compound or only the benzo group

An oxazine compound which may contain said bismaleimide compound and said benzo

Both oxazine compounds.

The effects of the present invention described in 1) to 5) can be exhibited by using the compound A. By using the compound a, the surface roughness (surface roughness) of a cured product can be appropriately reduced, and the plating peel strength can be improved. The surface roughness depends on the amount of resin etched. Etching is likely to occur at double-bond bonding sites of compounds contained in the resin material. Therefore, a compound having an imide bond and a skeleton derived from dimer diamine is easily etched. In the compound a, the content of the imide bond and the skeleton derived from dimer diamine can be controlled by controlling the molecular weight of a diamine compound other than dimer diamine, and therefore, the surface roughness after etching can be reduced and the plating peel strength can be improved. The compound a may have an aromatic skeleton or may not have an aromatic skeleton. The compound a may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The dimer diamine-derived backbone may or may not have aliphatic rings. The dimer diamine-derived skeleton may or may not have an aliphatic ring.

The skeleton derived from the diamine compound may or may 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 may or may 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: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, benzanthracene ring,

Cyclo, 9, 10-benzophenanthrene ring, benzanthrone ring, pyrene ring, pentacene ring, picene ring, perylene ring, and the like.

Examples of the alicyclic ring include: a monocycloparaffin ring, a bicycloalkane ring, a tricycloalkane ring, a tetracycloparaffin ring, and dicyclopentadiene.

From the viewpoint of effectively exerting the effects of the present invention of 1) to 5), it is preferable that in the compound a, the distance between the amino groups in the skeleton of the diamine compound other than the dimer diamine is smaller than the distance between the amino groups in the skeleton of the dimer diamine. That is, the total of B1, B2, and B3 shown below is preferably smaller than the total of a1 and a2 shown below.

The number of aliphatic rings of the dimer diamine skeleton was a 1. A1 represents an integer of 0 or more. The aliphatic ring refers to a ring other than an aromatic ring. The alicyclic ring may have a double bond in a part of the ring.

In the dimer diamine-derived skeleton, the number of carbon atoms not constituting an aromatic ring or an aliphatic ring among carbon atoms present between a nitrogen atom constituting one amino group and a nitrogen atom constituting the other amino group is a 2. A2 represents an integer of 1 or more.

Since dimer diamines are natural products (mixtures), it is difficult to define the structures of dimer diamines as identical structures. Therefore, in order to calculate a1 and a2, the skeleton of formula (3) used in the items of the following examples can be used as a representative skeleton of dimer diamine (dimer diamine skeleton). When the skeleton of formula (3) was used as the dimer diamine skeleton for the calculation of a1 and a2, the total of a1 and a2 was 17. Even if the total of a1 and a2 is 17, the effects of the present invention are not impaired. The dimer diamine skeleton may or may not have an unsaturated bond.

The number of aromatic rings in the skeleton of the diamine compound other than dimer diamine is B1, and the number of aliphatic rings in the skeleton of the diamine compound other than dimer diamine is B2. B1 and B2 each represent an integer of 0 or more. The aliphatic ring refers to a ring other than an aromatic ring. The alicyclic ring may have a double bond in a part of the ring. In addition, the condensed rings are counted as 1 aromatic ring.

In the skeleton of the diamine compound derived from other than dimer diamine, the number of carbon atoms, nitrogen atoms, and oxygen atoms not constituting the aromatic ring or the aliphatic ring among carbon atoms, nitrogen atoms, and oxygen atoms present between a nitrogen atom constituting one amino group and a nitrogen atom constituting the other amino group is B3. B3 represents an integer of 1 or more. The one amino group and the other amino group in the case of obtaining B3 are each preferably a primary amino group. In the case where 3 or more primary amino groups are present in the skeleton of the diamine compound other than dimer diamine, the value of B3 is a large value.

From the viewpoint of effectively exerting the effects of the present invention of 1) to 5), it is preferable that the total of B1, B2, and B3 be smaller than the total of a1 and a 2. 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 more effectively exhibiting the effects of the present invention of 1) to 5), the absolute value of the difference between the total of a1 and a2 and the total of B1, B2, and B3 is preferably 5 or more, more preferably 7 or more, and preferably 14 or less, more preferably 10 or less.

< bismaleimide Compound having a skeleton derived from dimer diamine and having a skeleton derived from a diamine Compound other than dimer diamine (bismaleimide Compound A) >

The resin material of the present invention preferably contains, as the compound a, a bismaleimide compound having a skeleton derived from a dimer diamine and having a skeleton derived from a diamine compound other than dimer diamine (hereinafter, sometimes referred to as "bismaleimide compound a"). The bismaleimide compound a may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

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 carbon atoms constituting a double bond between carbon atoms in a maleimide group. The citraconimide compound has lower reactivity than a maleimide compound, and thus can improve storage stability.

The bismaleimide compound a preferably has the dimer diamine-derived skeleton at both ends of the main chain. In this case, the bismaleimide compound a may have the dimer diamine-derived skeleton in the main chain both ends and in the skeleton other than the main chain both ends, or may have the dimer diamine-derived skeleton only in the main chain both ends. The skeleton derived from dimer diamine is a skeleton having flexibility. Therefore, in the case where the bismaleimide compound a has the dimer diamine-derived skeleton at both ends of the main chain, the reactivity of the maleimide group can be improved, 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.

The bismaleimide compound a more preferably has the dimer diamine-derived skeleton only at both ends of the main chain. When the bismaleimide compound a has the dimer diamine-derived skeleton only at both ends of the main chain, the softening point of the bismaleimide compound a can be further increased, and therefore the glass transition temperature of a cured product of the resin material can be further effectively increased. Therefore, the thermal dimensional stability of the cured product can be further improved, and the adhesion between the insulating layer and the metal layer can be further improved. In addition, in the case where the bismaleimide compound a has the dimer diamine-derived skeleton only at both ends of the main chain, the compatibility between the skeleton other than the dimer diamine-derived skeleton of the main chain of the bismaleimide compound a and another thermosetting resin (an epoxy compound, a curing agent, or the like) can be improved, and the viscosity of the film can be reduced particularly at the time of shearing at low temperature.

The bismaleimide compound a preferably includes a1 st bismaleimide compound having a skeleton derived from dimer diamine only at both ends of the main chain, and a2 nd bismaleimide compound having a skeleton derived from dimer diamine in a skeleton other than both ends of the main chain and having 2 or more imide skeletons. In this case, the effects of the present invention of 1) to 5) described above can be effectively exhibited.

The bismaleimide compound a can be obtained by reacting tetracarboxylic dianhydride, dimer diamine, and a diamine compound other than dimer diamine to obtain a reactant, and then reacting the reactant with maleic anhydride. 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 the dimer diamine-derived skeleton only at both ends of the main chain can be obtained, for example, as follows. A1 st reactant is obtained by reacting a tetracarboxylic dianhydride with a diamine compound other than dimer diamine. The obtained 1 st reactant is reacted with dimer diamine to obtain 2 nd reactant having amino groups at both ends. The resulting 2 nd reactant is reacted with maleic anhydride.

Examples of the tetracarboxylic dianhydride include: pyromellitic dianhydride, 3',4,4' -benzophenonetetracarboxylic dianhydride, 3',4,4' -biphenylsulfonetetracarboxylic dianhydride, 1,4,5, 8-naphthalenetetracarboxylic dianhydride, 2,3,6, 7-naphthalenetetracarboxylic dianhydride, 3',4,4' -biphenylethertetracarboxylic dianhydride, 3',4,4' -dimethyldiphenylsilanetetracarboxylic dianhydride, 3',4,4' -tetraphenylsilanetetracarboxylic dianhydride, 1,2,3, 4-furantetracarboxylic dianhydride, 4,4' -bis (3, 4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4' -bis (3, 4-dicarboxyphenoxy) diphenyl sulfone dianhydride, 4,4' -bis (3, 4-dicarboxyphenoxy) diphenyl propane dianhydride, 3,3',4,4' -perfluoroisopropylidene diphthalic dianhydride, 3',4,4' -biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-benzene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4 '-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4' -diphenylmethane dianhydride, and the like.

Examples of commercially available products of the dimer diamine include: versamine 551 (trade name, manufactured by BASF Japan, 3, 4-bis (1-aminoheptyl) -6-hexyl-5- (1-octenyl) cyclohexene), Versamine 552 (trade name, manufactured by Cognis Japan, the hydride of Versamine 551), PRIAMINE1075, PRIAMINE1074 (trade name, both manufactured by Croda Japan), and the like.

Examples of the diamine compound other than the dimer diamine 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-bis (4-aminophenyl) cyclohexane, 1, 3-cyclohexanediamine, 1, 4-cyclohexanediamine, 2, 7-diaminofluorene, 4' -ethylenedianiline, isophoronediamine, 4' -methylenebis (cyclohexylamine), 4' -methylenebis (2, 6-diethylaniline), 4' -methylenebis (2-ethyl-6-methylaniline), 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.

