JP2024009109A - Resin material and multilayer printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin material which can reduce a dielectric loss tangent, and can suppress generation of delamination.

SOLUTION: A resin material contains an epoxy compound, an inorganic filler, a curing agent, and a silane coupling agent having a triazine skeleton, wherein a specific surface area of the inorganic filler is 1 m²/g or more and 50 m²/g or less.

SELECTED DRAWING: Figure 1

COPYRIGHT: (C)2024,JPO&INPIT

Description

The present invention relates to a resin material containing an epoxy compound, an inorganic filler, and a curing agent. 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, laminates, and printed wiring boards. For example, in a multilayer printed wiring board, a resin material is used to form an insulating layer for insulating between internal layers, and to form an insulating layer located on a surface layer. 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 may be used as the resin material. The above-mentioned resin materials are used as insulating materials for multilayer printed wiring boards including build-up films (for example, Patent Document 1).

WO2009/28493A1

Insulating layers formed on multilayer printed wiring boards and the like are required to have a low dielectric loss tangent. In some cases, an inorganic filler is added to the resin material for the purpose of lowering the dielectric loss tangent. However, the interface between the inorganic filler and the resin easily absorbs water, and if the amount of the inorganic filler is large, delamination occurs between the insulating layer formed of the resin material and the metal layer of the circuit, etc. There are things to do.

Further, during the reflow process, the insulating layer and the metal layer are exposed to high temperatures (for example, 260° C. or higher), so delamination is likely to occur. Furthermore, if the insulating layer absorbs moisture or generates gas due to exposure to high temperatures, delamination is likely to occur.

With conventional epoxy resin compositions such as those described in Patent Document 1, it is difficult to lower the dielectric loss tangent and suppress the occurrence of delamination.

An object of the present invention is to provide a resin material that can lower the dielectric loss tangent and suppress the occurrence of delamination. 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, the inorganic filler includes an epoxy compound, an inorganic filler, a curing agent, and a silane coupling agent having a triazine skeleton, and the inorganic filler has a specific surface area of 1 m ² /g or more and 50 m ² /g or less is provided.

In a particular aspect of the resin material according to the present invention, the silane coupling agent is a silane coupling agent having a diaminotriazine skeleton.

In a particular aspect of the resin material according to the present invention, the curing agent includes an active ester compound, a cyanate compound, a benzoxazine compound, a carbodiimide compound, or a maleimide compound.

In a particular aspect of the resin material according to the present invention, the content of the silane coupling agent is 0.1% by weight or more and 3% by weight based on 100% by weight of the components excluding the inorganic filler and the solvent in the resin material. It is as follows.

In a particular aspect of the resin material according to the present invention, the content of the inorganic filler is 30% by weight or more based on 100% by weight of the components excluding the solvent in the resin material.

In a particular aspect of the resin material according to the present invention, the resin material is a thermosetting material.

In a particular 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 broad aspect of the present invention, the invention includes a circuit board, a plurality of insulating layers disposed on a surface of the circuit board, and a metal layer disposed between the plurality of insulating layers. A multilayer printed wiring board is provided, in which at least one layer is a cured product of the resin material described above.

The resin material according to the present invention includes an epoxy compound, an inorganic filler, a curing agent, and a silane coupling agent having a triazine skeleton, and the inorganic filler has a specific surface area of 1 m ² /g or more and 50 m ² /g. g or less, the dielectric loss tangent can be lowered and the occurrence of delamination can be suppressed.

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

The present invention will be explained in detail below.

The resin material according to the present invention includes an epoxy compound, an inorganic filler, a curing agent, and a silane coupling agent having a triazine skeleton, and the inorganic filler has a specific surface area of 1 m ² /g or more and 50 m ² /g. g or less.

In the present invention, since the above configuration is provided, the dielectric loss tangent can be lowered, and the occurrence of delamination can be suppressed.

With conventional resin materials, it is difficult to lower the dielectric loss tangent and suppress the occurrence of delamination. In particular, even if it is possible to suppress the occurrence of delamination when the amount of inorganic filler blended is small, it is difficult to suppress the occurrence of delamination when the amount of inorganic filler blended is large. . In contrast, in the present invention, the occurrence of delamination can be suppressed even if the amount of inorganic filler blended is large.

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

The resin material according to the present invention is preferably a thermosetting material. The resin material according to the present invention is preferably curable by heating. When the resin material is a resin film, the resin film is preferably a thermosetting resin film. It is preferable that the resin film is curable by heating.

