JP2019178198A - Thermosetting resin composition, coreless substrate, printed wiring board, and semiconductor device - Google Patents

Abstract

To provide a thermosetting resin composition that can be suitably used for materials of an insulating layer of a coreless substrate having reduced occurrence of warpage.SOLUTION: A thermosetting resin composition is used for forming an insulating layer constituting a build-up layer of a printed wiring board. The thermosetting resin composition has a thermosetting resin and an inorganic filler. The ratio of shrinkage amounts X1/X2, measured under specific measurement conditions, using a thermomechanical analyzer, is 0.5 or more and 4.0 or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a thermosetting resin composition, a coreless substrate, a printed wiring board, and a semiconductor device. More specifically, a thermosetting resin composition used for forming an insulating layer constituting a build-up layer of a printed wiring board, a coreless substrate provided with a cured product of the thermosetting resin composition as an insulating layer, The present invention relates to a printed wiring board including a coreless substrate and a semiconductor device including the printed wiring board.

  Various technologies have been developed in the field of a coreless substrate that does not have a core substrate having an excellent rigidity function such as a metal plate. For example, in Patent Document 1, a cover film, a conductor such as copper plating, a first insulator having a first fiber layer, a conductor, and a second insulator having a second fiber layer are formed in this order on a substrate. A coreless substrate obtained by separating a substrate and a cover film is described. In Patent Document 1, a fiber layer is formed by weaving a fiber bundle in a first direction in a plan view and a fiber bundle in a second direction different from the first direction in a plan view, and performing heat pressing in the thickness direction. In Patent Document 1, the heat shrinkability of each insulator is adjusted using the orientation of the fiber bundle and the rigidity of the fiber bundle.

JP 2008-085107 A

  In the coreless substrate described in Patent Document 1, the present inventors still accumulate internal stress in a plurality of buildup layers formed on the sacrificial substrate, and peel off the sacrificial substrate and the buildup layer. At this time, it was found that the internal stress is released and the build-up layer is warped, and the coreless substrate is warped.

  This invention is made | formed in view of the said situation, and provides the thermosetting resin composition which can be used conveniently as a material of the insulating layer of the coreless board | substrate with which generation | occurrence | production of curvature was reduced.

According to the present invention, a thermosetting resin composition used for forming an insulating layer constituting a build-up layer of a printed wiring board,
The thermosetting resin composition includes a thermosetting resin and an inorganic filler,
A thermosetting resin composition having a shrinkage ratio X1 / X2 of 0.5 or more and 4 or less, measured under the following measurement conditions using a thermomechanical analyzer, is provided.
(Measurement condition)
-Shrinkage measurement conditions: After impregnating and drying the thermosetting resin in a glass cloth, the prepreg having a flow direction of 20 mm and a width of 4 mm is obtained by cutting with scissors. A prepreg with a copper foil is obtained by sticking a small copper foil having a length of 7 mm, a width of 4 mm, and a thickness of 12 um at a total of four positions on both ends of the prepreg in the longitudinal direction. Both ends of the prepreg copper cut out with the copper foil are fixed with a chuck, and measurement is performed under the following heat treatment conditions using a thermomechanical analyzer (TMA). The amount of shrinkage of the prepreg with copper foil after the first heat treatment process after the first temperature raising process is X1 [ppm], and the copper foil after the second heat treatment process after the second temperature raising process. The shrinkage amount of the attached prepreg is set to X2 [ppm]. Thereby, the ratio X1 / X2 of the contraction amount is calculated.
Heat treatment conditions: First, as the first temperature raising process, the prepreg with copper foil is heated from a temperature of 30 ° C. to 180 ° C. at a temperature rising rate of 3 ° C./min. Next, as a first heat treatment process, the temperature is maintained at 180 ° C. for 90 minutes. Next, as a first cooling process, the temperature is lowered from a temperature of 180 ° C. to 30 ° C. at a temperature lowering rate of 5 ° C./min. Next, as a second temperature raising process, the temperature is raised from 30 ° C. to 220 ° C. at a temperature raising rate of 3 ° C./min. Next, as a second heat treatment process, the temperature is maintained at 220 ° C. for 90 minutes. Next, as a second cooling process, the temperature is decreased from 220 ° C. to 30 ° C. at a temperature decrease rate of 5 ° C./min.

  Moreover, according to this invention, a coreless board | substrate provided with the buildup layer containing the insulating layer comprised by the hardened | cured material of the said thermosetting resin composition and a circuit layer is provided.

  Moreover, according to this invention, a printed wiring board provided with the said coreless board | substrate is provided.

  In addition, according to the present invention, there is provided a semiconductor device comprising: the printed wiring board; and a semiconductor element mounted on the circuit layer of the printed wiring board or built in the printed wiring board. The

  ADVANTAGE OF THE INVENTION According to this invention, the thermosetting resin composition used in order to form the insulating layer of the coreless board | substrate with which generation | occurrence | production of curvature was reduced, and a coreless board | substrate, a printed wiring board, and a semiconductor device using the same are provided. .

