JP2020111695A - Resin material and multilayer printed wiring board - Google Patents

Abstract

To provide a resin material capable of lowering the dielectric loss tangent of a cured product and enhancing plating peel strength.SOLUTION: The resin material according to the present invention contains an epoxy compound and a curing agent. The curing agent contains an active ester compound. The ratio of the total number of epoxy groups of the epoxy compound in the resin material to the total number of reactive groups of the curing agent in the resin material is 1.2 or more and 1.8 or less. The total number of active ester groups of the active ester compound in the resin material is 70% or more in 100% of the total number of the reactive groups of the curing agent in the resin material.SELECTED DRAWING: Figure 1

Description

The present invention relates to a resin material containing an epoxy compound. The present invention also relates to a multilayer printed wiring board using the above resin material.

Conventionally, various resin materials have been used to obtain electronic components such as semiconductor devices, laminated boards and printed wiring boards. For example, in a multilayer printed wiring board, a resin material is used to form an insulating layer for insulating the inner layers and to form an insulating layer located on the surface layer portion. Wiring, which is generally metal, is laminated on the surface of the insulating layer. Further, in order to form the insulating layer, a resin film obtained by filmizing 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.

Patent Document 1 below discloses a resin composition containing (A) an epoxy resin, (B) a cyanate ester resin, (C) an active ester curing agent, and (D) a curing accelerator. .. In the example of Patent Document 1, a resin composition in which the total number of epoxy groups of the epoxy resin in the resin composition is smaller than the total number of reactive groups of the curing agent in the resin composition is used.

In addition, Patent Document 2 below discloses an epoxy resin composition containing (A) an epoxy resin, (B) an active ester compound, and (C) an alicyclic structure-containing phenoxy resin. In the example of Patent Document 2, the ratio of the total number of epoxy groups of the epoxy resin in the epoxy resin composition to the total number of reactive groups of the curing agent in the epoxy resin composition is less than 1.15, Alternatively, a resin composition in which the total number of active ester groups is 60% or less in 100% of the total number of reactive groups in the curing agent is used.

JP, 2010-285594, A JP, 2010-111859, A

It is desirable that the cured product of the resin material has a low dielectric loss tangent. However, when an insulating layer is formed by using a resin material that is designed to have a low dielectric loss tangent, the surface roughness after etching may not be sufficiently reduced. If the surface roughness after etching is not sufficiently low, the resin that contributes to the anchor effect will be partially thinned, so the strength of the insulating layer will not be sufficiently high, and the cured product (insulating layer) after etching will be However, the plating peel strength with the metal layer laminated on the surface of the insulating layer by the plating treatment may not be sufficiently high.

For this reason, it may be difficult to sufficiently lower the dielectric loss tangent of the cured product and sufficiently enhance the plating peel strength with the conventional resin materials described in Patent Documents 1 and 2.

Further, in recent years, in order to cope with an increase in the amount of information transmitted and to achieve high-speed communication, printed wiring boards and the like have become multi-layered, large-sized, and have fine wiring. With the conventional resin materials described in Patent Documents 1 and 2, it is difficult to sufficiently lower the dielectric loss tangent of the cured product and to sufficiently enhance the plating peel strength. It may not be suitable for use as a material for an insulating layer of a printed wiring board that has been made into a thin film.

An object of the present invention is to provide a resin material which can lower the dielectric loss tangent of a cured product and can enhance the plating peel strength. Another object of the present invention is to provide a multilayer printed wiring board using the above resin material.

According to a broad aspect of the present invention, an epoxy compound and a curing agent, wherein the curing agent contains an active ester compound, the total number of epoxy groups of the epoxy compound in the resin material, The ratio of the reactive group of the curing agent to the total number of reactive groups is 1.2 or more and 1.8 or less, and 100% of the total number of reactive groups of the curing agent in the resin material accounts for 100% of the active ester compound in the resin material. Provided is a resin material having a total number of active ester groups of 70% or more.

In a specific aspect of the resin material according to the present invention, the epoxy compound contains an epoxy compound having 3 or more epoxy groups, and the epoxy compound having 3 or more epoxy groups is contained in 100% by weight of the epoxy compound. The amount is 3% by weight or more.

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

In one specific aspect of the resin material according to the present invention, the resin material contains an inorganic filler, and the content of the inorganic filler is 60% by weight or more in 100% by weight of the component excluding the solvent in the resin material. is there.

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

The resin material according to the present invention is suitably used for forming an insulating layer in a multilayer printed wiring board.

According to a wide aspect of the present invention, a circuit board, a plurality of insulating layers arranged on a surface of the circuit board, and a metal layer arranged between the plurality of insulating layers, the plurality of insulating layers Provided is a multilayer printed wiring board, in which at least one layer is a cured product of the above resin material.