The weight ratio of the content of the bismaleimide compound a to the total content of the epoxy compound and the following component X (the content of the bismaleimide compound a/the total content of the epoxy compound and the component X) is preferably 0.05 or more, more preferably 0.1 or more, and preferably 0.15 or more. The weight ratio of the content of the bismaleimide compound a to the total content of the epoxy compound and the component X described below (the content of the bismaleimide compound a/the total content of the epoxy compound and the component X) is preferably 0.9 or less, and more preferably 0.75 or less. When the weight ratio is not less than the lower limit and not more than the upper limit, the dielectric loss tangent can be further reduced, and the thermal dimensional stability can be further improved. When the weight ratio is not less than the lower limit and not more than the upper limit, the surface roughness after etching can be further reduced, and the plating peel strength can be further improved.

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

From the viewpoint of effectively exerting the effects of the present invention of 1) to 5), the molecular weight of the bismaleimide compound a is preferably 500 or more, more preferably 1000 or more, and preferably less than 20000, more preferably less than 15000, and preferably less than 7500, and particularly preferably less than 5000. When the molecular weight is not less than the upper limit, the melt viscosity of the resin material may be higher than that in the case where the molecular weight is less than the upper limit, and the embedding property into the holes or the recesses and projections of the circuit board may be deteriorated.

The molecular weight of the bismaleimide compound a means a molecular weight calculated by a structural formula in the case where the bismaleimide compound a is a non-polymer and the structural formula of the bismaleimide compound a can be specified. In addition, the molecular weight of the bismaleimide compound a represents a weight average molecular weight in terms of polystyrene measured by Gel Permeation Chromatography (GPC) in the case where the bismaleimide compound a is a polymer.

In the bismaleimide compound having a skeleton derived from the dimer diamine but not having a skeleton derived from a diamine compound other than the dimer diamine, when the molecular weight of the bismaleimide compound is large (for example, when the number average molecular weight is 1500 or more), the bismaleimide compound tends to excessively aggregate, and the viscosity of the resin material may become excessively high. Examples of commercially available bismaleimide compounds having a skeleton derived from dimer diamine but not having a skeleton derived from a diamine compound other than dimer diamine include "BMI 3000J" and "BMI 5000" manufactured by designer polymers inc.

The softening point of the bismaleimide compound a is preferably 75 ℃ or higher, and more preferably 90 ℃ or higher, from the viewpoint of further improving the thermal dimensional stability of the cured product and further improving the adhesion between the insulating layer and the metal layer.

The softening point can be determined from the inflection point of the reverse heat flow by heating from-30 ℃ to 200 ℃ at a heating rate of 3 ℃/min under a nitrogen atmosphere using a differential scanning calorimeter ("Q2000" manufactured by TA Instruments, for example).

<Benzo having skeleton derived from dimer diamine and having skeleton derived from diamine compound other than dimer diamine

Oxazine compounds (benzo

Oxazine compound A)>

The resin material of the present invention is preferably a material containing a benzo group having a skeleton derived from a dimer diamine and having a skeleton derived from a diamine compound other than dimer diamine

Oxazine compound (hereinafter, sometimes referred to as "benzo

Oxazine compound a ") as said compound a. Said benzene

The oxazine compound a may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

Said benzene

The oxazine compound a preferably has the dimer diamine-derived skeleton at both ends of the main chain. In this case, the benzene

The oxazine compound A may be at both ends of the main chain and a bone other than at both ends of the main chainThe skeleton derived from dimer diamine may be provided in the skeleton, or the skeleton derived from dimer diamine may be provided only at both ends of the main chain. The skeleton derived from dimer diamine has a flexible skeleton. Thus, in said benzo

The oxazine compound A having the dimer diamine-derived skeleton at both ends of the main chain can improve the benzo group

The reactivity of the oxazine group allows the curing reaction to proceed sufficiently. 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.

Said benzene

The oxazine compound a more preferably has the dimer diamine-derived backbone only at both ends of the main chain. In said benzene

In the case where the oxazine compound a has the dimer diamine-derived skeletons only at both ends of the main chain, the benzo group of the benzoxazine compound a can be further improved

The softening point of the oxazine compound a can therefore be further effective in increasing the glass transition temperature of the cured product of the resin material. 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. In addition, in said benzene

The oxazine compound A can enhance benzo group only in the case where the skeleton derived from dimer diamine is present at both ends of the main chain

The compatibility of the skeleton other than the skeleton derived from the dimer diamine in the main chain of the oxazine compound a with other thermosetting resins (epoxy compound, curing agent, etc.), particularly, can reduce the viscosity of the film when sheared at low temperature.

Said benzene

The oxazine compound a may be obtained by reacting tetracarboxylic dianhydride, dimer diamine, and a diamine compound other than dimer diamine to obtain a reactant, and then reacting the reactant, phenol, and paraformaldehyde. The reaction product of the tetracarboxylic dianhydride and the dimer diamine is preferably a compound having amino groups at both ends.

Benzo having the dimer diamine-derived skeleton only at both ends of the main chain

The oxazine compound a may be obtained, for example, as follows. A1 st reactant is obtained by reacting a tetracarboxylic dianhydride with a diamine compound other than dimer diamine. The obtained 1 st reactant is reacted with dimer diamine to obtain 2 nd reactant having amino groups at both ends. The obtained 2 nd reactant, phenol and paraformaldehyde are reacted.

The tetracarboxylic dianhydride may be mentioned, for example, as mentioned above.

The commercially available dimer diamine may be exemplified by the commercially available dimer diamine.

The diamine compound other than the dimer diamine may be the diamine compound.

Said benzene

The weight ratio of the content of the oxazine compound A to the total content of the epoxy compound and the following component X (the benzo

Of oxazine compounds AContent/total content of the epoxy compound and the component X) is preferably 0.05 or more, more preferably 0.1 or more, and preferably 0.15 or more. Said benzene

The weight ratio of the content of the oxazine compound A to the total content of the epoxy compound and the following component X (the benzo

The content of the oxazine compound a/the 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 not less than the lower limit and not more than the upper limit, the dielectric loss tangent can be further reduced, and the thermal dimensional stability can be further improved. When the weight ratio is not less than the lower limit and not more than the upper limit, the surface roughness after etching can be further reduced, and the plating peel strength can be further improved.

The benzo compound is contained in 100 wt% of the resin material excluding the inorganic filler and the solvent

The content of the oxazine compound a is preferably 5% by weight or more, more preferably 10% by weight or more, and preferably 15% by weight or more, and preferably 80% by weight or less, more preferably 70% by weight or less. If said benzene is

When the content of the oxazine compound a is not less than the lower limit, the dielectric loss tangent can be further reduced, the adhesion between the insulating layer and the metal layer can be further improved, and the surface roughness after etching can be further reduced. If said benzene is

When the content of the oxazine compound a is less than the upper limit, the thermal dimensional stability can be further improved.

From the effective exertion of the 1)5) From the viewpoint of the effects of the present invention, the benzene ring

The molecular weight of the oxazine compound a is preferably 500 or more, more preferably 1000 or more, and preferably less than 20000, more preferably less than 15000, and preferably less than 7500, and especially preferably less than 5000. When the molecular weight is not less than the upper limit, the melt viscosity of the resin material may be higher than that in the case where the molecular weight is less than the upper limit, and the embedding property into the holes or the recesses and projections of the circuit board may be deteriorated.

Said benzene

The molecular weight of the oxazine compound A being in said benzene

In the case where the oxazine compound A is non-polymeric, and the benzo group can be identified

The structural formula of the oxazine compound A means the molecular weight which can be calculated from the structural formula. In addition, the benzene

The molecular weight of the oxazine compound A being in said benzene

When the oxazine compound a is a polymer, it represents the weight average molecular weight in terms of polystyrene as measured by Gel Permeation Chromatography (GPC).

The benzo group is used from the viewpoint of further improving the thermal dimensional stability of a cured product and further improving the adhesion between an insulating layer and a metal layer

The softening point of the oxazine compound A is preferably 75 ℃ or higher, more preferably 90 ℃ or higher.

The softening point can be determined from the inflection point of the countercurrent flow by heating the steel from-30 ℃ to 200 ℃ at a heating rate of 3 ℃/min under a nitrogen atmosphere using a differential scanning calorimeter ("Q2000" manufactured by TA Instruments).

[ epoxy Compound ]

The resin material preferably comprises an epoxy compound. As the epoxy compound, a conventionally known epoxy compound can be used. The epoxy compound means an organic compound having at least 1 epoxy group. The epoxy compounds can be used alone in 1 kind, also can be combined with more than 2 kinds.

As the epoxy compound, there can be mentioned: bisphenol a type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, phenol novolac type epoxy compounds, biphenyl type epoxy compounds, biphenol novolac type epoxy compounds, biphenol type epoxy compounds, naphthalene type epoxy compounds, fluorene type epoxy compounds, phenol aralkyl type epoxy compounds, naphthol aralkyl type epoxy compounds, dicyclopentadiene type epoxy compounds, anthracene type epoxy compounds, epoxy compounds having an adamantane skeleton, epoxy compounds having a tricyclodecane skeleton, naphthylene ether type epoxy compounds, epoxy compounds having a triazine nucleus as a skeleton, and the like.

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, and preferably contains an epoxy compound having an aromatic skeleton, and particularly preferably contains an epoxy compound having a naphthalene skeleton. In this case, the dielectric loss tangent can be further reduced, and the thermal dimensional stability and flame retardancy of the cured product can be improved.