It is a schematic diagram which shows an example of the manufacturing method of the coreless board | substrate which concerns on this embodiment. It is a schematic diagram of an example of the printed wiring board which concerns on this embodiment. It is a mimetic diagram of an example of a semiconductor device concerning this embodiment.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, the same reference numerals are given to the same components, and the description will be omitted as appropriate.

According to this embodiment, a thermosetting resin composition used for forming an insulating layer constituting a build-up layer of a printed wiring board,
The thermosetting resin composition includes a thermosetting resin and an inorganic filler,
A thermosetting resin composition having a shrinkage ratio X1 / X2 of 0.5 or more and 4.0 or less, measured under the following measurement conditions using a thermomechanical analyzer, is provided.
(Measurement condition)
-Shrinkage measurement conditions: After impregnating and drying the thermosetting resin in a glass cloth, the prepreg having a flow direction of 20 mm and a width of 4 mm is obtained by cutting with scissors. A prepreg with a copper foil is obtained by sticking a small copper foil having a length of 7 mm, a width of 4 mm, and a thickness of 12 um at a total of four positions on both ends of the prepreg in the longitudinal direction. Both ends of the prepreg with copper foil attached with copper are fixed with a chuck, and measurement is performed under the following heat treatment conditions using a thermomechanical analyzer (TMA). The amount of shrinkage of the prepreg with copper foil after the first heat treatment process after the first temperature raising process is X1 [ppm], and the copper foil after the second heat treatment process after the second temperature raising process. The shrinkage amount of the attached prepreg is set to X2 [ppm]. Thereby, the ratio X1 / X2 of the contraction amount is calculated.
Heat treatment conditions: First, as the first temperature raising process, the prepreg with copper foil is heated from a temperature of 30 ° C. to 180 ° C. at a temperature rising rate of 3 ° C./min. Next, as a first heat treatment process, the temperature is maintained at 180 ° C. for 90 minutes. Next, as a first cooling process, the temperature is lowered from a temperature of 180 ° C. to 30 ° C. at a temperature lowering rate of 5 ° C./min. Next, as a second temperature raising process, the temperature is raised from 30 ° C. to 220 ° C. at a temperature raising rate of 3 ° C./min. Next, as a second heat treatment process, the temperature is maintained at 220 ° C. for 90 minutes. Next, as a second cooling process, the temperature is decreased from 220 ° C. to 30 ° C. at a temperature decrease rate of 5 ° C./min.

  The inventor, for example, heats at 180 ° C. a first laminating step of forming a first thermosetting resin layer made of the thermosetting resin composition of the present embodiment on at least one surface of the sacrificial substrate. Thus, the first curing step of precuring the first thermosetting resin layer, and the first thermosetting resin layer of the present embodiment on the precured first thermosetting resin layer. A coreless substrate, including a second laminating step for forming the second thermosetting resin layer and a second curing step for fully curing the second thermosetting resin layer by heating at 220 ° C. In the manufacturing method of a body, when the ratio X1 / X2 of the said shrinkage | contraction amount of a thermosetting resin composition is 0.5 or more and 4.0 or less, it discovered that the curvature of the laminated body obtained was reduced.

  The thermosetting resin composition of the present embodiment includes a thermosetting resin and an inorganic filler. The ratio X1 / X2 of the shrinkage amount of the thermosetting resin composition can be adjusted by changing the types and blending amounts of the thermosetting resin and the inorganic filler.

<Thermosetting resin>
As the thermosetting resin used in the thermosetting resin composition of the present embodiment, it is preferable to use a resin having a glass transition temperature of 180 ° C to 240 ° C. By using such a resin, the shrinkage ratio X1 / X2 of the resulting thermosetting resin composition can be adjusted to 0.5 or more and 4.0 or less.

  Examples of thermosetting resins that can be used include maleimide compounds, epoxy resins, acrylic resins, melamine resins, polyurethane resins, diallyl phthalate resins, and silicone resins. As a thermosetting resin, it can use 1 type or in combination of 2 or more types. As the thermosetting resin, for example, a maleimide compound is preferably used among the above specific examples.

  In the present embodiment, the maleimide group of the maleimide compound has a five-membered planar structure, and the double bond of the maleimide group is likely to interact between molecules and has high polarity. It shows strong intermolecular interaction with a compound having a planar structure, etc., and can suppress molecular motion. Therefore, the thermosetting resin composition can reduce the linear expansion coefficient of the obtained insulating layer and improve the glass transition temperature by including a maleimide compound. Therefore, the thermosetting resin composition according to this embodiment can reduce internal stress by including a maleimide resin as the thermosetting resin, and can further reduce the amount of warping of the coreless substrate.