The resin material according to the present invention contains an epoxy compound and a curing agent, and the curing agent contains an active ester compound. In the resin material according to the present invention, the ratio of the total number of epoxy groups of the epoxy compound in the resin material to the total number of reactive groups of the curing agent in the resin material is 1.2 or more and 1.8 or less. The total number of active ester groups of the active ester compound in the resin material is 70% or more in 100% of the total number of reactive groups of the curing agent in the resin material. Since the resin material according to the present invention is provided with the above configuration, the dielectric loss tangent of the cured product can be lowered and the plating peel strength can be increased.

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

Hereinafter, the present invention will be described in detail.

The resin material according to the present invention contains an epoxy compound and a curing agent, and the curing agent contains an active ester compound. In the resin material according to the present invention, the ratio of the total number of epoxy groups of the epoxy compound in the resin material to the total number of reactive groups of the curing agent in the resin material is 1.2 or more and 1.8 or less. The total number of active ester groups of the active ester compound in the resin material is 70% or more in 100% of the total number of reactive groups of the curing agent in the resin material.

The reactive group means a functional group capable of reacting with an epoxy group.

Since the resin material according to the present invention is provided with the above configuration, the dielectric loss tangent of the cured product can be lowered and the plating peel strength can be increased. INDUSTRIAL APPLICABILITY The resin material according to the present invention can be suitably used as a material for an insulating layer of a printed wiring board having a multilayer structure, a large size, and fine wiring.

In the resin material according to the present invention, the ratio of the total number of epoxy groups of the epoxy compound in the resin material to the total number of reactive groups of the curing agent in the resin material (the total number of epoxy groups of the epoxy compound /Total number of reactive groups of curing agent) (hereinafter sometimes referred to as ratio (X)) is 1.2 or more and 1.8 or less. Therefore, in the resin material according to the present invention, the self-polymerization reaction of the epoxy compound effectively proceeds in addition to the copolymerization reaction of the epoxy compound and the curing agent. Since no hydroxyl group is generated during the self-polymerization reaction of the epoxy compound, the dielectric loss tangent of the obtained cured product can be lowered. Further, with a cured product containing a self-polymerized product of an epoxy compound, etching can be favorably performed, and as a result, the plating peel strength can be increased. If the ratio (X) is less than 1.2, the plating peel strength may decrease. If the ratio (X) exceeds 1.8, the dielectric loss tangent may not be sufficiently lowered.

From the viewpoint of more effectively exerting the effect of the present invention, the ratio (X) is preferably 1.25 or more, preferably 1.7 or less, and more preferably 1.6 or less.

In the resin material according to the present invention, the total number of active ester groups of the active ester compound in the resin material is 100% of the total number of reactive groups of the curing agent in the resin material (hereinafter, the total number (Y )) is 70% or more. In the resin material according to the present invention, the total number of active ester groups of the active ester compound in the resin composition is relatively large. Therefore, the dielectric loss tangent of the cured product can be further reduced, and the plating peel strength can be further enhanced. When the total number (Y) is less than 70%, it is difficult to sufficiently lower the dielectric loss tangent and further enhance the plating peel strength. For example, a curing agent (second curing agent) such as a phenol compound and a cyanate compound is contained as the curing agent, and the total number of reactive groups of the curing agent in the resin material is 100%, and In the resin material in which the total number of reactive groups of the second curing agent exceeds 30%, the copolymerization reaction between the second curing agent and the epoxy compound proceeds rapidly. For this reason, the self-polymerization reaction of the epoxy compound is less likely to proceed, and the dielectric loss tangent may be increased or the plating peel strength may be decreased.

From the viewpoint of more effectively exerting the effects of the present invention, the total number (Y) is preferably 73% or more, more preferably 75% or more. The upper limit of the total number (Y) is not particularly limited. The total number (Y) may be 100% (total number) or 90% or less.

The above ratio (total number of epoxy groups of epoxy compound/total number of reactive groups of curing agent) (ratio (X)) can be determined as follows.

For example, the resin material contains B% by weight of an epoxy compound having an epoxy equivalent of Ag/eq in 100% by weight of the resin material, and D% by weight of a curing agent having a reactive group equivalent of Cg/eq. When it is included, the ratio (X) (the total number of epoxy groups of the epoxy compound/the total number of reactive groups of the curing agent) is calculated by the following formula (11).

Ratio (X)=[(B/100)/A]/[(D/100)/C] (11)

In addition, the resin material may include two kinds of epoxy compounds. The epoxy equivalent of the first type epoxy compound is A1 g/eq, and the content of the first type epoxy compound in 100% by weight of the resin material is B1% by weight. The epoxy equivalent of the second type epoxy compound is A2 g/eq, and the content of the second type epoxy compound in 100% by weight of the resin material is B2% by weight. In this case, “(B/100)/A” in the above formula (11) becomes “(B1/100)/A1+(B2/100)/A2”.