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

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

The above-mentioned epoxy compounds include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, phenol novolak type epoxy compounds, biphenyl type epoxy compounds, biphenyl novolac type epoxy compounds, biphenol type epoxy compounds, and naphthalene type epoxy compounds. , fluorene type epoxy compound, phenol aralkyl type epoxy compound, naphthol aralkyl type epoxy compound, dicyclopentadiene type epoxy compound, anthracene type epoxy compound, epoxy compound having an adamantane skeleton, epoxy compound having a tricyclodecane skeleton, naphthylene ether type Examples include epoxy compounds and epoxy compounds having a triazine nucleus in their skeleton.

From the viewpoint of further lowering the coefficient of linear expansion and further suppressing the occurrence of delamination, the epoxy compound preferably contains an epoxy compound having an aromatic skeleton, and preferably contains an epoxy compound having a naphthalene skeleton or a phenyl skeleton. It is more preferable to include.

The above-mentioned epoxy compound may include an epoxy compound that is liquid at 25°C, or may include an epoxy compound that is solid at 25°C. From the viewpoint of further lowering the dielectric loss tangent, improving the coefficient of linear expansion (CTE) of the cured product, and further suppressing the occurrence of delamination, the above epoxy compound is an epoxy compound that is liquid at 25°C, and an epoxy compound that is liquid at 25°C. It is preferable to include a solid epoxy compound.

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

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

It is more preferable that the molecular weight of the epoxy compound is 1000 or less. In this case, even if the components excluding the solvent in the resin material are 100% by weight and the content of the inorganic filler is 50% by weight or more, a resin material with high fluidity can be obtained when forming the insulating layer. Therefore, when an uncured resin material or a B-staged resin material is laminated on a circuit board, the inorganic filler can be uniformly present.

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

From the viewpoint of further increasing the adhesive strength between the cured product and the metal layer and further suppressing the occurrence of delamination, the content of the above-mentioned epoxy compound is preferably 20% by weight of the components excluding the solvent in the resin material. It is at least 30% by weight, more preferably at least 80% by weight, more preferably at most 70% by weight.

[Inorganic filler]
The resin material includes an inorganic filler. By using an inorganic filler, the dielectric loss tangent of the cured product becomes even lower. Further, by using an inorganic filler, the dimensional change due to heat of the cured product is further reduced. Furthermore, the use of an inorganic filler further increases the adhesive strength between the cured product and the metal layer. Only one kind of the above-mentioned inorganic filler may be used, or two or more kinds thereof may be used in combination.

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

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

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

From the viewpoint of suppressing the occurrence of delamination, the specific surface area of the inorganic filler is 1 m ² /g or more and 50 m ² /g or less. If the specific surface area of the inorganic filler is less than 1 m ² /g or more than 50 m ² /g, delamination may occur.

From the viewpoint of further suppressing the occurrence of delamination, the specific surface area of the inorganic filler is preferably 2 m ² /g or more, more preferably 3 m ² /g or more, and preferably 40 m ² /g or less.

The specific surface area of the inorganic filler can be measured by the BET method using nitrogen gas. When the resin material contains two or more types of inorganic fillers, the specific surface area of the inorganic filler is measured for the entire inorganic filler contained in the resin material. The specific surface area of the inorganic filler may be measured using the inorganic filler used to obtain the resin material.

The average particle size of the inorganic filler is preferably 100 nm or more, more preferably 200 nm or more, even more preferably 500 nm or more, preferably 1.5 μm or less, more preferably 1.3 μm or less, and still more preferably 1.0 μm or less. be. When the average particle size of the inorganic filler is not less than the above lower limit and not more than the above upper limit, the occurrence of delamination can be further suppressed.

As the average particle size of the inorganic filler, a value of the median diameter (d50) that is 50% is adopted. The above average particle size can be measured using a laser diffraction scattering type particle size distribution measuring device. When the resin material contains two or more types of inorganic fillers, the average particle size of the inorganic fillers is measured as a whole of the inorganic fillers contained in the resin material. The average particle size of the inorganic filler may be measured using the inorganic filler used to obtain the resin material.

The inorganic filler is preferably spherical, 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, and as a result, the occurrence of delamination can be further suppressed. can. 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 surface-treated with a coupling agent, and even more preferably surface-treated with a silane coupling agent. By surface-treating the inorganic filler, the surface roughness of the roughened cured product is further reduced, and the adhesive strength between the cured product and the metal layer is further increased. As a result, the occurrence of delamination can be further suppressed. Furthermore, since the inorganic filler is surface-treated, finer wiring can be formed on the surface of the cured product, and even better inter-wiring insulation reliability and interlayer insulation reliability can be achieved on 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, acrylicsilane, aminosilane, imidazolesilane, vinylsilane, and epoxysilane.