The epoxy compound preferably contains an epoxy compound that is liquid at 25 ℃ and an epoxy compound that is solid at 25 ℃ from the viewpoint of further reducing the dielectric loss tangent and improving the coefficient of linear expansion (CTE) of the cured product.

The viscosity of the epoxy compound which is liquid at 25 ℃ is preferably 1000 mPas or less, more preferably 500 mPas or less, at 25 ℃.

For measuring the viscosity of the epoxy compound, for example, a dynamic viscoelasticity measuring apparatus ("VAR-100" manufactured by reorganics instruments) or the like can be used.

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

The molecular weight of the epoxy compound means a molecular weight calculated by a structural formula of the epoxy compound in the case where the epoxy compound is a non-polymer and the structural formula of the epoxy compound can be specified. When the epoxy compound is a polymer, the weight average molecular weight is referred to.

From the viewpoint of further improving 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, and preferably 50% by weight or less, more preferably 40% by weight or less, of 100% by weight of the components other than the solvent in the resin material.

The weight ratio of the content of the epoxy compound to the total content of the bismaleimide compound a and the component X described below (the content of the epoxy compound/the total content of the bismaleimide compound a and the component X described below) is preferably 0.1 or more, more preferably 0.2 or more, and preferably 0.9 or less, more preferably 0.8 or less. When the weight ratio is not less than the lower limit and not more than the upper limit, the dielectric loss tangent can be further reduced, and the thermal dimensional stability can be further improved.

Content of the epoxy compound and the benzene

The weight ratio of the total content of the oxazine compound A and the following component X (the epoxy resin)Content of Compound/said benzo

The total content of the oxazine compound a and the component X) is preferably 0.1 or more, more preferably 0.2 or more, and preferably 0.9 or less, more preferably 0.8 or less. When the weight ratio is not less than the lower limit and not more than the upper limit, the dielectric loss tangent can be further reduced, and the thermal dimensional stability can be further improved.

[ inorganic Filler ]

The resin material contains an inorganic filler material. By using the inorganic filler, the dielectric loss tangent of the cured product can be further reduced. Further, by using the inorganic filler, dimensional change due to heat of the cured product becomes further small. The inorganic filler may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

Examples of the inorganic filler include: silica, talc, clay, mica, hydrotalcite, alumina, magnesia, aluminum hydroxide, aluminum nitride, boron nitride, and the like.

The inorganic filler is preferably silica or alumina, more preferably silica, and preferably fused silica, from the viewpoints of reducing the surface roughness of the surface of the cured product, further improving the bonding strength between the cured product and the metal layer, forming further fine wiring on the surface of the cured product, and imparting good insulation reliability by the cured product. By using silica, the thermal expansion coefficient 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 bonding strength between the cured product and the metal layer is effectively improved. The shape of the silica is preferably spherical.

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

The average particle diameter of the inorganic filler is preferably 50nm or more, more preferably 100nm or more, and preferably 500nm or more, and preferably 5 μm or less, more preferably 3 μm or less, and preferably 1 μm or less. When the average particle diameter of the inorganic filler is not less than the lower limit and not more than the upper limit, the surface roughness after etching can be reduced, the peeling strength of the plating layer can be improved, and the adhesion between the insulating layer and the metal layer can be further improved.

As the average particle diameter of the inorganic filler, a value that becomes a median particle diameter (d50) of 50% was used. The average particle diameter can be measured using a particle size distribution measuring apparatus of a laser diffraction scattering system.

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 bonding strength between the cured product and the metal layer is effectively improved. When the inorganic filler is spherical, the aspect ratio of the inorganic filler is preferably 2 or less, and more preferably 1.5 or less.

The inorganic filler is preferably surface-treated, more preferably surface-treated with a coupling agent, and preferably surface-treated with a silane coupling agent. By surface-treating the inorganic filler, the surface roughness of the roughened cured product surface is further reduced, and the bonding strength between the cured product and the metal layer is further improved. Further, by subjecting the inorganic filler to a surface treatment, it is possible to form further fine wiring on the surface of the cured product and to impart further excellent reliability of insulation between wirings and interlayer insulation to the cured product.

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

The content of the inorganic filler is preferably 50% by weight or more, more preferably 60% by weight or more, and preferably 65% by weight or more, particularly preferably 68% by weight or more, and preferably 90% by weight or less, more preferably 85% by weight or less, and preferably 80% by weight or less, particularly preferably 75% by weight or less, in 100% by weight of the components other than the solvent in the resin material. When the content of the inorganic filler is not less than the lower limit, the dielectric loss tangent is effectively reduced. When the content of the inorganic filler is not more than the upper limit, thermal dimensional stability can be improved and warpage of a cured product can be effectively suppressed. When the content of the inorganic filler is not less than the lower limit and not more than the upper limit, the surface roughness of the surface of the cured product can be further reduced, and further fine wiring can be formed on the surface of the cured product. Further, the amount of the inorganic filler can reduce the thermal expansion coefficient of the cured product and improve the detergency.

[ Maleimide Compound having no skeleton derived from dimer diamine ]

The resin material preferably contains a maleimide compound having no skeleton derived from dimer diamine. The maleimide compound having no skeleton derived from dimer diamine is different from the bismaleimide compound a. The effect of the present invention can be further exhibited by using the bismaleimide compound a in combination with the maleimide compound having no skeleton derived from dimer diamine, and the thermal dimensional stability of a cured product can be particularly improved. The maleimide compound having no skeleton derived from dimer diamine preferably has a skeleton derived from a diamine compound other than dimer diamine. The maleimide compound having no skeleton derived from dimer diamine preferably has an aromatic skeleton. The maleimide compound having an aromatic skeleton may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

In the maleimide compound having no skeleton derived from dimer diamine, it is preferable that a nitrogen atom in the maleimide skeleton is bonded to an aromatic ring.

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

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

From the viewpoint of effectively exerting the effects of the present invention of 1) to 5), the molecular weight of the maleimide compound having no skeleton derived from dimer diamine is preferably 500 or more, more preferably 1000 or more, and is preferably less than 50000, more preferably less than 20000.

The molecular weight of the maleimide compound having no skeleton derived from dimer diamine refers to a molecular weight that can be calculated by the structural formula in the case where the maleimide compound having no skeleton derived from dimer diamine is a non-polymer and the structural formula of the maleimide compound having no skeleton derived from dimer diamine can be determined. In addition, the molecular weight of the maleimide compound having no skeleton derived from dimer diamine represents a weight average molecular weight in terms of polystyrene measured by Gel Permeation Chromatography (GPC) in the case where the maleimide compound having no skeleton derived from dimer diamine is a polymer.

Examples of commercially available products of the maleimide compound having no skeleton derived from dimer diamine include "BMI 4000" and "BMI 5100" manufactured by yokuwa chemical industry co.

[ curing agent ]

The resin material preferably contains a curing agent. The curing agent is not particularly limited. As the curing agent, a conventionally known curing agent can be used. The curing agent can be used alone in 1 kind, also can be combined with the use of 2 or more.

Examples of the curing agent include: cyanate ester compound (cyanate curing agent), amine compound (amine curing agent), thiol compound (thiol curing agent), imidazole compound, phosphine compound, dicyandiamide, phenol compound (phenol curing agent), acid anhydride, active ester compound, carbodiimide compound (carbodiimide curing agent), and benzo group having no skeleton derived from dimer diamine

Oxazine compounds (benzo

An oxazine curing agent), and the like. The curing agent preferably has a functional group capable of reacting with an epoxy group of the epoxy compound.

The curing agent is preferably a compound containing a phenol compound, a cyanate ester compound, an acid anhydride, an active ester compound, a carbodiimide compound, and a benzene compound having no skeleton derived from a dimer diamine

At least 1 component of an oxazine compound. By using these preferred curing agents, the thermal dimensional stability can be further improved.

Hereinafter, the "phenol compound, cyanate compound, acid anhydride, active ester compound, carbodiimide compound, and benzo having no skeleton derived from dimer diamine" may be

At least 1 component "of the oxazine compound is described as" component X ".

Therefore, the resin material preferably contains a curing agent containing the component X. The ingredient X more preferably contains at least a phenol compound. The component X may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

As the phenol compound, there may be mentioned: novolak-type phenols, biphenol-type phenols, naphthalene-type phenols, dicyclopentadiene-type phenols, aralkyl-type phenols, dicyclopentadiene-type phenols, and the like.

As the commercial products of the phenol compounds, there can be mentioned: novolak-type phenols ("TD-2091" manufactured by DIC), diphenolnovolak-type phenols ("MEH-7851" manufactured by Ming and Kang corporation), aralkyl-type phenol compounds ("MEH-7800" manufactured by Ming and Kang corporation), phenols having an aminotriazine skeleton ("LA 1356" and "LA 3018-50P" manufactured by DIC), and the like.

As the cyanate ester compound, there can be mentioned: novolac cyanate resin, bisphenol cyanate resin, and prepolymers in which these resins are partially trimerized. Examples of the novolak type cyanate ester resin include a phenol novolak type cyanate ester resin and an alkylphenol type cyanate ester resin. Examples of the bisphenol type cyanate ester resin include bisphenol a type cyanate ester resin, bisphenol E type cyanate ester resin, and tetramethyl bisphenol F type cyanate ester resin.

