TWI881041B - Resin composition, prepreg, laminate, metal foil-clad laminate, and printed wiring board - Google Patents

Abstract

A resin composition containing black particles (A), an inorganic filler (B) and a resin (C), wherein the amount of the black particles (A) is within a range from 15 to 100 parts by mass per 100 parts by mass of the resin (C), and the amount of the inorganic filler (B) is within a range from 20 to 110 parts by mass per 100 parts by mass of the resin (C).

Description

Resin composition, prepreg, laminate, metal-clad laminate, and printed wiring board

The present invention relates to a resin composition, and a prepreg, a laminate, a metal-clad laminate, a printed wiring board, and a method for producing the printed wiring board using the composition.

In recent years, with the rapid progress of electronic components in terms of high performance, high functionality, and miniaturization, electronic materials used in electronic components are also required to have higher functionality. For example, electronic materials used in light-emitting components such as displays and LEDs need to have light-shielding properties to prevent unnecessary light leakage to the outside, and electronic materials used in light-receiving components such as optical sensors in cameras need to have light-shielding properties to prevent light from entering from the outside. Thus, printed wiring boards used in light-emitting components, light-receiving components, or other electronic optical components are required to have light-shielding properties.

For example: Patent document 1 discloses a black polyimide film that contains aniline black and other substances to ensure light-shielding properties as a flexible printed wiring board. [Prior art document] [Patent document]

Patent document 1: Japanese Patent Application Publication No. 2016-047863

(The problem to be solved)

In recent years, it is desired to improve the light shielding property of rigid substrates impregnated or coated with resin compositions. As described in Patent Document 1, it is known that a method for improving the light shielding property of flexible printed wiring boards is to use aniline black, etc. However, it is known that if a black component is added to the resin composition constituting the rigid substrate in the same manner as the flexible printed wiring board, the thermal expansion rate may increase or the formability may decrease.

In view of the above problems, the present invention aims to provide a resin composition capable of obtaining a rigid substrate having excellent light-shielding properties and low thermal expansion properties, and a prepreg, a laminate, a metal-clad laminate, a printed wiring board, and a method for manufacturing a printed wiring board using the resin composition. (Method for solving the problem)

The inventors of this case have made great efforts to study and find that the above-mentioned problem can be solved by using a predetermined amount of black particles (A) and a predetermined amount of inorganic filler (B), and thus the present invention has been completed.

That is, the present invention is as follows. [1] A resin composition comprising black particles (A), an inorganic filler (B), and a resin (C), wherein the content of the black particles (A) is 15 to 100 parts by mass relative to 100 parts by mass of the resin (C), and the content of the inorganic filler (B) is 20 to 110 parts by mass relative to 100 parts by mass of the resin (C). [2] The resin composition as described in [1], wherein the black particles (A) comprise a mixed oxide containing La and Mn. [3] The resin composition of [2], wherein the mixed oxide has a calcium titanate phase, the calcium titanate phase has a diffraction peak with maximum intensity in the range of 31° to 34° of the diffraction angle 2θ in X-ray diffraction measurement using CuKα rays as the X-ray source, and the mixed oxide contains Mn ₃ O ₄ having a spinel structure as the Mn oxide. [4] The resin composition of [2] or [3], wherein the content of La in the mixed oxide is 35 to 70 mass% relative to 100 mass% of the total amount of the mixed oxide when converted to La ₂ O ₃ , and the content of Mn in the mixed oxide is 25 to 60 mass% relative to 100 mass% of the total amount of the mixed oxide when converted to MnO ₂ . [5] The resin composition of any one of [1] to [4], wherein the volume resistivity of the black particles (A) is greater than 1.0×10 ⁷ Ω·cm. [6] The resin composition of any one of [1] to [5], wherein the black particles (A) are not coated with an insulating material. [7] The resin composition of any one of [1] to [6], wherein the inorganic filler (B) contains at least one selected from the group consisting of silica, aluminum hydroxide, aluminum oxide, alumina, magnesium oxide, molybdenum oxide, zinc molybdate, and magnesium hydroxide. [8] The resin composition of any one of [1] to [7], wherein the resin (C) contains at least one selected from the group consisting of a cyanate compound (D), an epoxy compound (E), a maleimide compound (F), a phenol compound (G), an oxycyclobutane resin (H), a benzophenone compound (I), and a compound having a polymerizable unsaturated group (J). [9] The resin composition of [8], wherein the resin (C) includes an epoxy compound (E), a phenol compound (G) and/or a cyanate compound (D). [10] The resin composition of [8] or [9], wherein the epoxy compound (E) includes a compound represented by the following formula (I): [Chemical 1] In formula (I), n1 represents an integer from 1 to 10. [11] The resin composition of any one of [8] to [10], wherein the phenol compound (G) comprises a compound represented by the following formula (II) or formula (III); [Chemical 2] In formula (II), n2 represents an integer from 1 to 10; In formula (III), n3 represents an integer of 1 to 10. [12] The resin composition of any one of [8] to [11], wherein the maleimide compound (F) comprises at least one selected from the group consisting of bis(4-maleimidephenyl)methane, 2,2-bis{4-(4-maleimidephenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, a maleimide compound represented by the following formula (IV), and a maleimide compound represented by the following formula (V); [Chemical 4] In formula (IV), R ³ each independently represents a hydrogen atom or a methyl group, and n4 represents an integer of 1 to 10; [Chemical 5] In formula (V), there are a plurality of R ^4s , each independently representing a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n5 is an average value, which represents 1＜n5≦5. [13] A prepreg, comprising: a substrate; and a resin composition as described in any one of [1] to [12] impregnated in or coated on the substrate. [14] A resin sheet with a support, comprising: a support; and a resin composition as described in any one of [1] to [12] laminated on one or both sides of the support. [15] A laminated board is formed by laminating the prepregs as described in [13]. [16] A metal-clad laminate comprising one or more laminates selected from the group consisting of a prepreg as in [13] and a resin sheet with a support as in [14], and having metal foil disposed on one or both sides of the laminate. [17] A metal-clad laminate as in [16], wherein, in a substrate after the metal foil is removed from the metal-clad laminate, the transmittance of light in the wavelength range of 400 to 2000 nm is less than 0.1%, and the thermal expansion coefficient in the plane direction at 60°C to 120°C is less than 10 ppm/°C. [18] A printed wiring board manufactured using a prepreg as in [13] as a build-up material. [19] A printed wiring board, which is manufactured using a resin sheet with a support as described in [14] as a build-up material. [20] A printed wiring board, which is manufactured using a metal-clad laminate as described in [16] or [17] as a build-up material. [21] A printed wiring board, which comprises: an insulating layer containing a resin composition as described in any one of [1] to [12], and a conductive layer formed on the surface of the insulating layer. (Effect of the invention)