The content of the inorganic filler is preferably 30% by weight or more, more preferably 40% by weight or more, even more preferably 50% by weight or more, and particularly preferably 55% by weight in 100% by weight of the components excluding the solvent in the resin material. % or more, most preferably 60% or more by weight. The content of the inorganic filler is preferably 85% by weight or less, more preferably 83% by weight or less, even more preferably 80% by weight or less, particularly preferably 78% by weight in 100% by weight of the components excluding the solvent in the resin material. % or less. When the content of the inorganic filler is equal to or higher than the lower limit, the dielectric loss tangent can be effectively lowered, the coefficient of thermal expansion of the cured product can be lowered, and the smear removability can be improved. When the content of the inorganic filler is at most the above upper limit, the handleability and flexibility of the resin film can be further improved. When the content of the inorganic filler is not less than the above lower limit and not more than the above upper limit, the surface roughness of the surface of the cured product can be further reduced, and finer wiring can be formed on the surface of the cured product. Can be done.

[Curing agent]
The resin material includes a curing agent. As the curing agent, conventionally known curing agents can be used. Only one kind of the above curing agent may be used, or two or more kinds thereof may be used in combination.

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

From the viewpoint of suppressing the occurrence of blisters and further suppressing the occurrence of delamination while lowering the dielectric loss tangent, the curing agent contains an active ester compound, a cyanate compound, a benzoxazine compound, a carbodiimide compound, or a maleimide compound. It is preferable. From the viewpoint of suppressing the occurrence of blisters and further suppressing the occurrence of delamination while lowering the dielectric loss tangent, the above-mentioned curing agent is preferably an active ester compound.

The cyanate compound may be a cyanate ester compound (cyanate ester curing agent). Examples of the cyanate ester compound include novolak-type cyanate ester resins, bisphenol-type cyanate ester resins, and prepolymers obtained by partially trimerizing these. Examples of the novolac cyanate ester resins include phenol novolac cyanate ester resins and alkylphenol cyanate ester resins. Examples of the bisphenol type cyanate ester resin include bisphenol A type cyanate ester resin, bisphenol E type cyanate ester resin, and tetramethylbisphenol F type cyanate ester resin.

Commercial products of the above cyanate ester compounds include phenol novolak cyanate ester resins (PT-30 and PT-60 manufactured by Lonza Japan), and prepolymers in which bisphenol cyanate ester resins are trimerized (Lonza Japan). ``BA-230S'', ``BA-3000S'', ``BTP-1000S'', and ``BTP-6020S'' manufactured by the company.

Examples of the above-mentioned phenol compounds include novolac-type phenol, biphenol-type phenol, naphthalene-type phenol, dicyclopentadiene-type phenol, aralkyl-type phenol, and dicyclopentadiene-type phenol.

Commercially available products of the above-mentioned phenol compounds include novolac type phenol ("TD-2091" manufactured by DIC Corporation), 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 phenols having an aminotriazine skeleton (“LA1356” and “LA3018-50P” manufactured by DIC Corporation).

The active ester compound refers to a compound that contains at least one ester bond in its structure and has aromatic rings bonded to both sides of the ester bond. The active ester compound is obtained, for example, by a condensation reaction between a carboxylic acid compound or a thiocarboxylic acid compound and a hydroxy compound or a thiol compound. Examples of active ester compounds include compounds represented by the following formula (1).

In the above formula (1), X1 and X2 each represent a group containing an aromatic ring. Preferred examples of the group containing the aromatic ring include a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, and the like. Examples of the above-mentioned substituents include hydrocarbon groups. The number of carbon atoms in the hydrocarbon group is preferably 12 or less, more preferably 6 or less, still more preferably 4 or less.

Examples of the combination of X1 and A combination with a naphthalene ring which may have a group is exemplified. Further, examples of the combination of X1 and X2 include a combination of a naphthalene ring that may have a substituent and a naphthalene ring that may have a substituent.

The above active ester compound is not particularly limited. From the viewpoint of lowering the dielectric loss tangent of the cured product and increasing the thermal dimensional stability of the cured product, it is more preferable that the active ester has a naphthalene ring in its main chain skeleton. Examples of commercially available active ester compounds include "HPC-8000-65T", "EXB9416-70BK" and "EXB8100-65T" manufactured by DIC Corporation.

Examples of the above-mentioned benzoxazine compounds include Pd type benzoxazine and Fa type benzoxazine.

Examples of commercially available benzoxazine compounds include "P-d type" manufactured by Shikoku Kasei Kogyo Co., Ltd.