Examples of commercially available products of the cyanate ester compound include: phenol novolak-type cyanate ester resins ("PT-30" and "PT-60" manufactured by Lonza Japan) and prepolymers obtained by trimerizing bisphenol-type cyanate ester resins ("BA-230S", "BA-3000S", "BTP-1000S" and "BTP-6020S" manufactured by Lonza Japan) are known.

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

As a commercially available product of the acid anhydride, RIKACID TDA-100 manufactured by Nissian chemical and physical Co., Ltd.

The active ester compound is a compound containing at least 1 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 hydroxyl compound or a thiol compound. Examples of the active ester compound include compounds represented by the following formula (1).

[ chemical formula 1]

In the formula (1), X1 represents an aliphatic chain-containing group, an aliphatic ring-containing group or an aromatic ring-containing group, and X2 represents an aromatic ring-containing group. Preferable examples of the aromatic ring-containing group 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 number of carbon atoms of the hydrocarbon group is preferably 12 or less, more preferably 6 or less, and preferably 4 or less.

Examples of the combination of X1 and X2 include: a combination of a benzene ring which may have a substituent and a benzene ring which may have a substituent, a combination of a benzene ring which may have a substituent and a naphthalene ring which may have a substituent. Further, as a combination of X1 and X2, there can be mentioned: a combination of an aliphatic ring which may have a substituent and a benzene ring which may have a substituent, a combination of a naphthalene ring which may have a substituent and a naphthalene ring which may have a substituent.

The active ester compound is not particularly limited. The active ester is preferably an active ester compound having 2 or more aromatic skeletons from the viewpoint of improving thermal dimensional stability and flame retardancy. From the viewpoint of reducing the dielectric loss tangent of a cured product and improving the thermal dimensional stability of a cured product, it is more preferable that the active ester has a naphthalene ring in the main chain skeleton.

Examples of commercially available products of the active ester compound include: "HPC-8000-65T", "EXB 9416-70 BK", "EXB 8100-65T", 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 bonding sites between the right and left end portions and other groups. The carbodiimide compound may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

[ chemical formula 2]

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

In a preferred embodiment, at least 1X is an alkylene group, a group having a substituent bonded to the alkylene group, a cycloalkylene group, or a group having a substituent bonded to the cycloalkylene group.

Examples of commercially available products of the carbodiimide compound include: "Carbodilite V-02B", "Carbodilite V-03", "Carbodilite V-04K", "Carbodilite V-07", "Carbodilite V-09", "Carbodilite 10M-SP", and "Carbodilite 10M-SP (modified)", manufactured by Nisshinbo Chemical company, "Stabaxol P", "Stabaxol P400", and "HIKAZIL 510", manufactured by Rhein Chemie company, and the like.

As the benzene having no skeleton derived from dimer diamine

Oxazine compounds, which may be mentioned by the list of P-d-type benzo

Oxazines and benzo of the F-a type

Oxazines, and the like.

As the benzene having no skeleton derived from dimer diamine

Examples of commercially available oxazine compounds include "P-d type" manufactured by chemical industries of four countries.

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

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

[ curing accelerators ]

The resin material preferably contains a curing accelerator. By using the curing accelerator, the curing speed becomes further faster. By rapidly curing the resin material, the crosslinked structure of the cured product becomes uniform, and the number of unreacted functional groups decreases, resulting in an increase in crosslinking density. The curing accelerator is not particularly limited, and conventionally known curing accelerators can be used. The curing accelerator may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

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

As the imidazole compound, there may be mentioned: 2-undecylimidazole, 2-heptadecylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1, 2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole

Trimellitate ester, 1-cyanoethyl-2-phenylimidazole

Trimellitate ester, 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-sym-tris, 2, 4-diamino-6- [2 '-methylimidazolyl- (1')]Ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-dihydroxymethylimidazole, and the like.

As the amine compound, there may be mentioned: diethylamine, triethylamine, diethylenetetramine, triethylenetetramine, 4-dimethylaminopyridine, and the like.

Examples of the phosphorus compound include a triphenylphosphine compound and the like.

As the organometallic compound, there can be mentioned: zinc naphthenate, cobalt naphthenate, tin octylate, cobalt (II) bisacetoacetonate, cobalt (III) triacetylacetonate and the like.

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

From the viewpoint of suppressing the curing temperature further low 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 suppressing the curing temperature to a lower level and effectively suppressing the warpage of the cured product, the content of the anionic curing accelerator in 100 wt% of the curing accelerator is preferably 20 wt% or more, more preferably 50 wt% or more, and preferably 70 wt% or more, and most preferably 100 wt% (total amount). Therefore, the curing accelerator is most preferably the anionic curing accelerator. By using the anionic curing accelerator in combination with the radical curing accelerator, the curing behavior may be more precisely controlled. In addition, when an epoxy compound and an active ester compound are used, the curing behavior can be more precisely controlled 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 wt% or more, more preferably 0.05 wt% or more, and preferably 5 wt% or less, more preferably 3 wt% or less, based on 100 wt% of the components other than the inorganic filler and the solvent in the resin material. When the content of the curing accelerator is not less than the lower limit and not more than the upper limit, the resin material is efficiently cured. When the content of the curing accelerator is in a more preferable range, the storage stability of the resin material is further improved, and a further excellent 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. The thermoplastic resin can be used alone in 1, also can be combined with more than 2.

The thermoplastic resin is preferably a phenoxy resin from the viewpoint of effectively reducing the dielectric loss tangent regardless of the curing environment and effectively improving the adhesion of the metal wiring. By using the phenoxy resin, deterioration of the embedding property of the resin film into the holes or irregularities of the circuit board and unevenness of the inorganic filler can be suppressed. In addition, by using the phenoxy resin, the melt viscosity can be adjusted, and therefore the dispersibility of the inorganic filler becomes good, and the resin composition or the B-staged product becomes less likely to wet and spread in unintended areas during the curing process.

The phenoxy resin contained in the resin material is not particularly limited. As the phenoxy resin, conventionally known phenoxy resins can be used. The phenoxy resin can be used alone in 1 kind, also can be combined with more than 2 kinds.

Examples of the phenoxy resin include: phenoxy resins having a bisphenol a type skeleton, a bisphenol F type skeleton, a bisphenol S type skeleton, a biphenyl skeleton, a novolac skeleton, a naphthalene skeleton, an imide skeleton, and the like.

Examples of commercially available products of the phenoxy resin include: "YP 50", "YP 55" and "YP 70" manufactured by shinaiwa chemical company, and "1256B 40", "4250", "4256H 40", "4275", "YX 6954BH 30" and "YX 8100BH 30" manufactured by mitsubishi chemical company, and the like.

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

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

The tetracarboxylic dianhydride may be mentioned, for example, as mentioned above.

The commercially available dimer diamine may be exemplified by the commercially available dimer diamine.

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 may be reacted with an epoxy resin. By reacting the polyimide compound with an epoxy resin, the thermal dimensional stability of a cured product can be improved.

From the viewpoint of obtaining a resin material having still more excellent storage stability, the weight average molecular weight of the thermoplastic resin, the polyimide resin, and the phenoxy resin is preferably 5000 or more, more preferably 10000 or more, and preferably 100000 or less, more preferably 50000 or less.

The weight average molecular weights of the thermoplastic resin, the polyimide resin, and the phenoxy resin represent weight average molecular weights in terms of polystyrene 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 the case where the thermoplastic resin is a polyimide resin or a phenoxy resin, the content of the polyimide resin or the phenoxy resin) in 100 wt% of the components other than the inorganic filler and the solvent in the resin material is preferably 1 wt% or more, more preferably 2 wt% or more, and preferably 30 wt% or less, more preferably 20 wt% or less. When the content of the thermoplastic resin is not less than the lower limit and not more than the upper limit, the embedding property of the resin material into the holes or the recesses and projections of the circuit board becomes good. When the content of the thermoplastic resin is not less than the lower limit, the formation of the resin film is further facilitated, and a further excellent insulating layer can be obtained. When the content of the thermoplastic resin is not more than the upper limit, the thermal expansion coefficient of the cured product is further decreased. When the content of the thermoplastic resin is not more than the upper limit, the surface roughness of the surface of the cured product is further reduced, and the bonding strength between the cured product and the metal layer is further improved.

[ solvent ]

The resin material contains no solvent or contains a solvent. By using the solvent, the viscosity of the resin material can be controlled to a preferable range, and the coatability of the resin material can be improved. In addition, the solvent may be used to obtain a slurry containing the inorganic filler material. The solvent can be used alone in 1, also can be combined with more than 2.

As the solvent, there may be mentioned: acetone, methanol, ethanol, butanol, 2-propanol, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 2-acetoxy-1-methoxypropane, toluene, xylene, methyl ethyl ketone, 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 shape. Therefore, the boiling point of the solvent is preferably 200 ℃ or less, more preferably 180 ℃ or less. The content of the solvent in the resin composition is not particularly limited. The content of the solvent may be appropriately changed in consideration of coatability of the resin composition, etc.

In the case where the resin material is a B-staged film, the content of the solvent is preferably 1 wt% or more, more preferably 2 wt% or more, and preferably 10 wt% or less, more preferably 5 wt% or less, in 100 wt% of the B-staged film.