According to the present invention, an object is to provide a resin composition capable of obtaining a rigid substrate having excellent light-shielding properties and low thermal expansion properties, and a prepreg, a laminate, a metal-clad laminate, a printed wiring board, and a method for manufacturing the printed wiring board using the resin composition.

The following is a detailed description of an embodiment of the present invention (hereinafter referred to as "this embodiment"), but the present invention is not limited thereto and various modifications can be made without departing from the gist of the invention.

[Resin composition] The resin composition of this embodiment is a resin composition used in a rigid substrate formed by impregnating or coating a prepreg, especially a glass cloth, as a substrate. The resin composition includes black particles (A), an inorganic filler (B), and a resin (C), and may contain other components as needed.

In the resin composition of this embodiment, the predetermined composition is set such that the content of the black particles (A) is 15-100 parts by mass relative to 100 parts by mass of the resin (C), and the content of the inorganic filler (B) is 20-110 parts by mass relative to 100 parts by mass of the resin (C). In this way, a rigid substrate having excellent light shielding properties in the visible to near-infrared region, such as the wavelength region of 400-2000nm, can be obtained, and the thermal expansion coefficient of the obtained rigid substrate is further reduced. The following is a detailed description of each component.

[Black particles (A)] There are no particular restrictions on the black particles (A), but a mixed oxide containing La and Mn is preferred, and a mixed oxide containing La, Mn, and Cu is more preferred. By using such black particles (A), the obtained rigid substrate tends to have better light shielding properties and lower thermal expansion coefficient. In addition, the insulation reliability tends to be better.

In the mixed oxide containing La and Mn, and the mixed oxide containing La, Mn, and Cu, the La content is preferably 35-70 mass %, more preferably 40-70 mass %, relative to 100 mass % of the total amount of the mixed oxide when converted to La ₂ O _3. When the La content is within the above range, the blackness is increased, and the stability as the mixed oxide tends to be better.

In the mixed oxide containing La and Mn, and the mixed oxide containing La, Mn, and Cu, the Mn content is preferably 25 to 60 mass % relative to 100 mass % of the total amount of the mixed oxide when converted as MnO _2. When the Mn content is within the above range, the blackness is increased, and the stability as the mixed oxide tends to be better.

In the mixed oxide containing La, Mn, and Cu, the content of Cu is preferably 0.5-10 mass% based on 100 mass% of the total amount of the mixed oxide, as converted into CuO. When the content of Cu is within the above range, the black color tends to increase.

The mixed oxide containing La and Mn and the mixed oxide containing La, Mn, and Cu may also contain Mo. The content of Mo is 0.01 to 5% by mass relative to 100% by mass of the total amount of the mixed oxide when converted as MoO _3. When the content of Mo is within the above range, the blackness tends to increase.