The resin material may contain three kinds of epoxy compounds. The epoxy equivalent of the first type epoxy compound is A1 g/eq, and the content of the first type epoxy compound in 100% by weight of the resin material is B1% by weight. The epoxy equivalent of the second type epoxy compound is A2 g/eq, and the content of the second type epoxy compound in 100% by weight of the resin material is B2% by weight. The epoxy equivalent of the third type epoxy compound is A3 g/eq, and the content of the third type epoxy compound in 100% by weight of the resin material is B3% by weight. In this case, “(B/100)/A” in the above formula (11) becomes “(B1/100)/A1+(B2/100)/A2+(B3/100)/A3”.

Even when the resin material contains four or more kinds of epoxy compounds, the value of “(B/100)/A” is similarly obtained from the epoxy equivalent and the content of each epoxy compound.

In addition, the resin material may include two types of curing agents. The equivalent amount of the reactive group of the first type curing agent is C1 g/eq, and the content of the first type curing agent in 100% by weight of the resin material is D1% by weight. The reactive group equivalent of the second type curing agent is C2 g/eq, and the content of the second type curing agent in 100% by weight of the resin material is D2% by weight. In this case, “(D/100)/C” in the above formula (11) becomes “(D1/100)/C1+(D2/100)/C2”. The first type curing agent may be an active ester compound and the second type curing agent may be an active ester compound. The first type curing agent may be an active ester compound, and the second type curing agent may be a curing agent other than the active ester compound.

The resin material may include three kinds of curing agents. The equivalent amount of the reactive group of the first type curing agent is C1 g/eq, and the content of the first type curing agent in 100% by weight of the resin material is D1% by weight. The reactive group equivalent of the second type curing agent is C2 g/eq, and the content of the second type curing agent in 100% by weight of the resin material is D2% by weight. The equivalent of the reactive group of the third type curing agent is C3 g/eq, and the content of the third type curing agent in 100% by weight of the resin material is D3% by weight. In this case, “(D/100)/C” in the above formula (11) becomes “(D1/100)/C1+(D2/100)/C2+(D3/100)/C3”.

When the resin material contains four or more types of curing agents, as in the case where the resin material contains two or three types of curing agents, from the equivalent and content of the reactive group of each curing agent, The value of “(D/100)/C” is obtained.

The total number (total number (Y)) of active ester groups of the active ester compound in the resin material in 100% of the total number of reactive groups of the curing agent in the resin material is calculated as follows. be able to.

When all of the curing agents in the resin material are active ester compounds, the active ester of the active ester compound in the resin material in 100% of the total number of reactive groups of the curing agent in the resin material The total number of groups is 100% (total number).

The resin material may include an active ester compound and a curing agent other than the active ester compound. In 100% by weight of the above resin material, an active ester compound having an active ester group equivalent of Eg/eq is included in an amount of F% by weight, and a curing agent other than the active ester compound having a reactive group equivalent of Gg/eq is used. When H weight% is included, the above total number (Y) is obtained by the following formula (12).

Total number (Y)=[(F/100)/E]/[(F/100)/E+(H/100)/G]*100...(12)

When the resin material contains two or more kinds of active ester compounds, from the equivalent and content of the active ester group of each active ester compound, as in the above description of “(D/100)/C”, The values of “(F/100)/E” and “(F/100)/E+(H/100)/G” are obtained.

When the resin material contains a curing agent other than two or more kinds of active ester compounds, the reactive group of the curing agent other than each active ester compound is the same as the above description of “(D/100)/C”. The value of “(F/100)/E+(H/100)/G” can be obtained from the equivalent weight and the content.

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

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

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

[Epoxy compound]
The resin material contains an epoxy compound. As the epoxy compound, a conventionally known epoxy compound can be used. The epoxy compound is an organic compound having at least one epoxy group. As for the said epoxy compound, only 1 type may be used and 2 or more types may be used together.

Examples of the epoxy compound include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, phenol novolac type epoxy compounds, biphenyl type epoxy compounds, biphenyl 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, adamantane skeleton epoxy compounds, tricyclodecane skeleton epoxy compounds, naphthylene ether type Examples thereof include epoxy compounds and epoxy compounds having a triazine nucleus in the skeleton.

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

The epoxy equivalent of the epoxy compound is preferably 120 g/eq or more, more preferably 130 g/eq or more, preferably 900 g/eq or less, more preferably 800 g/eq or less. When the epoxy equivalent is not less than the lower limit and not more than the upper limit, the dielectric loss tangent can be further lowered, and the plating peel strength can be further enhanced.

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

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

The viscosity of the epoxy compound can be measured using, for example, a dynamic viscoelasticity measuring device ("VAR-100" manufactured by Rheological Instruments).