  From the viewpoint of reducing the amount of warping of the coreless substrate described above, as the maleimide compound, for example, a maleimide compound having two or more maleimide groups in the molecule is preferable.

Specific examples of the maleimide compound include 4,4′-diphenylmethane bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, bis -(3-ethyl-5-methyl-4-maleimidophenyl) methane, 4-methyl-1,3-phenylenebismaleimide, N, N'-ethylenedimaleimide, N, N'-hexamethylenedimaleimide, bis ( Two maleimide groups in the molecule such as 4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, bisphenol A diphenyl ether bismaleimide Such as polyphenylmethane maleimide Compounds and the like having three or more maleimide groups within.
As a maleimide compound, it can use 1 type or in combination of 2 or more types among the said specific examples.

Specific examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, bisphenol M type epoxy resin (4,4 ′-(1,3 -Phenylenediisopridiene) bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4 '-(1,4-phenylenediisopridiene) bisphenol type epoxy resin), bisphenol Z type epoxy resin (4,4 Bisphenol type epoxy resins such as' -cyclohexyldiene bisphenol type epoxy resins); phenol novolac type epoxy resins, cresol novolac type epoxy resins, tetraphenol group ethane type novolac type epoxy resins, condensed ring aromatic hydrocarbon structures Novolak-type epoxy resins such as volac-type epoxy resins; biphenyl-type epoxy resins; aralkyl-type epoxy resins such as xylylene-type epoxy resins and biphenyl-aralkyl-type epoxy resins; naphthylene ether-type epoxy resins, naphthol-type epoxy resins, naphthalenediol-type epoxy resins Naphthalene type epoxy resins such as bifunctional to tetrafunctional naphthalene type epoxy resins, binaphthyl type epoxy resins, naphthalene aralkyl type epoxy resins; anthracene type epoxy resins; phenoxy type epoxy resins; dicyclopentadiene type epoxy resins; norbornene type epoxy resins; Examples thereof include adamantane type epoxy resins and fluorene type epoxy resins.
As an epoxy resin, it can use 1 type or in combination of 2 or more types among the said specific examples.

<Inorganic filler>
Examples of the inorganic filler used in the thermosetting resin composition of the present embodiment include silica such as fused silica and crystalline silica, alumina, aluminum hydroxide, silicon nitride, barium sulfate, talc, boron nitride, and aluminum nitride. One type or two or more types of inorganic fillers selected from the group consisting of: Among them, it is preferable to use silica in that the shrinkage ratio X1 / X2 can be set to 0.5 or more and 4.0 or less.

  The inorganic filler is preferably 50 parts by mass or more and 80 parts by mass or less with respect to the total solid content of the thermosetting resin composition.

<Solvent>
The thermosetting resin composition of this embodiment can be used as a varnish by dissolving and dispersing raw material components in a solvent.
Specific examples of the solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethyl acetate, cyclohexane, heptane, cyclohexane, cyclohexanone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene glycol, cellosolve, and carbitol. , Anisole, and N-methylpyrrolidone. As the solvent, among the above specific examples, one kind or a combination of two or more kinds can be used.

<Other ingredients>
The thermosetting resin composition according to the present embodiment may further contain a curing agent, a curing accelerator, and the like as necessary.
Hereinafter, representative components will be described.

<Curing agent>
The thermosetting resin composition according to the present embodiment may include a curing agent, for example, according to the above-described thermosetting resin. Specifically, a phenol resin, a cyanate resin, a benzoxazine resin, an active ester resin, or the like can be used as the curing agent.

Examples of the phenol resin include monomers, oligomers, and polymers in general having two or more phenolic hydroxyl groups in one molecule, and the molecular weight and molecular structure thereof are not limited. Specific examples of the phenol resin include novolak type phenol resins such as phenol novolak resin, cresol novolak resin, and naphthol novolak resin; polyfunctional phenol resins such as triphenolmethane type phenol resin; terpene modified phenol resin, dicyclopentadiene Modified phenol resins such as modified phenol resins; Aralkyl type resins such as phenol aralkyl resins having a phenylene skeleton and / or biphenylene skeleton, naphthol aralkyl resins having phenylene and / or biphenylene skeletons; and bisphenol compounds such as bisphenol A and bisphenol F Can be mentioned. As a phenol resin, it can use 1 type or in combination of 2 or more types among the said specific examples.
In addition, as a phenol resin, it is preferable to contain the liquid phenol resin which is liquid at room temperature 25 degreeC.