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

In the above formula (2), represents a group, and p represents an integer of 1 to 5. When a plurality of Xs exist, the plurality of Xs may be the same or different.

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

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

Examples of the maleimide compound include N-alkyl bismaleimide compounds and N-phenyl bismaleimide compounds.

Commercially available maleimide compounds include Designer Molecules Inc. "BMI-1500", "BMI-1700" and "BMI-3000" manufactured by Daiwa Chemical Industries, Ltd., "BMI-1000", "BMI-2000", "BMI-3000" and "BMI-4000" manufactured by Daiwa Kasei Co., Ltd. Can be mentioned.

The content of the curing agent is preferably 25 parts by weight or more, more preferably 50 parts by weight or more, preferably 200 parts by weight or less, and more preferably 150 parts by weight or less, based on 100 parts by weight of the epoxy compound. When the content of the curing agent is at least the above lower limit and below the above upper limit, the curability is even better, and dimensional changes in the cured product due to heat and volatilization of residual unreacted components can be further suppressed.

The total content of the epoxy compound and the curing agent in 100% by weight of the components excluding the inorganic filler and solvent in the resin material is preferably 65% by weight or more, more preferably 70% by weight or more, preferably It is 99% by weight or less, more preferably 97% by weight or less. When the total content of the epoxy compound and the curing agent is not less than the above lower limit and not more than the above upper limit, an even better cured product can be obtained, and dimensional changes due to heat in the cured product can be further suppressed.

[Silane coupling agent]
The resin material includes a silane coupling agent. The silane coupling agent has a triazine skeleton. The resin material includes a silane coupling agent having a triazine skeleton. By using the above silane coupling agent, the dielectric loss tangent can be lowered and the occurrence of delamination can be suppressed. By using the above-mentioned silane coupling agent, it is possible to suppress the occurrence of delamination even during a reflow process or when a large amount of inorganic filler is blended. Moreover, by using the above-mentioned silane coupling agent, it is possible to suppress the occurrence of blisters and also to suppress the occurrence of delamination. Only one type of the above-mentioned silane coupling agent may be used, or two or more types may be used in combination.

In order to effectively exhibit the effects of the present invention, the triazine skeleton is preferably a diaminotriazine skeleton. That is, the silane coupling agent is preferably a silane coupling agent having a diaminotriazine skeleton. The diaminotriazine skeleton is a skeleton in which an amino group is bonded to each of the two carbon atoms constituting the triazine skeleton.

Examples of commercially available silane coupling agents having the diaminotriazine skeleton include "VD-5" manufactured by Shikoku Kasei Kogyo Co., Ltd.

The content of the silane coupling agent is preferably 0.1% by weight or more, more preferably 0.2% by weight or more, and even more preferably The content is 0.4% by weight or more, preferably 3% by weight or less, more preferably 2.5% by weight or less, even more preferably 2% by weight or less. When the content of the silane coupling agent is not less than the lower limit and not more than the upper limit, delamination can be further suppressed. When the content of the silane coupling agent is at most the above upper limit, it is possible to prevent the dielectric loss tangent from increasing.

[Thermoplastic resin]
Preferably, the resin material includes a thermoplastic resin. Examples of the thermoplastic resin include polyvinyl acetal resin and phenoxy resin. Only one kind of the above-mentioned thermoplastic resin may be used, or two or more kinds thereof may be used in combination.

From the viewpoint of effectively lowering the dielectric loss tangent and effectively increasing the adhesion of metal wiring regardless of the curing environment, the thermoplastic resin is preferably a phenoxy resin. By using the phenoxy resin, deterioration in the ability of the resin film to fill holes or irregularities in the circuit board and non-uniformity of the inorganic filler can be suppressed. Further, by using a phenoxy resin, the melt viscosity can be adjusted, so the dispersibility of the inorganic filler is improved, and the resin composition or B-staged product is less likely to wet and spread to 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. Only one type of the above phenoxy resin may be used, or two or more types may be used in combination.

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

Commercially available products of the above phenoxy resin include, for example, "YP50", "YP55" and "YP70" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., and "1256B40", "4250", "4256H40" and "4256H40" manufactured by Mitsubishi Chemical Corporation. 4275'', ``YX6954BH30'', and ``YX8100BH30''.