The molecular weight of the epoxy compound is more preferably 1000 or less. In this case, even if the content of the inorganic filler is 50% by weight or more in 100% by weight of the component excluding the solvent in the resin material, a resin material having high fluidity at the time of forming the insulating layer can be obtained. Therefore, when the uncured resin material or the B-staged 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 that can be calculated from the structural formula when the epoxy compound is not a polymer and when the structural formula of the epoxy compound can be specified. Moreover, when the said epoxy compound is a polymer, it means a weight average molecular weight.

The epoxy compound preferably contains an epoxy compound having three or more epoxy groups. In this case, the self-polymerization reaction of the epoxy compound can be efficiently progressed, and as a result, the dielectric loss tangent can be further lowered and the plating peel strength can be further enhanced.

When the epoxy compound contains an epoxy compound having 3 or more epoxy groups, the content of the epoxy compound having 3 or more epoxy groups is preferably 3% by weight or more, and more preferably 100% by weight or more, based on 100% by weight of the epoxy compound. It is preferably 4% by weight or more, more preferably 5% by weight or more, preferably 80% by weight or less, more preferably 70% by weight or less. When the content of the epoxy compound having three or more epoxy groups is not less than the lower limit and not more than the upper limit, the dielectric loss tangent can be further reduced and the plating peel strength can be further enhanced.

[Curing agent]
The resin material contains a curing agent. As for the said hardening|curing agent, only 1 type may be used and 2 or more types may be used together.

<Active ester compound>
The resin material contains an active ester compound as a curing agent. As for the said active ester compound, only 1 type may be used and 2 or more types may be used together.

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

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

In the above formula (1), the combination of X1 and X2 is a combination of a benzene ring which may have a substituent and a benzene ring which may have a substituent, and a combination of which has a substituent. And a naphthalene ring which may have a substituent. Further, in the above formula (1), examples of the combination of X1 and X2 include a combination of a naphthalene ring which may have a substituent and a naphthalene ring which may have a substituent.

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

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

The active ester group equivalent of the active ester compound is preferably 120 g/eq or more, more preferably 130 g/eq or more, preferably 900 g/eq or less, more preferably 800 g/eq or less. When the active ester group equivalent is not less than the above lower limit and not more than the above upper limit, the dielectric loss tangent can be further lowered, and the plating peel strength can be further raised.

<Second curing agent>
The resin material may include a curing agent (second curing agent) other than the active ester compound. The resin material may not include the second curing agent. As for the said 2nd hardening|curing agent, only 1 type may be used and 2 or more types may be used together.

The second curing agent preferably has a functional group (reactive group) capable of reacting with the epoxy group of the epoxy compound. Examples of the reactive group include a group having a carbon-carbon unsaturated bond such as a vinyl group, a hydroxyl group, a glycidyl group, an isocyanate group, an amino group, a carboxyl group and an acid anhydride group. When the resin material contains the second curing agent, the total number of reactive groups in the second curing agent is less than 30% in 100% of the total number of reactive groups in the curing agent.

Examples of the second curing agent include cyanate compound (cyanate curing agent), amine compound (amine curing agent), thiol compound (thiol curing agent), phosphine compound, dicyandiamide, phenol compound (phenol curing agent), acid anhydride, Examples thereof include a carbodiimide compound (carbodiimide curing agent) and a benzoxazine compound (benzoxazine curing agent).

From the viewpoint of further lowering the dielectric loss tangent and further improving the thermal dimensional stability, the second curing agent is at least one of a phenol compound, a cyanate compound, an acid anhydride, a carbodiimide compound, and a benzoxazine compound. It is preferred to include seed components. That is, the resin material preferably contains a curing agent containing at least one component selected from the group consisting of a phenol compound, a cyanate compound, an acid anhydride, a carbodiimide compound, and a benzoxazine compound.

In the present specification, "at least one component of a phenol compound, a cyanate compound, an acid anhydride, a carbodiimide compound, and a benzoxazine compound" may be referred to as "component X".

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

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

Examples of commercially available phenol compounds include novolac type phenol (“TD-2091” manufactured by DIC), biphenyl novolac type phenol (“MEH-7851” manufactured by Meiwa Kasei Co., Ltd.), and aralkyl type phenol compound (“MEH manufactured by Meiwa Kasei Co., Ltd.” -7800"), and a phenol having an aminotriazine skeleton ("LA-1356" and "LA-3018-50P" manufactured by DIC) and the like.

The cyanate compound may be a cyanate ester compound (cyanate ester curing agent).

Examples of the cyanate ester compound include novolac type cyanate ester resin, bisphenol type cyanate ester resin, and prepolymers obtained by partially trimming these. Examples of the novolac type cyanate ester resin include a phenol novolac type cyanate ester resin and an alkylphenol type cyanate ester resin. Examples of the bisphenol type cyanate ester resin include a bisphenol A type cyanate ester resin, a bisphenol E type cyanate ester resin, and a tetramethylbisphenol F type cyanate ester resin.