Specific examples of the benzoxazine resin include o-cresol aniline type benzoxazine resin, m-cresol aniline type benzoxazine resin, p-cresol aniline type benzoxazine resin, phenol-aniline type benzoxazine resin, phenol-methyl. Amine type benzoxazine resin, phenol-cyclohexylamine type benzoxazine resin, phenol-m-toluidine type benzoxazine resin, phenol-3,5-dimethylaniline type benzoxazine resin, bisphenol A-aniline type benzoxazine resin, bisphenol A- Amine type benzoxazine resin, bisphenol F-aniline type benzoxazine resin, bisphenol S-aniline type benzoxazine resin, dihydroxydiphenylsulfate -Aniline type benzoxazine resin, dihydroxydiphenyl ether-aniline type benzoxazine resin, benzophenone type benzoxazine resin, biphenyl type benzoxazine resin, bisphenol AF-aniline type benzoxazine resin, bisphenol A-methylaniline type benzoxazine resin, phenol- Examples thereof include diaminodiphenylmethane type benzoxazine resin, triphenylmethane type benzoxazine resin, and phenolphthalein type benzoxazine resin.
Moreover, as a commercial item of a benzoxazine resin, BF-BXZ, BS-BXZ, BA-BXZ (above, Konishi Chemical Industry Co., Ltd. product) etc. can be used, for example.

As the cyanate resin, a cyanate ester resin can be used.
Specific examples of the cyanate ester resin include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4, 4'-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5- Bifunctional cyanate resins such as dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, bis (4-cyanatephenyl) ether; phenol Novolac and Cresor Novolak, multifunctional cyanate resin derived from dicyclopentadiene structure-containing phenol resins; and prepolymer portion of the illustrated cyanate ester resin is a triazine of the like.
Here, as a commercial item of cyanate ester resin, for example, PT30, BA230, DT-4000, DT-7000 manufactured by Lonza Japan Co., Ltd. can be used.

Specifically, the active ester resin has an ester group with high reaction activity such as a phenol ester compound, a thiophenol ester compound, an N-hydroxyamine ester compound, a compound in which a heterocyclic hydroxy group is esterified, and the like. What has the hardening effect | action of an epoxy resin can be used.
As an active ester resin, it is preferable to use what is obtained from a carboxylic acid compound and a hydroxy compound among the said specific examples, for example. Here, specific examples of the hydroxy compound include phenol compounds and naphthol compounds.
Specific examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.
Specific examples of the phenol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, and o-cresol. M-cresol, p-cresol, catechol, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadienyl diphenol, phenol novolac and the like.
Specific examples of the naphthol compound include α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, and the like.

<Curing accelerator>
As the curing accelerator described above, one that promotes the reaction between the thermosetting resin and the curing agent can be used. Specific examples of the curing accelerator include zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, zinc octylate, bisacetylacetonate cobalt (II), trisacetylacetonate cobalt (III) and the like. Organic metal salts, tertiary amines such as triethylamine, tributylamine, diazabicyclo [2,2,2] octane, tetraphenylphosphonium / tetraphenylborate (TPP-K), tetraphenylphosphonium / tetrakis (4-methylphenyl) borate (TPP-MK), quaternary phosphonium compounds such as bis (naphthalene-2,3-dioxy) phenylsilicate adduct of tetraphenylphosphonium, 2-phenyl-4-methylimidazole, 2-ethyl-4-ethylimidazole 2 Imidazoles such as phenyl-4-ethylimidazole, 2-phenyl-4-methyl-5-hydroxyimidazole, 2-phenyl-4,5-dihydroxyimidazole, phenolic compounds such as phenol, bisphenol A, nonylphenol, acetic acid, benzoic acid , Organic acids such as salicylic acid and p-toluenesulfonic acid, and onium salt compounds.

  The thermosetting resin of this embodiment is provided as a varnish-like resin composition by dissolving and dispersing the above components in a solvent.

(Manufacturing method of coreless substrate)
Next, a method for producing a coreless substrate using the thermosetting resin composition of the present embodiment will be described.
For example, the coreless substrate of the present embodiment is heated at 180 ° C. in a first lamination step of forming a first thermosetting resin layer made of the thermosetting resin composition on at least one surface of a sacrificial substrate. Thus, a first curing step of precuring the first thermosetting resin layer, and a second curing layer comprising the thermosetting resin layer of the present embodiment on the precured first thermosetting resin layer. And the second thermosetting resin layer and the second thermosetting resin layer that have been precured by heating at 220 ° C. are fully cured, respectively. The first buildup layer and the second buildup layer are produced by a second curing step and a peeling step of peeling the sacrificial substrate from the first buildup layer.
Hereinafter, details of each process will be described based on FIG. 1 which is a schematic diagram of an example of a method of manufacturing a coreless substrate.

  Focusing on the first buildup layer provided in the coreless substrate of the present embodiment, the shrinkage ratio X1 / X2 of the first buildup layer, in other words, the shrinkage of the thermosetting resin layer precured at 180 ° C. Since the ratio between X1 and the shrinkage amount X2 of the curable resin layer that is fully cured at 220 ° C. is relatively small, warpage of the obtained coreless substrate is reduced.