Furthermore, the mixed oxide containing La and Mn, and the mixed oxide containing La, Mn, and Cu may each contain other atoms other than the above. There is no particular limitation on the other atoms, for example, any of Li, B, Na, Mg, Al, Si, P, K, Ca, Ti, V, Fe, Zn, Sr, Y, Zr, Nb, Sn, Sb, Ba, Ta, W, Bi, Ce, Pr, Nd, or Er.

The content of these other atoms is preferably 20 mass % or less in terms of the converted value of oxides such as Li ₂ O, B ₂ O ₃ , Na ₂ O, MgO, Al ₂ O ₃ , SiO ₂ , P ₂ O ₅ , K ₂ O, CaO, TiO ₂ , V ₂ O ₅ , Fe ₃ O ₃ , ZnO, SrO, Y ₂ O ₃ , ZrO ₂ , Nb ₂ O ₃ , SnO ₂ , Sb ₂ O ₃ , BaO, Ta ₂ O ₅ , WO ₃ , Bi ₂ O ₃ , CeO ₂ , Pr ₆ O ₁₁ , Nd ₂ O ₅ , or Er ₂ O ₃ , relative to 100 mass % of the total amount of the above-mentioned mixed oxide. When the content of other atoms is within the above range, the black color increases and the stability as a mixed oxide tends to be better.

The "mixed oxide" in this embodiment includes not only a mixture of a plurality of oxides but also a complex oxide (also referred to as a "complex oxide"). Complex oxides may also include those having a calcite structure, a spinel structure, and the like.

For example, when the mixed oxide contains a complex oxide, the complex oxide is preferably a calcium titanite phase having a maximum intensity diffraction peak in the diffraction angle 2θ range of 31° to 34° in X-ray diffraction measurement using CuKα rays as an X-ray source. With such a crystal structure, the obtained rigid substrate tends to have better insulation.

Furthermore, the mixed oxide preferably contains Mn ₃ O ₄ having a spinel structure as the Mn oxide. By having such a crystal structure, the obtained rigid substrate tends to have better insulation properties.

Furthermore, the method for producing the above-mentioned mixed oxide is not particularly limited, for example, a method having the following steps: a primary pulverizing step, mixing and pulverizing the oxide raw materials of La and Mn to obtain a primary pulverized product with an average particle size of less than 5 μm; a raw material calcining step, calcining the primary pulverized product at 700 to 1200°C to obtain a raw material calcined product; and a secondary pulverizing step, pulverizing the raw material calcined product into an average particle size of less than 50 μm.

In addition, the black particles (A) of this embodiment are not limited to the above-mentioned mixed oxides, and carbon particles (carbon particles) such as carbon black, graphite powder, activated carbon powder, flaky graphite powder, acetylene black, Ketjen black, fullerene, single-layer carbon nanotubes, multi-layer carbon nanotubes, and carbon nanocones; and titanium particles such as titanium black can also be used. The black particles (A) can be used alone or in combination of two or more.

Regarding black particles (A), from the perspective of insulation, at least a portion of the surface of the black particles (A) may be covered with an insulating material such as a resin, or the surface of the black particles (A) may be not covered with an insulating material. In particular, mixed oxides containing La and Mn, and mixed oxides containing La, Mn, and Cu may be used because of their high insulation properties. By using such black particles (A), the resin composition may have better formability (hereinafter referred to as "formability") and insulation reliability when it is made into a resin sheet, a prepreg, etc.

On the other hand, for other black particles such as carbon black, it is preferred to have a coating layer made of an insulating material from the perspective of formability and insulation reliability. There is no particular restriction on the insulating material, and examples thereof include inorganic substances such as silica, and resins such as thermosetting resins. There is no particular restriction on the thermosetting resin used to coat the surface of the black particles (A), and examples thereof include epoxy resins, polyurethane resins, acrylic resins, polyethylene resins, polycarbonate resins, and polyamide resins.

The volume resistivity of the black particles (A) is preferably 1.0×10 ⁷ Ω·cm or more, and more preferably 1.0×10 ⁸ Ω·cm or more. When the volume resistivity of the black particles (A) is 1.0×10 ⁷ Ω·cm or more, the insulation reliability tends to be better. On the other hand, the higher the volume resistivity of the black particles (A), the better, and there is no special upper limit, for example: 1.0×10 ¹⁵ ·cm. In addition, the volume resistivity can be adjusted by the type of black particles (A) used and the coating layer. Among them, for mixed oxides containing La and Mn, and mixed oxides containing La, Mn, and Cu, the above-mentioned volume resistivity can be achieved even without a coating layer.