As commercial products of the above cyanate ester compound, a phenol novolac type cyanate ester resin (“PT-30” and “PT-60” manufactured by Lonza Japan Co., Ltd.), and a prepolymer (Lonza Japan produced by trimerizing a bisphenol type cyanate ester resin are used. "BA-230S", "BA-3000S", "BTP-1000S", and "BTP-6020S") manufactured by the company are listed.

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

Examples of commercially available products of the acid anhydride include "Rikacid TDA-100" manufactured by Shin Nippon Rika Co., Ltd. and the like.

The carbodiimide compound has a structural unit represented by the following formula (2). In the following formula (2), the right end and the left end are binding sites with other groups.

In the above formula (2), X is an alkylene group, a group in which a substituent is bonded to an alkylene group, a cycloalkylene group, a group in which a substituent is bonded to a cycloalkylene group, an arylene group, or a substituent is bonded to an arylene group. Represents a 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 one preferable form, at least one X is an alkylene group, a group having a substituent bonded to an alkylene group, a cycloalkylene group, or a group having a substituent bonded to a cycloalkylene group.

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

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

As a commercial item of the said benzoxazine compound, "Pd type" by Shikoku Chemicals Co., Ltd. etc. are mentioned.

[Inorganic filler]
The resin material preferably contains an inorganic filler. The use of the inorganic filler can further lower the dielectric loss tangent of the cured product. In addition, the use of the above-mentioned inorganic filler further reduces the dimensional change of the cured product due to heat. As for the said inorganic filler, only 1 type may be used and 2 or more types may be used together.

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

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

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

The average particle size of the inorganic filler is preferably 50 nm or more, more preferably 100 nm or more, still more preferably 500 nm or more, preferably 5 μm or less, more preferably 3 μm or less, still more preferably 1 μm or less. When the average particle diameter of the inorganic filler is not less than the above lower limit and not more than the above upper limit, it is possible to reduce the surface roughness after etching and to increase the plating peel strength, and also between the insulating layer and the metal layer. The adhesiveness can be further enhanced.

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

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

The inorganic filler is preferably surface-treated, more preferably a surface-treated product with a coupling agent, and further preferably a surface-treated product with a silane coupling agent. By surface-treating the inorganic filler, the surface roughness of the surface of the roughened cured product is further reduced, and the adhesive strength between the cured product and the metal layer is further enhanced. Further, since the inorganic filler is surface-treated, it is possible to form finer wiring on the surface of the cured product, and further improve the inter-wiring insulation reliability and interlayer insulation reliability in the cured product. Can be granted.

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

In 100% by weight of the component excluding the solvent in the resin material, the content of the inorganic filler is preferably 50% by weight or more, more preferably 60% by weight or more, further preferably 65% by weight or more, particularly preferably 68% by weight. % Or more, preferably 90% by weight or less, more preferably 85% by weight or less, further preferably 80% by weight or less, and particularly preferably 78% by weight or less. When the content of the inorganic filler is at least the above lower limit, the dielectric loss tangent becomes effectively low. When the content of the inorganic filler is less than or equal to the above upper limit, the thermal dimensional stability can be improved and the warp of the cured product can be effectively suppressed. When the content of the inorganic filler is not less than the above lower limit and not more than the above upper limit, it is possible to further reduce the surface roughness of the surface of the cured product, and to form finer wiring on the surface of the cured product. You can Furthermore, if the content of this inorganic filler is used, it is possible to reduce the coefficient of thermal expansion of the cured product and at the same time improve the smear removability.

[Curing accelerator]
The resin material preferably contains a curing accelerator. By using the above curing accelerator, the curing speed is further increased. By rapidly curing the resin material, the crosslinked structure in the cured product becomes uniform, the number of unreacted functional groups decreases, and as a result, the crosslink density increases. The curing accelerator is not particularly limited, and conventionally known curing accelerators can be used. As for the said hardening accelerator, only 1 type may be used and 2 or more types may be used together.

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

Examples of the imidazole compound include 2-undecylimidazole, 2-heptadecylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl- 2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-un Decylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2' -Methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino- 6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s -Triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-dihydroxymethylimidazole Etc.

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

Examples of the phosphorus compound include triphenylphosphine compounds.

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

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

From the viewpoint of further suppressing the curing temperature, promoting the self-polymerization of the epoxy group, and effectively suppressing the warp of the cured product, the curing accelerator preferably contains the anionic curing accelerator. From the viewpoints of further lowering the curing temperature and more effectively suppressing the warp of the cured product, the curing accelerator preferably contains the imidazole compound, more preferably the imidazole compound. Moreover, when the said hardening accelerator is the said imidazole compound, the self-polymerization reaction of the said epoxy compound can be advanced efficiently.