Hereinafter, each step will be described with reference to the drawings.
(First lamination step)
In the first laminating step, as shown in FIG. 1A, a first thermosetting resin layer 40 made of the thermosetting resin composition is formed on at least one surface of the sacrificial substrate 20. The first thermosetting resin layer 40 may be formed on at least one surface of the sacrificial substrate, and is preferably formed on both surfaces of the sacrificial substrate, for example. Thereby, the productivity of the coreless board | substrate which reduced the curvature can be improved.
Moreover, as shown to Fig.1 (a), the 1st thermosetting resin layer may be provided with the conductor circuit pattern 30 or the electrode pad which is not illustrated in the inside. Here, the conductor circuit pattern 30 may be formed by laminating a copper foil on a sacrificial substrate and photolithography or etching the copper foil, or by directly forming the conductor circuit pattern by a semi-additive process method. Also good.

As a method of forming the first thermosetting resin layer 40 made of the thermosetting resin composition, a method of coating the varnish-like thermosetting resin composition on the sacrificial substrate 20, a varnish-like thermosetting For example, the thermosetting resin layer 40 that is a resin film is produced by drying the curable resin composition and laminated on the sacrificial substrate 20.
Alternatively, the thermosetting resin layer 40 may be formed, for example, by impregnating a thermosetting resin composition into a fiber substrate such as a glass cloth or a paper substrate to form a resin film.
In addition, as a method of laminating the first thermosetting resin layer 40 which is a resin film on the sacrificial substrate 20, a method of vacuum heating and pressure molding or the like can be specifically mentioned.

  For example, the first thermosetting resin layer 40 according to the present embodiment may include a via hole 32 as illustrated in FIG. The via hole 32 may be a hole for electrically connecting layers, and may be either a through hole or a non-through hole. The via hole 32 may be formed by burying a metal, for example. The buried metal may have a structure covered with an electroless metal plating film.

  Examples of the sacrificial substrate 20 include a core material in which a metal layer 24 / carrier layer / prepreg / carrier layer / metal layer 24 are laminated in this order. For example, the conductor circuit pattern 30 may be provided on the sacrificial substrate 20 by performing electrolytic metal plating in a state where a resist is previously formed on a non-circuit portion on the surface of the metal layer 24. Alternatively, the conductive circuit pattern 30 may be provided by performing electrolytic metal plating on the surface of the metal layer 24 and then photolithography or etching the electrolytic metal plating layer. The conductor circuit formed by these methods can be made into a conductor circuit embedded in a prepreg by removing the metal layer 24 by metal etching after peeling from the sacrificial substrate.

(First curing step)
In the first curing step, the first thermosetting resin layer 40 formed in the first lamination step is pre-cured by heating at 180.

(Second lamination step)
In the second lamination step, the second thermosetting resin layer 50 is formed on the precured first thermosetting resin layer.
Here, as shown in FIG.1 (c), it is preferable that the 2nd thermosetting resin layer 50 equips the inside with the conductor circuit pattern 34 or the electrode pad which is not shown in figure, for example. Here, the conductor circuit pattern 34 can be formed by the same method as the conductor circuit pattern 30 mentioned above, for example.

  The 2nd thermosetting resin layer 50 is comprised by the thermosetting resin composition of this embodiment. The method for forming the second thermosetting resin layer 50 can be the same as the method for forming the first thermosetting resin layer 40 described above.

  Moreover, the 2nd thermosetting resin layer 50 which concerns on this embodiment may be provided with the via hole 38, for example, as shown in FIG.1 (d). The via hole 38 may be a hole for electrically connecting layers, and may be either a through hole or a non-through hole. The via hole 38 may be formed by burying a metal, for example. The buried metal may have a structure covered with an electroless metal plating film.

  Moreover, the 2nd thermosetting resin layer 50 which concerns on this embodiment may be provided with the conductor circuit pattern 39 connected with the via hole 38 on the surface, for example, as shown in FIG.1 (d). Here, the conductor circuit pattern 39 can be formed by the same method as the conductor circuit pattern 30 described above.

(Second curing step)
In the second curing step, the second thermosetting resin layer 50 formed in the second lamination step is fully cured by heating at 220. Thereby, the first thermosetting resin layer 40 and the second thermosetting resin layer 50 are fully cured to form the first buildup layer 42 and the second buildup layer 52, respectively. The thermosetting resin composition of the present embodiment for forming these build-up layers has a shrinkage ratio X1 / X2 as small as 0.5 or more and 4.0 or less, so the difference in displacement due to heat shrinkage between the build-up layers. It can suppress that the internal stress resulting from is produced. Therefore, the amount of warpage of the obtained coreless substrate can be reduced.