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

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

The contents of the thermoplastic resin and the phenoxy resin are not particularly limited. The content of the thermoplastic resin (if the thermoplastic resin is a phenoxy resin, the content of the phenoxy resin) is preferably 1% by weight out of 100% by weight of the components excluding the inorganic filler and solvent in the resin material. The content is more preferably 2% by weight or more, preferably 30% by weight or less, and more preferably 20% by weight or less. When the content of the thermoplastic resin is not less than the lower limit and not more than the upper limit, the resin material has good embedding properties in holes or irregularities of the circuit board. When the content of the thermoplastic resin is equal to or higher than the lower limit, the resin film can be formed even more easily, and an even better insulating layer can be obtained. When the content of the thermoplastic resin is below the above upper limit, the coefficient of thermal expansion of the cured product becomes even lower. When the content of the thermoplastic resin is below the upper limit, the surface roughness of the surface of the cured product becomes even smaller, and the adhesive strength between the cured product and the metal layer becomes even higher.

[Curing accelerator]
The resin material preferably contains a curing accelerator. By using the above-mentioned curing accelerator, the curing speed becomes even faster. By rapidly curing the resin material, the crosslinked structure in the cured product becomes uniform, the number of unreacted functional groups decreases, and the crosslinking density increases as a result. 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 imidazole compounds, phosphorus compounds, amine compounds, and organometallic compounds.

The above imidazole compounds include 2-undecylimidazole, 2-heptadecyl imidazole, 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 phosphorus compound include triphenylphosphine.

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

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

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

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

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

It is preferable that most of the solvent be removed when the resin composition is formed into a film. Therefore, the boiling point of the above 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 changed as appropriate in consideration of the coatability of the resin composition.

[Other ingredients]
In order to improve impact resistance, heat resistance, resin compatibility, workability, etc., the above resin materials contain leveling agents, flame retardants, coupling agents, coloring agents, antioxidants, ultraviolet deterioration inhibitors, and erasers. Foaming agents, thickeners, thixotropic agents, thermosetting resins other than epoxy compounds, etc. may be added.

Examples of the coupling agent include a silane coupling agent that does not have a triazine skeleton, a titanium coupling agent, and an aluminum coupling agent. Examples of the silane coupling agent without a triazine skeleton include vinylsilane, aminosilane, imidazolesilane, and epoxysilane.

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

(resin film)
A resin film (B-staged product/B-stage film) is obtained by molding the above-described resin composition into a film. It is preferable that the resin material is a resin film. Preferably, the resin film is a B-stage film.

The resin material is preferably a thermosetting material.

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

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

A film-like 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. A semi-cured product is not completely cured and may be further cured.

The resin film does not need to be prepreg. If the resin film is not a prepreg, migration will not occur along the glass cloth or the like. Moreover, when laminating or pre-curing the resin film, unevenness caused by the glass cloth will not occur on the surface. The resin film can be used in the form of a laminated film including a metal foil or a base material and a resin film laminated on the surface of the metal foil or base material. Preferably, the metal foil is copper foil.

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

From the viewpoint of controlling the degree of curing of the resin film more uniformly, the thickness of the resin film is preferably 5 μm or more, 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 of the resin film is preferably greater than or equal to 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 laminates, and multilayer printed wiring boards)
The resin material described above is suitably used to form a mold resin in which a semiconductor chip is embedded in a semiconductor device.

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

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

Metal foil can be laminated on one or both sides of the resin film. The method for laminating the resin film and metal foil is not particularly limited, and any known method can be used. For example, the resin film can be laminated onto the metal foil using a parallel plate press or a roll laminator while heating or pressing without heating.

The above resin material is suitably used to obtain a copper-clad laminate. An example of the above-mentioned copper-clad laminate includes 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 within the range of 1 μm to 50 μm. Moreover, in order to increase the adhesive strength between the cured product of the resin material and the copper foil, it is preferable that the copper foil has fine irregularities on its surface. The method of forming the unevenness is not particularly limited. Examples of the method for forming the above-mentioned unevenness include a method of forming the unevenness by a treatment using a known chemical solution.

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

An example of the multilayer board is a multilayer board that includes a circuit board and an insulating layer laminated on the circuit board. The insulating layer of this multilayer board is formed from the above resin material. Further, 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. Preferably, a portion of the insulating layer is embedded between the circuits.

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

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

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

Another example of the multilayer board is a circuit board, an insulating layer laminated on the surface of the circuit board, and a surface of the insulating layer on the opposite side of the surface on which the circuit board is laminated. For example, a multilayer board may include a copper foil. It is preferable that the insulating layer is formed by using a copper-clad laminate including a copper foil and a resin film laminated on one surface of the copper foil, and by curing the resin film. Furthermore, it is preferable that the copper foil is etched and is a copper circuit.

Another example of the multilayer board is a multilayer board that includes a circuit board and a plurality of insulating layers stacked on the surface of the circuit board. At least one layer of the plurality of insulating layers arranged on the circuit board is formed using the resin material. Preferably, the multilayer board further includes a circuit laminated on at least one surface of the insulating layer formed using the resin film.