[ other ingredients ]

The resin material may contain a leveling agent, a flame retardant, a coupling agent, a colorant, an antioxidant, an ultraviolet deterioration preventing agent, a defoaming agent, a thickener, a thixotropy imparting agent, and a thermosetting resin other than an epoxy compound for the purpose of improving impact resistance, heat resistance, compatibility of the resin, workability, and the like.

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

Examples of the other thermosetting resin include: polyphenylene ether resin, divinylbenzyl ether resin, polyarylate resin, diallyl phthalate resin, polyimide resin, and benzo

Oxazine resin, benzo

Azole resins, bismaleimide resins, acrylate resins, and the like.

(resin film)

By forming the resin composition into a film shape, a resin film (B-staged material/B-staged film) can be obtained. The resin material is preferably a resin film. The resin film is preferably a B-stage film.

As a method for obtaining a resin film by molding the resin composition into a film shape, the following method can be mentioned. An extrusion molding method in which a resin composition is melt kneaded using an extruder, extruded, and then molded into a film shape using a T-die, a circular die, or the like. A casting method in which a resin composition containing a solvent is cast to form a film. Other film forming methods are known. In order to cope with the reduction in thickness, an extrusion molding method or a casting method is preferable. The film comprises a sheet.

The resin composition is molded into a film shape and is dried by heating at 50 to 150 ℃ for 1 to 10 minutes, for example, to such an extent that the curing by heat is not excessively performed, thereby obtaining a resin film as a B-stage film.

The film-like resin composition obtainable 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 curing may be further performed.

The resin film may be a non-prepreg. When the resin film is a non-prepreg, migration does not occur along a glass cloth or the like. In addition, when the resin film is laminated or precured, unevenness due to the glass cloth does not occur on the surface. The resin film may be used in the form of a laminate film including a metal foil or a substrate and a resin film laminated on the surface of the metal foil or the substrate. The metal foil is preferably a copper foil.

As the substrate of the laminated film, there may be mentioned: polyester resin films such as polyethylene terephthalate films and polybutylene terephthalate films; olefin resin films such as polyethylene films and polypropylene films; and polyimide resin films and the like. The surface of the substrate may be subjected to a release treatment as required.

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

The glass transition temperature of the resin material or the resin film is preferably 150 ℃ or higher, more preferably 170 ℃ or higher, from the viewpoint of further improving the thermal dimensional stability of the cured product and further improving the adhesion between the insulating layer and the metal layer.

The glass transition temperature is measured as follows.

When the resin material is a non-resin film, the resin material is formed into a film to obtain a resin film. The resin film is press-molded to obtain a measurement object. The obtained measurement object was measured with a viscoelasticity measuring apparatus (for example, "ARES-G2" manufactured by TAINSTRUMENTS), and the peak temperature of the loss tangent of the obtained measurement result was defined as the glass transition temperature Tg. The measurement was performed under conditions of decreasing the temperature from 100 ℃ to-10 ℃ at a cooling rate of 3 ℃/min, and under conditions of a frequency of 1Hz and a strain of 1%, using a parallel plate having a diameter of 8mm as a jig.

(semiconductor device, printed Wiring Board, copper-clad laminate, and multilayer printed Wiring Board)

The resin material can be suitably used for forming a mold resin embedding a semiconductor chip in a semiconductor device.

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

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

The resin film may be a member to be laminated having a metal layer on one or both surfaces thereof. A laminated structure including a member to be laminated having a metal layer on a surface thereof and a resin film laminated on the surface of the metal layer, wherein the resin film is the resin material, can be suitably obtained. The method for laminating the resin film and the member to be laminated having the metal layer on the surface thereof is not particularly limited, and a known method can be used. For example, the resin film may be laminated on a member to be laminated having a metal layer on the surface thereof by using a parallel plate press, a roll laminator, or the like while heating and pressing the resin film, or without applying heat and pressing the resin film.

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 can be suitably used for obtaining a copper-clad laminate. As an example of the copper-clad laminate, there is a copper-clad laminate including 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 to 50 μm. In order to improve the bonding strength between the cured product of the resin material and the copper foil, the copper foil preferably has fine irregularities on the surface. The method of forming the unevenness is not particularly limited. Examples of the method for forming the irregularities include a method of forming the irregularities by treatment using a known chemical solution.

The resin material can be suitably used to obtain a multilayer substrate.

As an example of the multilayer substrate, there is a multilayer substrate including a circuit board and an insulating layer laminated on the circuit board. The insulating layer of the multilayer substrate is formed of the resin material. Further, the insulating layer of the multilayer substrate can be formed by using a laminate film and using the resin film of the laminate film. The insulating layer is preferably laminated on the surface of the circuit substrate on which the circuit is provided. A portion of the insulating layer preferably embeds the circuitry.

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

The roughening treatment method may be any conventionally known roughening treatment method, and is not particularly limited. The surface of the insulating layer may be subjected to swelling treatment before roughening treatment.

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

In addition, another example of the multilayer substrate includes a circuit board, an insulating layer laminated on a surface of the circuit board, and a copper foil laminated on a surface of the insulating layer opposite to the surface on which the circuit board is laminated. The insulating layer is preferably formed by curing a resin film by using a copper-clad laminate including a copper foil and the resin film laminated on one surface of the copper foil. Preferably, the copper foil is etched to form a copper circuit.

Another example of the multilayer substrate includes a multilayer substrate including a circuit board and a plurality of insulating layers stacked on a surface of the circuit board. At least 1 of the plurality of insulating layers disposed on the circuit board is formed using the resin material. The multilayer substrate preferably further includes a circuit laminated on at least one surface of the insulating layer formed using the resin film.

In a multilayer printed wiring board of a multilayer substrate, a low dielectric loss tangent is required, and high insulation reliability by an insulating layer is required. The resin material of the present invention can effectively improve insulation reliability by reducing dielectric loss tangent and improving adhesion between the insulating layer and the metal layer and etching performance. Therefore, the resin material of the present invention can be suitably used for forming an insulating layer in a multilayer printed wiring board.

The multilayer printed wiring board includes, for example: a circuit substrate; a multilayer insulating layer disposed on a surface of the circuit substrate; and a metal layer disposed between the plurality of insulating layers. At least 1 of the insulating layers is a cured product of the resin material.

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

In a multilayer printed wiring board 11 shown in fig. 1, a plurality of insulating layers 13 to 16 are laminated on an upper surface 12a of a circuit board 12. The insulating layers 13 to 16 are cured layers. A metal layer 17 is formed on a partial region of the upper surface 12a of the circuit board 12. Among the multiple insulating layers 13 to 16, a metal layer 17 is formed in a partial region of the upper surface of the insulating layers 13 to 15 except for the insulating layer 16 on the surface of the outer side opposite to the circuit board 12 side. The metal layer 17 is a circuit. A metal layer 17 is disposed between the circuit board 12 and the insulating layer 13 and between each of the stacked insulating layers 13 to 16. The lower metal layer 17 and the upper metal layer 17 are connected to each other by at least one of a via connection structure and a via connection structure, not shown.

In the multilayer printed wiring board 11, the insulating layers 13 to 16 are formed by 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. The metal layer 17 reaches the inside of the fine pores. In addition, 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. In the multilayer printed wiring board 11, good insulation reliability is provided between the upper metal layer and the lower metal layer which are not connected by a via connection structure and a via connection structure, not shown.

(roughening treatment and swelling treatment)

The resin material is preferably used for obtaining a cured product subjected to roughening treatment or desmutting treatment. The cured product includes a pre-cured product that can be further cured.

In order to form fine irregularities on the surface of a cured product obtained by precuring the resin material, it is preferable to roughen the cured product. Before the roughening treatment, the cured product is preferably subjected to swelling treatment. The cured product is preferably subjected to swelling treatment after the precuring and before the roughening treatment, and is cured after the roughening treatment. However, the cured product is not necessarily subjected to swelling treatment.

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

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

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

The arithmetic average roughness Ra of the surface of the cured product is preferably 10nm or more, and is preferably less than 300nm, more preferably less than 200nm, and still more preferably less than 150 nm. In this case, the bonding strength between the cured product and the metal layer is improved, and further fine wiring is formed on the surface of the insulating layer. Further, the conductor loss can be suppressed, and the signal loss can be suppressed to be low. The arithmetic average roughness Ra is measured in JIS B0601: 1994 as benchmark.

(decontamination treatment)

There are cases where a through hole is formed in a cured product obtained by precuring the resin material. In the multilayer substrate and the like, a via hole, a through hole, and the like are formed as a through hole. For example, the via hole can pass CO₂Laser light such as laser light. The diameter of the via hole is about 60 μm to 80 μm, but is not particularly limited. In many cases, the formation of the through-hole causes a stain, which is a residue of the resin derived from the resin component contained in the cured product, to be formed at the bottom of the through-hole.

In order to remove the stain, the surface of the cured product is preferably subjected to desmear treatment. Sometimes, the desmear treatment is accompanied by a roughening treatment.

The desmutting treatment uses, for example, a chemical acidifying agent such as a manganese compound, a chromium compound, or a persulfate compound, as in the roughening treatment. These chemical acidifying agents are used in the form of an aqueous solution or an organic solvent dispersion solution after adding water or an organic solvent. The desmear treatment liquid for desmear treatment generally contains an alkali. The decontamination treatment solution preferably contains sodium hydroxide.