(Peeling process)
In one embodiment, the method of manufacturing a coreless substrate may include a step of peeling the sacrificial substrate 20 from the first buildup layer. By this peeling step, the coreless substrate 100 can be obtained as shown in FIG. The coreless substrate according to the present embodiment has a laminated structure in which, for example, a metal layer, a first buildup layer, and a second buildup layer are laminated in this order, and a conductor circuit pattern is formed on the surface of the second buildup layer. 39.

(Etching process)
Here, in the first laminating step described above, the metal layer 24 exists between the first buildup layer 42 and the sacrificial substrate 20, that is, the sacrificial substrate, the metal layer, and the first thermosetting. When the three-layer laminated structure is formed by laminating the functional resin layer in this order, the metal layer remains, for example, laminated on the first buildup layer 42 by the peeling process. In this case, an etching process for etching and removing the metal layer may be further included.
It does not limit as a method to etch, A conventionally well-known method can be used.

  The coreless substrate of the present embodiment may include any number of additional buildup layers such as a third buildup layer and a fourth buildup layer as necessary, and these manufacturing methods are the same as described above. It is.

(Use)
The coreless substrate according to the present embodiment can be used as a substrate used for a panel level package, a printed wiring board, and the like. Since the coreless substrate according to the present embodiment has a small amount of warpage and is thinner than a substrate having a conventional core, it can be suitably used for the above-described applications.
Hereinafter, an example in which the coreless substrate according to the present embodiment is used for the printed wiring board 300 will be described with reference to FIG.

(Printed wiring board)
The printed wiring board 300 according to the present embodiment may have a structure including, for example, an insulating layer 301 (coreless substrate) and an insulating layer 401 (solder resist layer). By using the coreless substrate according to the present embodiment, a multilayer printed wiring board can be produced.

Further, the panel level package and the printed wiring board using the coreless substrate according to the present embodiment can be used for a semiconductor device, for example.
The semiconductor device according to the present embodiment will be described below using FIG. 3 as an example.

(Semiconductor device)
The semiconductor device 400 according to the present embodiment can include, for example, a printed wiring board 300 and a semiconductor element 407 mounted on the circuit layer of the printed wiring board 300 or built in the printed wiring board 300. .

  For example, the semiconductor device 400 shown in FIG. 3 has a structure in which a semiconductor element 407 is mounted on the printed wiring board 300 shown in FIG. The semiconductor element 407 is covered with a sealing material layer 413. Such a semiconductor package may have a flip chip structure in which the semiconductor element 407 is electrically connected to the printed wiring board 300 via the solder bump 410 and the metal layer 303.

  As mentioned above, although embodiment of this invention was described with reference to drawings, these are the illustrations of this invention, Various structures other than the above are also employable.

Hereinafter, although an example and a comparative example explain the present invention, the present invention is not limited to these.
First, raw material components used in Examples and Comparative Examples will be described.

(Thermosetting resin)
-Thermosetting resin 1: Epoxy resin (manufactured by DIC, HP-7200)
-Thermosetting resin 2: Cyanate resin (Lonza, PT-30)
Thermosetting resin 3: benzoxazine resin (Pd type benzoxazine, manufactured by Shikoku Kasei Kogyo Co., Ltd.)
Thermosetting resin 4: Bismaleimide resin (manufactured by Daiwa Kasei Kogyo Co., Ltd., BMI-1000)
・ Thermosetting resin 5: Allylphenol resin (manufactured by Daiwa Kasei Kogyo, DABPA)

(Other substances)
Inorganic filler 1: Silica (manufactured by Admatechs, SO-C4)
Curing accelerator 1: Imidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., Curesol 2PZ-PW)
Coupling agent 1: Epoxysilane coupling agent (Shin-Etsu Chemical Co., Ltd., KBM-403)

(Examples 1-2, Comparative Example 1)
The production methods of the thermosetting resin compositions of Examples 1 and 2 and Comparative Example 1 will be described.
First, each raw material component of the compounding amount shown in Table 1 was dissolved or dispersed, adjusted with methyl ethyl ketone to have a nonvolatile content of 70% by mass, and stirred using a high-speed stirring device to prepare a resin varnish. In addition, the unit of the compounding quantity of each raw material component is a mass part.

(Preparation of prepreg)
The varnish of the thermosetting resin composition of each example and each comparative example was applied to a fiber base (Unitika, # 1017E glass cloth), and then the solvent was removed by drying at a temperature of 170 ° C. for 2 minutes. A prepreg having a thickness of 30 μm was prepared.