Among multilayer substrates, multilayer printed wiring boards are required to have a low dielectric loss tangent and high insulation reliability due to the insulating layers. With the resin material according to the present invention, insulation reliability can be effectively improved by lowering the dielectric loss tangent and suppressing the occurrence of delamination. Therefore, the resin material according to the present invention is suitably used for forming an insulating layer in a multilayer printed wiring board. The resin material according to the present invention is preferably a resin material that can form an insulating layer in a multilayer printed wiring board. The resin material according to the present invention is preferably a resin material suitable 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 disposed on the surface of the circuit board, and a metal layer disposed between the plurality of insulating layers. At least one of the insulating layers is a cured product of the resin material.

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

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

In the multilayer printed wiring board 11, the insulating layers 13 to 16 are formed of a cured product of the resin material described above. In this embodiment, the surfaces of the insulating layers 13 to 16 are roughened, so that fine holes (not shown) are formed in the surfaces of the insulating layers 13 to 16. Further, a metal layer 17 extends inside the fine hole. Furthermore, 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 made smaller. Furthermore, in the multilayer printed wiring board 11, good insulation reliability is provided between the upper metal layer and the lower metal layer that are not connected by via hole connection or through hole connection (not shown).

(Roughening treatment and swelling treatment)
The resin material is preferably used to obtain a cured product that is subjected to a roughening treatment or a desmear treatment. The above-mentioned cured products also include pre-cured products 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 subjected to a roughening treatment. It is preferable that the cured product is subjected to a swelling treatment before the roughening treatment. It is preferable that the cured product is subjected to a swelling treatment after preliminary curing and before roughening treatment, and further hardened after roughening treatment. However, the cured product does not necessarily need to be subjected to swelling treatment.

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

For the roughening treatment, for example, a chemical oxidizing agent such as a manganese compound, a chromium compound, or a persulfuric compound is used. These chemical oxidants are used as an aqueous solution or an organic solvent dispersion solution after water or an organic solvent is added. The roughening liquid used in the roughening treatment generally contains an alkali as a pH adjuster. It is preferable that the roughening liquid contains sodium hydroxide.

Examples of the manganese compound include potassium permanganate and sodium permanganate. Examples of the chromium compound include potassium dichromate and potassium chromate anhydride. 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, even more preferably less than 150 nm. In this case, the adhesive strength between the cured product and the metal layer is increased, and further finer wiring is formed on the surface of the insulating layer. Furthermore, conductor loss can be suppressed, and signal loss can be kept low. The arithmetic mean roughness Ra is measured in accordance with JIS B0601:1994.

(Laser via opening and desmear processing)
Through holes may be formed in the cured product obtained by pre-curing the resin material. In the above-mentioned multilayer substrate, a via, a through hole, or the like is formed as a through hole. For example, vias can be formed by irradiation with a laser such as a CO ₂ laser. The diameter of the via is not particularly limited, but is approximately 60 μm to 80 μm. Due to the formation of the above-described through holes, a smear, which is a resin residue derived from a 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 subjected to a desmear treatment. Desmear treatment may also serve as roughening treatment.

Similar to the roughening treatment, the desmear treatment uses, for example, a chemical oxidizing agent such as a manganese compound, a chromium compound, or a persulfate compound. These chemical oxidants are used as an aqueous solution or an organic solvent dispersion solution after water or an organic solvent is added. Desmear processing liquid used for desmear processing generally contains an alkali. It is preferable that the desmear treatment liquid contains sodium hydroxide.

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

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

(epoxy compound)
Bisphenol A type epoxy compound (“850-S” manufactured by DIC, epoxy equivalent 187)
Biphenyl novolac type epoxy compound (Nippon Kayaku Co., Ltd. "NC-3000", epoxy equivalent 275)

(Inorganic filler)
Silica-containing slurry 1 (75% by weight silica: “SC4050-HOA” manufactured by Admatex, specific surface area 4.5 m ² /g, average particle size 1.0 μm, phenylaminosilane treatment, 25% by weight cyclohexanone)
Silica-containing slurry 2 (silica 60% by weight: "SC1050-HLA" manufactured by Admatex, specific surface area 17 m ² /g, average particle size 0.25 μm, phenylaminosilane treatment, cyclohexanone 40% by weight)
Silica-containing slurry 3 (silica 50% by weight: "YA100C" manufactured by Admatex, specific surface area 30 m ² /g, average particle size 0.10 μm, phenylaminosilane treatment, cyclohexanone 50% by weight)
Silica-containing slurry 4 (silica 50% by weight, "YA050C" manufactured by Admatex, specific surface area 65 m ² /g, average particle size 0.05 μm, phenylaminosilane treatment, cyclohexanone 50% by weight)