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

The present invention will be described in detail below 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)

Benzo (b) is

Oxazine Compound A1 (synthesized according to synthetic example 4 below)

(Synthesis example 1)

To a reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen gas inlet tube, 135.0g of tetracarboxylic dianhydride ("BisDA-1000" manufactured by SABIC Japan K.K.) and 400g of cyclohexanone were added, and the solution in the reaction vessel was heated to 60 ℃. Then, 17.5g of 1, 3-bisaminomethylcyclohexane (molecular weight 142.25, manufactured by Mitsubishi Gaschemical Co., Ltd.) was added dropwise to the reaction vessel to carry out a reaction, thereby obtaining a reaction product having acid anhydrides at both ends. Then, 148g of dimer diamine ("PRIAMINE 1075" manufactured by Croda Japan K.K.) was gradually added to the reaction vessel, and 60.0g of methylcyclohexane was added to the reaction vessel. A dean-stark separator and a condenser were attached to the flask, and the mixture was heated and refluxed for 2 hours to obtain an imide compound having an amine structure at both ends. Then, 28g of maleic anhydride was added, and the resulting mixture was further refluxed for 12 hours to perform maleimide-addition. After the reaction was completed, isopropanol was added to carry out reprecipitation, and then the precipitate was recovered and dried. Thus, an N-alkylbismaleimide compound (weight average molecular weight 10000) having a skeleton derived from a dimer diamine and having a skeleton derived from a diamine compound other than the dimer diamine was obtained. The recovery rate of the obtained N-alkylbismaleimide compound was 83%.

(Synthesis example 2)

55g of pyromellitic dianhydride (molecular weight 254.15, manufactured by Tokyo chemical Co., Ltd.) and 300g of cyclohexanone were charged into a reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen gas inlet tube, and the solution in the reaction vessel was heated to 60 ℃. Then, 26.7g of a solution of bis (aminomethyl) norbornane (molecular weight: 154.26, manufactured by Tokyo chemical Co., Ltd.) dissolved in cyclohexanone was dropped into the reaction vessel to carry out a reaction, thereby obtaining a reaction product having acid anhydrides at both ends. Thereafter, isopropanol was added to recover the imide compound having acid anhydrides at both ends. Then, the precipitate was dissolved again in cyclohexanone, 46.0g of dimer diamine ("PRIAMINE 1075" manufactured by Croda Japan K.K.) was slowly added to the reaction vessel, and 45.0g of methylcyclohexane was added to the reaction vessel. A dean-Stark separator and a condenser were attached to the flask, and the mixture was refluxed for 2 hours to obtain an imide compound having a dimer diamine structure at both terminals. Then, 8.7g of maleic anhydride was added, and the resulting mixture was further refluxed for 12 hours to perform maleimide-addition. After the reaction was completed, isopropanol was added to the reaction solution to reprecipitate, and then the precipitate was recovered and dried. In this manner, a bismaleimide compound (weight average molecular weight 8700) having a skeleton derived from dimer diamine and having a skeleton derived from a diamine compound other than dimer diamine 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)

55g of pyromellitic dianhydride (molecular weight 254.15, manufactured by Tokyo chemical Co., Ltd.) and 300g of cyclohexanone were charged into a reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen gas inlet tube, and the solution in the reaction vessel was heated to 60 ℃. Then, 39.1g of a solution obtained by dissolving 4,4' -methylenebis (2-methylcyclohexylamine) (molecular weight 238.42, manufactured by Tokyo chemical industries, Ltd.) in cyclohexanone was dropped into the reaction vessel to carry out a reaction, thereby obtaining a reaction product having acid anhydrides at both ends. Thereafter, isopropanol was added to recover the imide compound having acid anhydrides at both ends. Then, the precipitate was dissolved again in cyclohexanone, 46.0g of dimer diamine ("PRIAMINE 1075" manufactured by Croda Japan K.K.) was slowly added to the reaction vessel, and 45.0g of methylcyclohexane was added to the reaction vessel. A dean-Stark separator and a condenser were attached to the flask, and the mixture was refluxed for 2 hours to obtain an imide compound having a dimer diamine structure at both terminals. Then, 8.9g of maleic anhydride was added, and the resulting mixture was further refluxed for 12 hours to perform maleimide-addition. After the reaction was completed, isopropanol was added to the reaction solution to reprecipitate, and then the precipitate was recovered and dried. In this manner, a bismaleimide compound (weight average molecular weight 9800) having a skeleton derived from dimer diamine and having a skeleton derived from a diamine compound other than dimer diamine 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)

To a reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen gas inlet tube, 135.0g of tetracarboxylic dianhydride ("BisDA-1000" manufactured by SABIC Japan K.K.) and 400g of cyclohexanone were added, and the solution in the reaction vessel was heated to 60 ℃. Then, 17.5g of 1, 3-bisaminomethylcyclohexane (molecular weight 142.25, manufactured by Mitsubishi Gaschemical Co., Ltd.) was added dropwise to the reaction vessel to conduct a reactionA reaction product having acid anhydrides at both ends is obtained. Then, 148g of dimer diamine ("PRIAMINE 1075" manufactured by Croda Japan K.K.) was gradually added to the reaction vessel, and 60.0g of methylcyclohexane was added to the reaction vessel. A dean-stark separator and a condenser were attached to the flask, and the mixture was heated under reflux for 2 hours to obtain an imide compound having an amine structure at both ends. Then, phenol and paraformaldehyde were added, and the resulting mixture was further refluxed for 12 hours to effect benzo

And (4) carrying out oxazination. After the reaction was completed, isopropanol was added to carry out reprecipitation, and then the precipitate was recovered and dried. Thus, a benzene having a skeleton derived from dimer diamine and having a skeleton derived from a diamine compound other than dimer diamine is obtained

Oxazine compound (weight average molecular weight 11000). The resulting benzene

The yield of the oxazine compound was 83%.

Bismaleimide compounds A1, A2, A3 synthesized in Synthesis examples 1 to 3 and benzo compound synthesized in Synthesis example 4

The weight average molecular weight of the oxazine compound a1 was determined in the following manner.

GPC (gel permeation chromatography) assay:

the column temperature was 40 ℃ and the flow rate was 1.0ml/min, using Tetrahydrofuran (THF) as a developing solvent, using a high performance liquid chromatography system manufactured by Shimadzu corporation. "SPD-10A" was used as a detector, and a column was prepared by connecting 2 columns of "KF-804L" (molecular weight exclusion limit 400000) manufactured by Shodex K.K.K.in series. As the standard polystyrene, "TSK standard polystyrene" manufactured by Tosoh corporation was used, and calibration curves were prepared using materials having weight average molecular weights Mw of 354000, 189000, 98900, 37200, 17100, 9830, 5870, 2500, 1050, and 500, and the molecular weights were calculated.

The obtained bismaleimide compounds A1, A2, A3 and benzo

In the oxazine compound a1, the number of aliphatic rings of the dimer diamine skeleton, a1, was 1. The obtained bismaleimide compounds A1, A2, A3 and benzo

The number of carbon atoms not constituting the aromatic ring or the aliphatic ring, among carbon atoms present between the nitrogen atom constituting one amino group and the nitrogen atom constituting the other amino group in the dimer diamine skeleton in the oxazine compound a1, a2, was 16. An example of the structure of maleimide in the skeleton derived from dimer diamine is shown in the following formula (3). It should be noted that, since the dimer diamine is a natural product (mixture), the dimer diamine used is not limited to the dimer diamine having the structure of the following formula (3), but even when the total 17 of a1 and a2 is compared with the total of B1, B2 and B3, the properties of the bismaleimide compound do not affect the effects of the present invention.

In the obtained bismaleimide compound a1, the number of aromatic rings B1 and the number of aliphatic rings B2 in the skeleton derived from a diamine compound other than dimer diamine were 0 and 1, respectively. In the skeleton derived from a diamine compound other than dimer diamine in the obtained bismaleimide compound a1, the number B3 of carbon atoms, nitrogen atoms, and oxygen atoms not constituting an aromatic ring or an aliphatic ring among carbon atoms, nitrogen atoms, and oxygen atoms present between a nitrogen atom constituting one amino group and a nitrogen atom constituting the other amino group is 2. An example of a skeleton derived from a diamine compound other than dimer diamine is shown in the following formula (4).

[ chemical formula 3]

[ chemical formula 4]

In the obtained bismaleimide compound a2, the number of aromatic rings B1 and the number of aliphatic rings B2 in the skeleton derived from a diamine compound other than dimer diamine were 0 and 1, respectively. In the skeleton derived from a diamine compound other than dimer diamine in the obtained bismaleimide compound a2, the number B3 of carbon atoms, nitrogen atoms, and oxygen atoms of an aromatic ring and an aliphatic ring, which are not technically characterized, is 2, out of carbon atoms, nitrogen atoms, and oxygen atoms present between a nitrogen atom of one technically characterized amino group and a nitrogen atom of another technically characterized amino group.

In the obtained bismaleimide compound a3, the number of aromatic rings B1 and the number of aliphatic rings B2 in the skeleton derived from a diamine compound other than dimer diamine were 0 and 2, respectively. In the skeleton derived from a diamine compound other than dimer diamine in the obtained bismaleimide compound a3, the number B3 of carbon atoms, nitrogen atoms, and oxygen atoms not constituting an aromatic ring or an aliphatic ring among carbon atoms, nitrogen atoms, and oxygen atoms present between a nitrogen atom constituting one amino group and a nitrogen atom constituting the other amino group is 1.