(Glass-transition temperature)
The glass transition temperature of the prepreg was measured using the prepreg produced using the thermosetting resin composition of each example and each comparative example. Details will be described below.
First, in a state where the prepreg was suspended in a thermostat (PHH-101M, manufactured by Espec Corp.), the resin was cured by heat treatment at 220 ° C. for 2 hours. Next, the treated prepreg was cut into a size of 35 mm in the flow direction and 8 mm in width using scissors to prepare a sample for measuring the glass transition temperature.
The measurement was performed using dynamic viscoelasticity measurement. The deformation mode was the tensile mode at a measurement temperature of 30 ° C. to 450 ° C., a temperature increase rate of 5 ° C./min, and a frequency of 1 rad / sec, and the temperature at the peak of tan δ was evaluated as the glass transition temperature. The evaluation results are shown in Table 1 below. The unit is ° C.

(Shrinkage)
The shrinkage amounts X1 and X2 were measured using prepregs prepared using the thermosetting resin compositions of the examples and comparative examples, and the shrinkage ratio X1 / X2 was calculated. Details will be described below.
First, the prepreg was cut into a flow direction 20 mm × width 4 mm using scissors. Next, a small copper foil having a length of 7 mm, a width of 4 mm, and a thickness of 12 μm was pasted on the front and back in total at both ends in the longitudinal direction of the prepreg to obtain a prepreg with a copper foil.
The sample was fixed to a measurement jig, and measurement was performed under the following heat treatment conditions using a thermomechanical analyzer (TMA).
Here, the amount of shrinkage of the prepreg with copper foil after the first heat treatment process after the first heat treatment process is X1 [ppm], and after the second heat treatment process with respect to the second heat treatment process. The shrinkage amount of the prepreg with copper foil was evaluated as X2 [ppm]. Further, the shrinkage ratio X1 / X2 was calculated from the obtained X1 and X2. The evaluation results are shown in Table 1 below.
(Heat treatment conditions)
The following first temperature raising process, first heat treatment process, first cooling process, second temperature raising process, second heat treatment process, and second cooling process were successively performed in this order.
First, as the first temperature raising process, the prepreg with copper foil was heated from a temperature of 30 ° C. to 180 ° C. at a temperature raising rate of 3 ° C./min.
Next, as a first heat treatment process, the temperature was maintained at 180 ° C. for 90 minutes.
Subsequently, as a first cooling process, the temperature was decreased from 180 ° C. to 30 ° C. at a temperature decreasing rate of 5 ° C./min.
Next, as a second temperature raising process, the temperature was raised from 30 ° C. to 220 ° C. at a temperature raising rate of 3 ° C./min.
Next, as a second heat treatment process, the temperature was maintained at 220 ° C. for 90 minutes.
Next, as a second cooling process, the temperature was decreased from 220 ° C. to 30 ° C. at a temperature decrease rate of 5 ° C./min.

  Moreover, the coreless board | substrate was produced using the thermosetting resin composition of each Example and each comparative example. Details will be described below.

(Sacrificial substrate preparation)
As a sacrificial substrate, a core material (manufactured by Sumitomo Bakelite, LAZ-4785GH-G, thickness 0.1 mm) provided with peelable copper foil (manufactured by Mitsui Metal Mining Co., Ltd., MT-Ex-5 [mu] m) was prepared on both sides of the prepreg.

(First laminating step, first curing step)
Next, the prepreg was placed on both surfaces of the sacrificial substrate so as to cover the peelable copper foil of the sacrificial substrate, thereby forming a first thermosetting resin layer. Next, a copper foil was further laminated on the first thermosetting resin layer, and the first thermosetting resin layer was precured by heating to a temperature of 180 ° C. and vacuum laminating for 90 minutes. Next, the copper foil was etched and patterned to form a first circuit layer composed of a conductor circuit pattern.
Thus, the first circuit layer, the precured first thermosetting resin layer, the sacrificial substrate, the precured first thermosetting resin layer, and the first circuit layer are stacked in this order. Was made.

(Second laminating step, second curing step)
Next, the prepreg was disposed on both surfaces of the sacrificial substrate so as to cover the conductor circuit pattern provided on both surfaces of the first laminate, thereby forming a second thermosetting resin layer. Next, a copper foil was further laminated on the second thermosetting resin layer, and the second thermosetting resin layer was fully cured by heating to 220 ° C. and vacuum laminating for 90 minutes. Next, the copper foil was etched and patterned to form a second circuit layer made of a conductor circuit pattern.
Thus, the second circuit layer, the fully cured second thermosetting resin layer, the first circuit layer, the fully cured first thermosetting resin layer, the sacrificial substrate, and the fully cured first thermosetting resin layer. Then, a second laminated body was produced in which the first circuit layer, the fully cured second thermosetting resin layer, and the second circuit layer were laminated in this order.

(Peeling process)
Next, by peeling the peelable copper foil, the sacrificial substrate and the first buildup layer are peeled off, and the peelable copper foil, the first buildup layer, and the second buildup layer are laminated in this order. A substrate was produced.