From the viewpoint of further suppressing the curing temperature, promoting the self-polymerization of the epoxy group, and effectively suppressing the warp of the cured product, the content of the anionic curing accelerator in 100% by weight of the curing accelerator is It is preferably 20% by weight or more, more preferably 50% by weight or more, further preferably 70% by weight or more, and most preferably 100% by weight (total amount). Therefore, the curing accelerator is most preferably the anionic curing accelerator.

In 100% by weight of the components excluding the inorganic filler and the solvent in the resin material, the content of the curing accelerator is preferably 0.5% by weight or more, more preferably 0.8% by weight or more, further preferably 1% by weight. % Or more, preferably 5% by weight or less, more preferably 3% by weight or less. When the content of the curing accelerator is not less than the lower limit and not more than the upper limit, the resin material can be efficiently cured. When the content of the curing accelerator is in a more preferable range, the storage stability of the resin material can be increased and a better cured product can be obtained. In addition, the content of the curing accelerator means the total content of all the curing accelerators contained in the resin material.

[Thermoplastic resin]
The resin material preferably contains a thermoplastic resin. Examples of the thermoplastic resin include polyvinyl acetal resin, polyimide resin, and phenoxy resin. As for the said thermoplastic resin, only 1 type may be used and 2 or more types may be used together.

The thermoplastic resin is preferably a phenoxy resin from the viewpoint of effectively lowering the dielectric loss tangent and effectively improving the adhesion of the metal wiring regardless of the curing environment. By using the phenoxy resin, it is possible to suppress the deterioration of the embedding property of the resin film in the holes or the unevenness of the circuit board and the nonuniformity of the inorganic filler. Further, by using the phenoxy resin, the melt viscosity can be adjusted, so that the dispersibility of the inorganic filler is improved, and it becomes difficult for the resin composition or the B-staged product to wet and spread in an unintended region during the curing process.

The phenoxy resin contained in the resin material is not particularly limited. A conventionally known phenoxy resin can be used as the phenoxy resin. The phenoxy resin may be used alone or in combination of two or more.

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

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

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

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

Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfone tetra Carboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenyl ether Tetracarboxylic acid dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic acid dianhydride, 3,3',4,4'-Tetraphenylsilane tetracarboxylic acid 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)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic acid dianhydride, 3,3 ',4,4'-Biphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenyl Phthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4′-diphenylether dianhydride, and bis(triphenylphthalic acid)-4,4′-diphenylmethane dianhydride.

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

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

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

The weight average molecular weights of the thermoplastic resin, the polyimide resin, and the phenoxy resin indicate the weight average molecular weight 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. Content of the thermoplastic resin in 100% by weight of the component excluding the inorganic filler and the solvent in the resin material (when the thermoplastic resin is a polyimide resin or a phenoxy resin, the content of the polyimide resin or the phenoxy resin ) Is preferably 1% by weight or more, more preferably 2% by weight or more, preferably 30% by weight or less, more preferably 20% by weight or less. When the content of the thermoplastic resin is not less than the above lower limit and not more than the above upper limit, the embeddability of the resin material into the holes or the irregularities of the circuit board becomes good. When the content of the thermoplastic resin is at least the above lower limit, the formation of the resin film becomes easier, and a better insulating layer can be obtained. When the content of the thermoplastic resin is at most the above upper limit, the coefficient of thermal expansion of the cured product will be even lower. When the content of the thermoplastic resin is at most the above upper limit, the surface roughness of the surface of the cured product will be further reduced, and the adhesive strength between the cured product and the metal layer will be even higher.

[solvent]
The resin material does not include or includes a solvent. By using the above solvent, the viscosity of the resin material can be controlled within a suitable range, and the coating property of the resin material can be improved. Also, the solvent may be used to obtain a slurry containing the inorganic filler. As for the said solvent, only 1 type may be used and 2 or more types may be used together.

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

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

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

[Other ingredients]
For the purpose of improving impact resistance, heat resistance, resin compatibility, workability, etc., the above resin materials include leveling agents, flame retardants, coupling agents, coloring agents, antioxidants, ultraviolet deterioration inhibitors, and defoaming agents. It may contain agents, thickeners, thixotropic agents, 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.

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

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

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

The film-shaped resin composition that can be obtained by the drying process 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 can be further advanced.

The resin film may not be a prepreg. When the resin film is not a prepreg, migration does not occur along the glass cloth or the like. Further, when laminating or pre-curing the resin film, unevenness due to the glass cloth does not occur on the surface.

The resin film can be used in the form of a laminated film including a metal foil or a base film and a resin film laminated on the surface of the metal foil or the base. The metal foil is preferably copper foil.

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

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

(Semiconductor devices, printed wiring boards, copper clad laminated boards and multilayer printed wiring boards)
The resin material is preferably used to form a mold resin for embedding a semiconductor chip in a semiconductor device.