(hardening agent)
Active ester resin-containing liquid (“EXB9416-70BK” manufactured by DIC, solid content 70% by weight)

(Silane coupling agent)
Silane coupling agent having a triazine skeleton (silane coupling agent having a diaminotriazine skeleton, “VD-5” manufactured by Shikoku Kasei Kogyo Co., Ltd.)
Silane coupling agent without triazine skeleton (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd., N-phenyl-3-aminopropyltrimethoxysilane)

(hardening accelerator)
Dimethylaminopyridine (“DMAP” manufactured by Wako Pure Chemical Industries, Ltd.)

(Thermoplastic resin)
Phenoxy resin-containing liquid (“YX6954BH30” manufactured by Mitsubishi Chemical Corporation, solid content 30% by weight)

(others)
Phenol novolac resin with triazine skeleton (“LA-1356” manufactured by DIC)

(Examples 1 to 7 and Comparative Examples 1 to 3)
The components shown in Tables 1 and 2 below were blended in the amounts shown in Tables 1 and 2 below (unit: parts by weight of solid content), and stirred at room temperature until a uniform solution was obtained to obtain a resin material.

Preparation of resin film:
After applying the obtained resin material onto the release-treated surface of a release-treated PET film ("XG284" manufactured by Toray Industries, Inc., thickness 25 μm) using an applicator, it was placed in a gear oven at 100°C for 3 minutes. Dry and evaporate the solvent. In this way, a resin film (laminated film of PET film and resin film) having a thickness of 40 μm was obtained on the PET film.

Lamination process (preparation of lamination sample A):
A copper-clad laminate board (a laminate of a 150-μm-thick glass epoxy board and a 35-μm-thick copper foil) was prepared. Both surfaces of the copper-clad laminate were immersed in a copper surface roughening agent ("MEC Etch Bond CZ-8100" manufactured by MEC Corporation) to roughen the copper surface.

The obtained sheet-like resin film was stacked on the roughened copper surface of the copper-clad laminate board, and laminated at 0 pressure using a vacuum pressure laminator machine ("MVLP-500" manufactured by Meiki Manufacturing Co., Ltd.). 4 MPa and a lamination temperature of 100°C for 40 seconds, and further pressed for 40 seconds at a press pressure of 1.0 MPa and a pressing temperature of 100°C. In this way, a laminate in which a resin film was laminated on a copper-clad laminate substrate was produced. In the obtained laminate, after peeling off the PET film, it was heated at 180° C. for 30 minutes to harden the uncured resin material (resin film) to form an insulating layer. Thereafter, the laminate was cut into small pieces of 5 cm x 5 cm. In this way, a laminate sample A was produced in which a cured product of a resin material (resin film) was laminated on a copper-clad laminate substrate.

Next, the following wiring formation process was performed on the obtained laminated sample A.

Swelling process:
The above laminated sample A was placed in a swelling solution at 60°C (an aqueous solution containing "Swelling Dip Securigant P" manufactured by Atotech Japan Co., Ltd. and "sodium hydroxide" manufactured by Wako Pure Chemical Industries, Ltd.) at a swelling temperature of 60°C. Rocked for 20 minutes. Thereafter, it was washed with pure water to obtain a swelling-treated laminated sample A.

Roughening treatment (permanganate treatment):
The swelling-treated laminated sample A was placed in a sodium permanganate roughening aqueous solution (Atotech Japan Co., Ltd.'s "Concentrate Compact CP", Wako Pure Chemical Industries, Ltd.'s "Sodium Hydroxide") at 80°C, and the roughening temperature was increased. It was rocked at 80°C for 20 minutes. Thereafter, it was washed for 10 minutes with a 40°C cleaning solution ("Reduction Securigant P" manufactured by Atotech Japan, "Sulfuric acid" manufactured by Wako Pure Chemical Industries, Ltd.), and then further washed with pure water. In this way, a roughened cured product was formed on the glass epoxy substrate on which the inner layer circuit was formed by etching.

Electroless plating process:
The surface of the roughened cured product was treated with an alkaline cleaner ("Cleaner Securigant 902" manufactured by Atotech Japan Co., Ltd.) at 60° C. for 5 minutes to degrease and wash. After washing, the cured product was treated with a 25° C. pre-dip solution (“Pre-dip Neogant B” manufactured by Atotech Japan) for 2 minutes. Thereafter, the cured product was treated with a 40° C. activator solution (“Activator Neogant 834” manufactured by Atotech Japan Co., Ltd.) for 5 minutes to attach a palladium catalyst. Next, the cured product was treated with a 30° C. reducing solution (“Reducer Neogant WA” manufactured by Atotech Japan) for 5 minutes.