(War amount of coreless substrate)
In the peeling process, it was confirmed that the coreless substrate is warped when the peelable copper foil is peeled off.
Therefore, the amount of warpage generated in the coreless substrate of each example and each comparative example was measured. Details will be described below.
First, the obtained coreless substrate was placed on a flat surface so that the four corners of the warped coreless substrate were not grounded.
Next, the length from the plane to the four corners and the length from the four corners to the plane were measured, and the average value was evaluated as the amount of warpage of the coreless substrate. The evaluation results are shown in Table 1 below as w / copper evaluation results. The unit is mm.
Moreover, the peelable copper foil was removed by carrying out copper etching process about the coreless board | substrate obtained by the preparation method of the coreless board | substrate of each Example and each comparative example. The evaluation result of the warpage amount of the coreless substrate at this time is shown in the following Table 1 as the evaluation result of w / o copper. The unit is mm.
The coreless substrate warped so as to wind the second buildup layer inside was defined as a smile warp, and the sign of the warp amount was positive. The coreless substrate warped so that the first buildup layer was wound inside was defined as a cry warp, and the sign of the warp amount was negative. The evaluation results of Examples 1 to 3 and Comparative Example 1 were all positive, that is, a coreless substrate having a smile warp.

  As shown in Table 1 above, when the thermosetting resin composition of each example was prepared as a coreless substrate and the sacrificial substrate and the buildup layer were peeled off, the thermosetting resin composition of the comparative example was built. It was confirmed that the warp generated in the up layer can be reduced and the warp amount of the coreless substrate can be reduced.

Claims (10)

A thermosetting resin composition used for forming an insulating layer constituting a build-up layer of a printed wiring board,
The thermosetting resin composition includes a thermosetting resin and an inorganic filler,
A thermosetting resin composition having a shrinkage ratio X1 / X2 of 0.5 or more and 4.0 or less, measured using a thermomechanical analyzer under the following measurement conditions.
(Measurement condition)
-Measurement conditions of shrinkage amount: After impregnating and drying the thermosetting resin composition into a glass cloth, the prepreg having a flow direction of 20 mm and a width of 4 mm is obtained by cutting with scissors. A prepreg with a copper foil is obtained by sticking a small copper foil having a length of 7 mm, a width of 4 mm, and a thickness of 12 um at a total of four positions on both ends of the prepreg in the longitudinal direction. Both ends of the prepreg with copper foil attached with copper are fixed with a chuck, and measurement is performed under the following heat treatment conditions using a thermomechanical analyzer (TMA). The amount of shrinkage of the prepreg with copper foil after the first heat treatment process after the first temperature raising process is X1 [ppm], and the copper foil after the second heat treatment process after the second temperature raising process. The shrinkage amount of the attached prepreg is set to X2 [ppm]. Thereby, the ratio X1 / X2 of the contraction amount is calculated.
Heat treatment conditions: First, as the first temperature raising process, the prepreg with copper foil is heated from a temperature of 30 ° C. to 180 ° C. at a temperature rising rate of 3 ° C./min. Next, as a first heat treatment process, the temperature is maintained at 180 ° C. for 90 minutes. Next, as a first cooling process, the temperature is lowered from a temperature of 180 ° C. to 30 ° C. at a temperature lowering rate of 5 ° C./min. Next, as a second temperature raising process, the temperature is raised from 30 ° C. to 220 ° C. at a temperature raising rate of 3 ° C./min. Next, as a second heat treatment process, the temperature is maintained at 220 ° C. for 90 minutes. Next, as a second cooling process, the temperature is decreased from 220 ° C. to 30 ° C. at a temperature decrease rate of 5 ° C./min. The thermosetting resin composition according to claim 1,
The said thermosetting resin is a thermosetting resin composition containing an epoxy resin. The thermosetting resin composition according to claim 1 or 2,
The inorganic filler is a thermosetting resin composition containing silica. The thermosetting resin composition according to any one of claims 1 to 3,
The said inorganic filler is a thermosetting resin composition which is the quantity of 50 to 80 mass parts with respect to the total solid of the said thermosetting resin composition.   A coreless board provided with the buildup layer containing the insulating layer comprised by the hardened | cured material of the thermosetting resin composition of any one of Claim 1 to 4, and a circuit layer. The coreless substrate according to claim 5,
The insulating layer is a coreless substrate including glass fiber. The coreless substrate according to claim 5 or 6,
The coreless substrate includes two or more buildup layers,
A coreless substrate in which at least two or more of the build-up layers are successively laminated. A coreless substrate according to any one of claims 5 to 7,
The coreless substrate, wherein the build-up layer has a thickness of 10 μm or more and 100 μm or less.   A printed wiring board comprising the coreless substrate according to claim 5. A printed wiring board according to claim 9,
A semiconductor device comprising: a semiconductor element mounted on the circuit layer of the printed wiring board or built in the printed wiring board.

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