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

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

A member to be laminated having a metal layer on one surface or both surfaces thereof can be laminated on the resin film. It is possible to suitably obtain a laminated structure that includes a member to be laminated having a metal layer on the surface and a resin film laminated on the surface of the metal layer, and the resin film is the resin material described above. The method for laminating the resin film and the lamination target member having the metal layer on the surface thereof is not particularly limited, and a known method can be used. For example, the above-mentioned resin film can be laminated on a lamination target member having a metal layer on its surface while heating or applying pressure without heating using a device such as a parallel plate press or a roll laminator.

The material of the metal layer is preferably copper.

The lamination target member having the metal layer on its surface may be a metal foil such as a copper foil.

The resin material is preferably used to obtain a copper clad laminate. An example of the copper-clad laminate is a copper-clad laminate 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 μm to 50 μm. Further, in order to enhance the adhesive strength between the cured product of the resin material and the copper foil, the copper foil preferably has fine irregularities on the surface. The method of forming the unevenness is not particularly limited. Examples of the method of forming the unevenness include a method of forming by using a known chemical solution.

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

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

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.

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

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

As another example of the multilayer board, a circuit board, an insulating layer laminated on the surface of the circuit board, and an insulating layer laminated on the surface opposite to the surface on which the circuit board is laminated. And a copper foil. It is preferable that the insulating layer is formed by curing the resin film using a copper clad laminate including a copper foil and a resin film laminated on one surface of the copper foil. Furthermore, it is preferable that the copper foil has been subjected to an etching treatment and is a copper circuit.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The following materials were prepared.

(Epoxy compound)
Biphenyl type epoxy compound ("NC-3000" manufactured by Nippon Kayaku Co., epoxy equivalent 275 g/eq, solid at 25°C, average number of epoxy groups exceeds 2.2 (including epoxy compound having 3 or more epoxy groups)).
Bisphenol A type epoxy compound (“RE-410S” manufactured by Nippon Kayaku Co., epoxy equivalent 185 g/eq, solid at 25° C., average number of epoxy groups less than 2.2)

(Curing agent)
Liquid containing active ester compound ("EXB-9416-70BK" manufactured by DIC, solid content 70% by weight)
Phenol compound-containing liquid ("LA3018-50P" manufactured by DIC, solid content 50% by weight)

(Curing accelerator)
2-Phenyl-4-methylimidazole ("2P4MZ" manufactured by Shikoku Chemicals, an anionic curing accelerator)

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

(Example 1)
11.3 parts by weight of a biphenyl type epoxy compound, 16.2 parts by weight of an active ester compound-containing liquid, 0.5 parts by weight of 2-phenyl-4-methylimidazole, and 72.0 parts by weight of a silica-containing slurry are mixed. Then, the mixture was stirred at room temperature until a uniform solution was obtained to obtain a resin material (resin composition).

Production of resin film:
After coating the obtained resin material on the release-treated surface of a release-treated polyethylene terephthalate (PET) film (“XG284” manufactured by Toray Industries, Inc., thickness 25 μm) using an applicator, a gear oven at 100° C. It was dried inside for 2 minutes and 30 seconds to evaporate the solvent. Thus, a laminated film (laminated film of PET film and resin film) in which a resin film (B stage film) having a thickness of 40 μm was laminated on the PET film was obtained.

(Examples 2 to 16 and Comparative Examples 1 to 5)
A resin composition and a resin film were produced in the same manner as in Example 1 except that the types and amounts of the compounding ingredients were changed as shown in Tables 1 to 3 below.

(Evaluation)
(1) Dielectric loss tangent The obtained resin film was cut into a size having a width of 2 mm and a length of 80 mm and five sheets were stacked to obtain a laminate having a thickness of 200 μm. The obtained laminated body was heated at 190° C. for 90 minutes to obtain a cured product. The obtained cured product is subjected to a cavity resonance method at room temperature (23° C.) using “Cavity resonance perturbation method dielectric constant measuring device CP521” manufactured by Kanto Electronics Application Development Co., Ltd. and “Network Analyzer N5224A PNA” manufactured by Keysight Technology Co., Ltd. Then, the dielectric loss tangent was measured at a frequency of 1.0 GHz.