The resulting benzene

In the oxazine compound a1, the number of aromatic rings B1 and the number of aliphatic rings B2 in the skeleton derived from a diamine compound other than dimer diamine were 0 and 1, respectively. The resulting benzene

The number of carbon atoms, nitrogen atoms and oxygen atoms not constituting the aromatic ring or the aliphatic ring among carbon atoms, nitrogen atoms and oxygen atoms existing between a nitrogen atom constituting one amino group and a nitrogen atom constituting the other amino group in the skeleton derived from a diamine compound other than dimer diamine in the oxazine compound A1The amount B3 was 2.

The obtained bismaleimide compounds A1, A2, A3 and benzo

Details of oxazine compound a1 are shown in table 1.

[ Table 1]

(others)

N-alkylbismaleimide Compound 1 ("BMI-1700", softening Point 60 ℃ manufactured by Designer Molecules Inc.)

N-alkylbismaleimide Compound 2 ("BMI-1500" manufactured by Designer Molecules Inc.)

N-Phenylmaleimide Compound (BMI-4000, manufactured by Dahe Kasei Kogyo Co., Ltd.)

(epoxy compound)

Biphenyl epoxy Compound (NC-3000 manufactured by Nippon Kabushiki Kaisha)

Naphthalene type epoxy Compound (HP-4032D, manufactured by DIC corporation)

Resorcinol diglycidyl ether ("EX-201" manufactured by Nagase chemteX corporation)

Dicyclopentadiene type epoxy Compound (EP 4088S, manufactured by ADEKA corporation)

Naphthol aralkyl type epoxy Compound ("ESN-475V" manufactured by Nippon iron Japan chemical Co., Ltd.)

(inorganic Filler)

Slurry containing silica (75% by weight of silica, ` SC4050-HOA ` manufactured by Admatechs corporation, average particle diameter 1.0. mu.m, aminosilane treatment, 25% by weight of cyclohexanone)

(curing agent)

Component X:

solution containing a cyanate ester compound ("BA-3000S" manufactured by Lonza Japan K.K., solid content: 75 wt%)

Solution containing active ester Compound 1 ("EXB-9416-70 BK" manufactured by DIC corporation, solid content: 70 wt%)

Solution containing active ester Compound 2 ("HPC-8000L" manufactured by DIC corporation, solid content 65 wt%)

Active ester Compound 3-containing solution ("HPC-8150" manufactured by DIC corporation, solid content 62 wt%)

Phenol compound-containing solution ("LA-1356" manufactured by DIC corporation, solid content 60 wt%)

Carbodiimide compound-containing solution ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., "solid content: 50% by weight)

(curing accelerators)

Dimethylaminopyridine (DMAP available from Wako pure chemical industries, Ltd.)

2-phenyl-4-methylimidazole ("2P 4 MZ" manufactured by Siguo Kabushiki Kaisha)

2-Ethyl-4-methylimidazole ("2E 4 MZ" manufactured by Siguo Kabushiki Kaisha)

Dicumyl peroxide (Tokyo chemical industry Co., Ltd.)

(thermoplastic resin)

Polyimide compound (polyimide resin):

a solution containing a polyamideimide compound (nonvolatile content: 26.8 wt%) as a reaction product of tetracarboxylic dianhydride and dimer diamine was synthesized according to the following synthesis example 5.

(Synthesis example 5)

A reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen gas inlet was charged with 300.0g of tetracarboxylic dianhydride ("BisDA-1000" manufactured by SABIC Japan K.K.) and 665.5g of cyclohexanone, and the solution in the reaction vessel was heated to 60 ℃. Then, 89.0g of dimer diamine ("PRIAMINE 1075" manufactured by Croda Japan K.K.) and 54.7g of 1, 3-bisaminomethylcyclohexane (manufactured by Mitsubishi Gas Chemical) were added dropwise to the reaction vessel. Then, 121.0g of methylcyclohexane and 423.5g of ethylene glycol dimethyl ether were added to the reaction vessel, and imidization was performed at 140 ℃ for 10 hours. Thus, a solution containing the polyimide compound (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/the 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) assay:

the column temperature was 40 ℃ and the flow rate was 1.0ml/min, using Tetrahydrofuran (THF) as a developing solvent, using a high performance liquid chromatography system manufactured by Shimadzu corporation. "SPD-10A" was used as a detector, and a column was prepared by connecting 2 columns of "KF-804L" (excluding a limiting molecular weight of 400,000) manufactured by Shodex. As the standard polystyrene, "TSK standard polystyrene" manufactured by Tosoh corporation was used, and calibration curves were prepared using materials having weight average molecular weights Mw of 354000, 189000, 98900, 37200, 17100, 9830, 5870, 2500, 1050, and 500, and the molecular weights were calculated.

(examples 1 to 17 and comparative examples 1 to 3)

The components shown in tables 2 to 4 were blended at the blending amounts (unit is weight part of solid component) shown in tables 2 to 4, and stirred at room temperature until a uniform solution was obtained, thereby obtaining a resin material.

Preparation of resin film:

the obtained resin material was coated on a release-treated surface of a release-treated PET film ("XG 284" manufactured by Toray corporation, thickness 25 μm) using a coater, and then dried in a gill oven (geooven) at 100 ℃ for 2 minutes and 30 seconds to volatilize the solvent. Thus, a laminated film (laminated film of a PET film and a resin film) was obtained in which a resin film (B-stage film) having a thickness of 40 μm was laminated on a PET film.

(evaluation)

(1) Dielectric loss tangent

The obtained resin film was cut into a size of 2mm in width and 80mm in length, and 5 sheets were stacked to obtain a laminate having a thickness of 200 μm. The obtained laminate was heated at 190 ℃ for 90 minutes to obtain a cured product. The dielectric loss tangent of the obtained cured product was measured at a frequency of 1.0GHz at room temperature (23 ℃ C.) by the resonance cavity method using a "dielectric constant measuring apparatus CP521 by resonance cavity perturbation method" manufactured by Kanto electronic applications and a "network analyzer N5224 APNA" manufactured by Keysight technology.

(2) Thermal dimensional stability (mean coefficient of linear expansion (CTE))

The obtained resin film (B-stage film) having a thickness of 40 μm was heated at 190 ℃ for 90 minutes, and the obtained cured product was cut into a size of 3mm × 25 mm. The average linear expansion coefficient (ppm/. degree. C.) of the cut cured product at 25 to 150 ℃ was calculated under the conditions of a tensile load of 33mN and a temperature rise rate of 5 ℃/min using a thermomechanical analyzer ("EXSTAR TMA/SS 6100" manufactured by SIINano technology Co., Ltd.).

[ criterion for determining average linear expansion coefficient ]

O ^ O: the average linear expansion coefficient is below 25 ppm/DEG C

O: the average linear expansion coefficient is more than 25 ppm/DEG C and less than 30 ppm/DEG C

X: the average linear expansion coefficient exceeds 30 ppm/DEG C

(3) Adhesion (peel strength) between insulating layer and metal layer

A laminating step:

a double-sided copper-clad laminate ("MCL-E679 FG", manufactured by Hitachi chemical Co., Ltd.) was prepared, the thickness of each copper foil being 18 μm, the thickness of the substrate being 0.7mm, the substrate size being 100 mm. times.100 mm. Both sides of the copper foil surface of the double-sided copper-clad laminate were immersed in "Cz 8101" manufactured by MEC corporation, and the surface of the copper foil was roughened. On both sides of the roughened copper-clad laminate, a "batch vacuum laminator MVLP-500-IIA" manufactured by a company name was used, and the resin film (B-stage film) side of the laminate film was laminated on the copper-clad laminate to obtain a laminate structure. The lamination conditions were such that the pressure was reduced to 13hPa or less for 30 seconds and then increased at 100 ℃ and a pressure of 0.4MPa for 30 seconds.

A film peeling step:

in the obtained laminated structure, the double-sided PET film was peeled off.

Copper foil attaching step:

the smooth surface of a copper foil (35 μm in thickness, "Cz 8101" manufactured by MEC) was subjected to Cz treatment to etch the surface of the copper foil by about 1 μm. And bonding the etched copper foil to the laminated structure with the PET film peeled off to obtain the substrate with the copper foil. The obtained copper foil-attached substrate was heat-treated in a gill oven at 190 ℃ for 90 minutes to obtain an evaluation sample.

(3-1) measurement of peel strength (adhesion) at room temperature Environment:

the surface of the copper foil of the sample was evaluated by cutting a short strip-like slit having a width of 1 cm. An evaluation sample was set in a 90 ° peel tester ("TE-3001" manufactured by tesersatyo corporation), and an end portion of the copper foil having a notch was held by a jig, and the copper foil was peeled off by 20mm to measure peel strength (peel strength).

[ criterion for determining peel strength in a room temperature Environment ]

O ^ O: peel strength of 0.6kgf or more

O: a peel strength of 0.4kgf or more and less than 0.6kgf

X: peel strength less than 0.4kgf

(3-2) measurement of peel strength in a high temperature (260 ℃) atmosphere:

the surface of the copper foil of the sample was evaluated by cutting a short strip-like slit having a width of 1 cm. After a heating unit was placed at a position where an evaluation sample was placed in a 90 ° peel tester ("TE-3001" manufactured by sterstangyo corporation), the evaluation sample was placed, and the heating unit was set to 260 ℃. Thereafter, the copper foil having the notch was held by a jig at its end, and the copper foil was peeled off by 20mm to measure peel strength (peelstrength).