Next, the above-mentioned cured product was placed in a chemical copper solution (all manufactured by Atotech Japan, "Basic Print Gant MSK-DK", "Copper Print Gant MSK", "Stabilizer Print Gant MSK", "Reducer Cu"), and electroless plating was performed. This was carried out until the plating thickness was approximately 0.5 μm. After electroless plating, annealing treatment was performed at a temperature of 120° C. for 30 minutes to remove residual hydrogen gas. All steps up to the electroless plating step were carried out using a beaker scale with a treatment solution of 2 L and shaking the cured product.

Electrolytic copper plating process:
After electroless plating was formed, electrolytic copper plating was performed until the plating thickness reached 25 μm to form an electrolytic copper plating layer. For electrolytic copper plating, copper sulfate aqueous solution (“Copper Sulfate Pentahydrate” manufactured by Wako Pure Chemical Industries, Ltd., “Sulfuric Acid” manufactured by Wako Pure Chemical Industries, Ltd., “Basic Leveler Caparacid HL” manufactured by Atotech Japan, “Basic Leveler Caparacid HL” manufactured by Atotech Japan) A current of 0.6 A/cm ² was applied using a corrector (caparaside GS). Thereby, a layered structure after quick etching was obtained.

Main curing process:
An evaluation sample was prepared by heating the quick-etched laminated structure in a gear oven at 180° C. for 60 minutes to fully cure it.

(evaluation)
(1) Delamination (blister suppression)
Using the obtained evaluation sample, a moisture absorption test (40 hours at a temperature of 60° C. and a humidity of 60 RH%) was conducted in accordance with JEDEC LEVEL 3. Thereafter, nitrogen reflow treatment (peak top temperature 260° C.) was performed. Note that the reflow treatment was repeated 30 times. The presence or absence of blisters after reflow was visually confirmed.

[Determination criteria for delamination (blister suppression)]
○○: No blisters occur after 30 reflow treatments ○: Blisters occur after 21 to 29 reflow treatments ×: Blisters occur after 20 reflow treatments or less

(2) Dielectric Dissipation Tangent The obtained resin film was cut into pieces with a width of 2 mm and a length of 80 mm, and five pieces were stacked on top of each other to obtain a laminate with a thickness of 200 μm. The obtained laminate was heated to room temperature (23°C) using the cavity resonance method using the "Cavity Resonance Perturbation Method Permittivity Measurement Device CP521" manufactured by Kanto Denshi Application Development Co., Ltd. and the "Network Analyzer N5224A PNA" manufactured by Keysight Technologies. The dielectric loss tangent was measured at a frequency of 1.0 GHz.

[Judgment criteria for dielectric loss tangent]
○○: Dielectric loss tangent is 0.0050 or less ○: Dielectric loss tangent exceeds 0.0050 and 0.0055 or less ×: Dielectric loss tangent exceeds 0.0055

The composition and results are shown in Tables 1 and 2 below.

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

Claims (9)

Contains an epoxy compound, an inorganic filler, a curing agent, and a silane coupling agent having a triazine skeleton,
A resin material, wherein the inorganic filler has a specific surface area of 1 m ² /g or more and 50 m ² /g or less. The resin material according to claim 1, wherein the silane coupling agent is a silane coupling agent having a diaminotriazine skeleton. The resin material according to claim 1 or 2, wherein the curing agent contains an active ester compound, a cyanate compound, a benzoxazine compound, a carbodiimide compound, or a maleimide compound. Any one of claims 1 to 3, wherein the content of the silane coupling agent is 0.1% by weight or more and 3% by weight or less in 100% by weight of the components excluding the inorganic filler and solvent in the resin material. The resin material described in section. The resin material according to any one of claims 1 to 4, wherein the content of the inorganic filler is 30% by weight or more based on 100% by weight of components excluding the solvent in the resin material. The resin material according to any one of claims 1 to 5, which is a thermosetting material. The resin material according to any one of claims 1 to 6, which is a resin film. The resin material according to any one of claims 1 to 7, used for forming an insulating layer in a multilayer printed wiring board. a circuit board;
a plurality of insulating layers disposed on the surface of the circuit board;
a metal layer disposed between the plurality of insulating layers,
A multilayer printed wiring board, wherein at least one of the plurality of insulating layers is a cured product of the resin material according to any one of claims 1 to 8.

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