[Judgment criteria of dielectric loss tangent]
◯: Dielectric loss tangent is less than 0.0040 Δ: Dielectric loss tangent is 0.0040 or more and less than 0.0045 ×: Dielectric loss tangent is 0.0045 or more

(2) Plating peel strength Laminating process and semi-curing treatment:
A 100 mm square double-sided copper clad laminate (CCL substrate) ("E679FG" manufactured by Hitachi Chemical Co., Ltd.) was prepared. Both surfaces of the copper foil surface of this double-sided copper-clad laminate were immersed in "Cz8101" manufactured by MEC Co., Ltd. to roughen the surface of the copper foil. Using "Batch type vacuum laminator MVLP-500-IIA" manufactured by Meiki Seisakusho Co., Ltd., the resin film (B stage film) side of the laminated film is placed on the copper clad laminated plate on both sides of the roughened copper clad laminated plate. And laminated to obtain a laminated structure. The laminating conditions were such that the pressure was reduced for 30 seconds so that the atmospheric pressure was 13 hPa or less, and then the layers were laminated for 30 seconds at 100° C. and a pressure of 0.7 MPa, and further pressed at a pressing pressure of 0.8 MPa and a pressing temperature of 100° C. for 60 seconds. Then, with the PET film attached, the resin film in the laminated structure was heated at 100° C. for 30 minutes and further heated at 180° C. for 30 minutes to semi-cure the resin film. Then, the PET film was peeled off to obtain a laminate in which the semi-cured resin film was laminated on the CCL substrate.

Roughening treatment:
(A) Swelling treatment:
The obtained laminated body was put into a swelling liquid (“Swelling Dip Securigant P” manufactured by Atotech Japan Co., Ltd.) at 60° C. and shaken for 10 minutes. Then, it was washed with pure water.

(B) Permanganate treatment (roughening treatment and desmear treatment):
The laminated body after the swelling treatment was put into a roughened aqueous solution of potassium permanganate (“Concentrate Compact CP” manufactured by Atotech Japan Co., Ltd.) at 80° C. and shaken for 30 minutes. Next, after treatment for 2 minutes using a cleaning liquid (“Reduction Securigant P” manufactured by Atotech Japan) at 25° C., cleaning was performed with pure water and roughening treatment was performed.

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

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

Electrolytic plating process:
Next, the electroless-plated cured product was subjected to electrolytic plating until the plating thickness became 25 μm. Copper sulfate solution as electrolytic copper plating (“copper sulfate pentahydrate” manufactured by Wako Pure Chemical Industries, Ltd., “sulfuric acid” manufactured by Wako Pure Chemical Industries, “Basic Leveler Caparaside HL” manufactured by Atotech Japan, “Atotech Japan” Electrolytic plating was carried out by applying a current of 0.6 A/cm ^{2 to} a plating thickness of about 25 μm using a corrector Kaparaside GS”). After the copper plating treatment, the cured product was heated at 200° C. for 60 minutes to further cure the cured product. Thus, a cured product having the copper plating layer laminated on the upper surface was obtained.

Plating peel strength measurement:
Six strip-shaped cuts having a width of 10 mm were made at 5 mm intervals on the surface of the copper-plated layer of the cured product having the obtained copper-plated layer laminated on the upper surface. A cured product with a copper plating layer laminated on the upper surface was set in a 90° peeling tester (“TE-3001” manufactured by Tester Sangyo Co., Ltd.), and the end of the notched copper plating layer was picked up with a gripping tool, and the copper was cut. The plating layer was peeled by 20 mm and the peel strength (plating peel strength) was measured. The peel strength (plating peel strength) was measured for each of the six cut portions, and the average value of the plating peel strength was determined. The plating peel strength was judged according to the following criteria.

[Criteria for plating peel strength]
◯: The average value of the plating peel strength is 0.5 kgf/cm or more Δ: The average value of the plating peel strength is 0.4 kgf/cm or more and less than 0.5 kgf/cm ×: The average value of the plating peel strength is 0.4 kgf/cm Less than

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

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

The compositions and results are shown in Tables 1-3 below.

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

Claims (7)

Including an epoxy compound and a curing agent,
The curing agent contains an active ester compound,
The ratio of the total number of epoxy groups of the epoxy compound in the resin material to the total number of reactive groups of the curing agent in the resin material is 1.2 or more and 1.8 or less,
A resin material in which the total number of active ester groups of the active ester compound in the resin material is 70% or more in 100% of the total number of reactive groups of the curing agent in the resin material. The epoxy compound includes an epoxy compound having three or more epoxy groups,
The resin material according to claim 1, wherein the content of the epoxy compound having three or more epoxy groups is 3% by weight or more based on 100% by weight of the epoxy compound. Including a curing accelerator,
The resin material according to claim 1, wherein the curing accelerator is an imidazole compound. Including inorganic filler,
The resin material according to any one of claims 1 to 3, wherein the content of the inorganic filler is 60% by weight or more based on 100% by weight of the component excluding the solvent in the resin material. The resin material according to any one of claims 1 to 4, which is a resin film. The resin material according to claim 1, which is used for forming an insulating layer in a multilayer printed wiring board. Circuit board,
A plurality of insulating layers disposed on the surface of the circuit board,
A metal layer disposed between the plurality of insulating layers,
A multilayer printed wiring board, wherein at least one layer of the plurality of insulating layers is a cured product of the resin material according to any one of claims 1 to 6.

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