[ criterion for determining peel strength in high-temperature (260 ℃) environment ]

O ^ O: peel strength of 0.1kgf or more

O: a peel strength of 0.05kgf or more and less than 0.1kgf

X: peel strength less than 0.05kgf

(4) Surface roughness after etching (surface roughness)

Laminating and semi-curing:

a double-sided copper-clad laminate (CCL substrate) (E679 FG manufactured by hitachi chemical corporation) was prepared. Both sides of the copper foil surface of the double-sided copper-clad laminate were immersed in "Cz 8101" manufactured by MEC corporation, and the surface of the copper foil was roughened. On both sides of the roughened copper-clad laminate, a laminate structure was obtained by laminating the resin film (B-stage film) side of the laminate film on the copper-clad laminate using a "batch vacuum laminator MVLP-500-IIA" manufactured by a company name. The lamination conditions were that the pressure was reduced for 30 seconds to 13hPa or less, and then the pressure was increased for 30 seconds at 100 ℃ and 0.4 MPa. Thereafter, the resin film was semi-cured by heating at 180 ℃ for 30 minutes. In this manner, a laminate in which a semi-cured product of a resin film was laminated on a CCL substrate was obtained.

Roughening treatment:

(a) swelling treatment:

the obtained laminate was put into a Swelling solution ("Swelling Dip securigant p" manufactured by Atotech Japan corporation) at 60 ℃ and shaken for 10 minutes. Thereafter, the film was washed with pure water.

(b) Permanganate treatment (roughening treatment and desmutting treatment):

the laminate after the swelling treatment was put into a roughening aqueous solution of potassium permanganate ("Concentrate Compact CP" manufactured by Atotech Japan K.K.) at 70 ℃ and shaken for 30 minutes. Next, the sample was treated with a 25 ℃ washing solution ("Reduction Securigint P" manufactured by Atotech Japan K.K.) for 2 minutes and then washed with pure water to obtain an evaluation sample.

Measurement of surface roughness:

the surface of the evaluation sample (cured product subjected to roughening treatment) was measured for arithmetic mean roughness Ra in a measurement region of 94. mu. m.times.123. mu.m, using a non-contact three-dimensional surface shape measuring apparatus ("WYKO NT 1100" manufactured by Veeco). The arithmetic average roughness Ra is measured in accordance with JIS B0601: 1994 as benchmark. The surface roughness was determined according to the following criteria.

[ criterion for determining surface roughness ]

O ^ O: ra less than 50nm

O: ra is 50nm or more and less than 200nm

X: ra of 200nm or more

(5) Peel strength of plating

Electroless plating treatment:

the surface of the hardened material subjected to roughening treatment obtained in the evaluation of the surface roughness of (4) was treated with an alkali cleaning solution (Cleaner securigant902 manufactured by Atotech Japan K.K.) at 60 ℃ for 5 minutes, and then degreased and cleaned. After washing, the cured product was treated with a 25 ℃ Pre-dip (Pre-dip Neodant B manufactured by Atotech Japan K.K.) for 2 minutes. Thereafter, the cured product was treated with an Activator ("Activator neuron 834" manufactured by Atotech Japan K.K.) at 40 ℃ for 5 minutes, and a palladium catalyst was added. Next, the cured product WAs treated with a reducing solution (reducing neo WA manufactured by Atotech Japan) at 30 ℃ for 5 minutes.

Next, the cured product was added to a chemical Copper solution ("BasicPrintganth MSK-DK", "Copper Printganth MSK", "Stabilizer Printganth MSK", and "Reducer Cu" manufactured by Atotech Japan K.K.), and electroless plating was performed until the plating thickness became about 0.5. mu.m. After the electroless plating, annealing treatment was performed at a temperature of 120 ℃ for 30 minutes in order to remove residual hydrogen. All steps up to the step of electroless plating were performed while shaking the cured product with the treatment solution set to 2L at a beaker scale.

Electrolytic Dufu treatment:

next, the cured product subjected to the electroless plating treatment was subjected to electrolytic plating until the plating thickness became 25 μm. As the electrolytic copper plating, a copper sulfate solution (copper sulfate pentahydrate manufactured by Wako pure chemical industries, Ltd.) was used"sulfuric acid" manufactured by Wako pure chemical industries, Ltd., "Basic Leveller Curoacid HL" manufactured by Atotech Japan K.K., "correction agent Curoacid GS" manufactured by Atotech Japan K.K.), and a flow rate of 0.6A/cm²The electrolytic plating is performed until the plating thickness becomes about 25 μm. After the copper plating treatment, the cured product was heated at 190 ℃ for 90 minutes to further cure the cured product. Thus, a cured product having a copper plating layer laminated on the upper surface was obtained.

Determination of peel strength of plating:

a short slit having a width of 0.5cm was cut into the surface of the obtained copper plating layer on which the cured product of the copper plating layer was laminated. The cured product having the copper plating layer laminated on the upper surface thereof was set in a 90 ° peel TESTER ("TE-3001" manufactured by stester SANGYO corporation), and the copper plating layer was peeled 15mm by holding the edge of the copper plating layer having a notch with a jig to measure the peel strength (plating peel strength).

[ criterion for determining peel strength of plating ]

O ^ O: the peel strength of the plating layer is more than 0.5kgf

O: the peel strength of the plating layer is more than 0.3kgf and less than 0.5kgf

X: the peel strength of the plating layer is less than 0.3kgf

The compositions and the results are shown in tables 2 to 4 below. In tables 2 to 4, the contents of the respective components are shown in terms of pure amounts (parts by weight of solid matter components).

Symbol mark

11 … multilayer printed circuit board

12 … loop base plate

12a … upper surface

13 to 16 … insulating layer

17 … metal layer

Claims (18)

1. A resin material comprising a compound A and an inorganic filler, wherein,

the compound A is a bismaleimide compound having a skeleton derived from dimer diamine and having a skeleton derived from a diamine compound other than dimer diamine, and a benzo compound having a skeleton derived from dimer diamine and having a skeleton derived from a diamine compound other than dimer diamine

At least one of oxazine compounds.

2. The resin material according to claim 1, wherein a distance between amino groups in a skeleton of the diamine compound other than dimer diamine is smaller than a distance between amino groups in a skeleton of the dimer diamine.

3. The resin material according to claim 1 or 2, wherein the compound a has the dimer diamine-derived skeleton at both ends of a main chain.

4. The resin material according to any one of claims 1 to 3, wherein the compound A has the dimer diamine-derived skeleton only at both ends of a main chain.

5. The resin material according to any one of claims 1 to 4, wherein the molecular weight of the compound A is less than 20000.

6. The resin material according to any one of claims 1 to 5, wherein the inorganic filler has an average particle diameter of 1 μm or less.

7. The resin material according to any one of claims 1 to 6, wherein the inorganic filler is silica.

8. The resin material according to any one of claims 1 to 7, wherein the content of the inorganic filler is 50% by weight or more based on 100% by weight of the components other than the solvent in the resin material.

9. The resin material according to any one of claims 1 to 8, comprising a maleimide compound having no skeleton derived from a dimer diamine.

10. The resin material according to any one of claims 1 to 9,

the compound A contains the bismaleimide compound having a skeleton derived from dimer diamine and having a skeleton derived from a diamine compound other than dimer diamine,

the bismaleimide compound having a skeleton derived from dimer diamine and having a skeleton derived from a diamine compound other than dimer diamine includes a1 st bismaleimide compound having a skeleton derived from dimer diamine only at both ends of a main chain and a2 nd bismaleimide compound having a skeleton derived from dimer diamine in a skeleton other than both ends of a main chain and having 2 or more imide skeletons.

11. The resin material according to any one of claims 1 to 10, comprising an epoxy compound and a curing agent,

the curing agent contains a phenol compound, a cyanate ester compound, an acid anhydride, an active ester compound, a carbodiimide compound, and a benzene compound having no skeleton derived from a dimer diamine

At least 1 component of an oxazine compound.

12. The resin material according to any one of claims 1 to 11, comprising a curing accelerator,

the curing accelerator comprises an anionic curing accelerator.

13. The resin material according to claim 12, wherein the anionic curing accelerator is an imidazole compound.

14. The resin material according to claim 12 or 13, wherein the content of the anionic curing accelerator is 20% by weight or more based on 100% by weight of the curing accelerator.

15. The resin material according to any one of claims 1 to 14, which is a resin film.

16. A laminated structure comprising: a lamination object member having a metal layer on a surface thereof, and a resin film laminated on the surface of the metal layer,

the resin film is the resin material according to any one of claims 1 to 15.

17. The laminated structure of claim 16, wherein the material of the metal layer is copper.

18. A multilayer printed wiring board is provided with:

a circuit substrate;

a multilayer insulating layer disposed on a surface of the circuit substrate; and

a metal layer disposed between the plurality of insulating layers,

at least 1 of the plurality of insulating layers is a cured product of the resin material according to any one of claims 1 to 15.

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