For example, the volume resistivity of a mixed oxide containing La and Mn is about 1.0×10 ⁸ Ω·cm, the volume resistivity of carbon black coated with insulation is less than 1.0×10 ³ Ω·cm, the volume resistivity of zirconium nitride is about 1.0×10 ⁶ Ω·cm, and the volume resistivity of titanium black is about 1.0×10 ⁵ Ω·cm. However, this is just an example and is not necessarily limited to this.

The average particle size of the black particles (A) is preferably 2.0 μm or less, more preferably 1.5 μm or less, still more preferably 1 μm or less, and still more preferably 0.5 μm or less. When the average particle size is 2.0 μm or less, the resin composition has better formability, and the obtained rigid substrate has better light shielding properties and a lower thermal expansion rate. In addition, the average particle size of the black particles (A) is referred to as the average particle size after coating when the black particles (A) are coated with a thermosetting resin, and is referred to as the average particle size in an uncoated state when the black particles (A) are not coated with a thermosetting resin. Furthermore, the average particle size of the black particles (A) is expressed on a volume basis, and the highest frequency particle size can be measured using a known method such as dynamic light scattering.

The content of the black particles (A) is 15-100 parts by mass, preferably 20-100 parts by mass, more preferably 25-100 parts by mass, and even more preferably 30-90 parts by mass, relative to 100 parts by mass of the resin (C). When the content of the black particles (A) is within the above range, the light shielding property of the obtained rigid substrate and the formability of the resin composition tend to be better.

The content of the black particles (A) is preferably 15 to 500 parts by mass, more preferably 20 to 400 parts by mass, more preferably 30 to 200 parts by mass, and even more preferably 30 to 100 parts by mass relative to 100 parts by mass of the inorganic filler (B). When the content of the black particles (A) is within the above range relative to the content of the inorganic filler (B), the light shielding property of the obtained rigid substrate and the formability of the resin composition tend to be better.

[Inorganic filler (B)] The inorganic filler (B) is not particularly limited, and examples thereof include kaolin, calcined kaolin, calcined clay, uncalcined clay, silica (e.g., natural silica, fused silica, amorphous silica, hollow silica, wet silica, synthetic silica, Aerosil, etc.), aluminum compounds (e.g., alumina, aluminum hydroxide, aluminum oxide, hydrotalcite, aluminum borate, aluminum nitride, etc.), magnesium compounds (e.g., magnesium carbonate, magnesium oxide, magnesium hydroxide, etc.), calcium compounds (e.g., calcium carbonate, calcium hydroxide, calcium sulfate, calcium sulfite, etc.), , calcium borate, etc.), molybdenum compounds (such as molybdenum oxide, zinc molybdate, etc.), talc (such as natural talc, calcined talc, etc.), mica (mica), glass (such as A glass, NE glass, C glass, L glass, S glass, M glass G20, E glass, T glass, D glass, S glass, Q glass, etc., short fiber glass, spherical glass, fine powder glass, hollow glass, etc.), titanium oxide, zinc oxide, zirconium oxide, barium sulfate, zinc borate, barium metaborate, sodium borate, boron nitride, condensed boron nitride, silicon nitride, carbon nitride, strontium titanate, barium titanate, zinc stannate, etc. The inorganic filler (B) may be used alone or in combination of two or more in any combination and ratio.

Among them, the inorganic filler (B) preferably contains one or more selected from the group consisting of silicon dioxide, aluminum hydroxide, aluminum oxide, alumina, alumina, magnesium oxide, molybdenum oxide, zinc molybdate, and magnesium hydroxide. By using such an inorganic filler (B), there is a tendency for better formability and lower thermal expansion rate.

The average particle size of the inorganic filler (B) is preferably 10 μm or less, more preferably 5.0 μm or less, and even more preferably 3.0 μm or less. When the average particle size is 10 μm or less, the resin composition has better formability and the obtained rigid substrate tends to have a lower thermal expansion rate. Here, the average particle size of the inorganic filler (B) is the median diameter (D50) at which the large particle size and the small particle size each account for 50% when the powder is divided into two parts based on the particle size according to the volume basis, and can be measured by known methods such as dynamic light scattering.

The content of the inorganic filler (B) is 20-110 parts by mass, preferably 25-110 parts by mass, and more preferably 25-100 parts by mass relative to 100 parts by mass of the resin (C). When the content of the inorganic filler (B) is within the above range, the moldability tends to be better and the thermal expansion rate tends to be lower.

The total content of the inorganic filler (B) and the black particles (A) is preferably 90 to 150 parts by mass, more preferably 100 to 140 parts by mass, even more preferably 110 to 130 parts by mass, and even more preferably 110 to 120 parts by mass relative to 100 parts by mass of the resin (C). When the total content of the inorganic filler (B) and the black particles (A) is within the above range, there is a tendency for better formability and lower thermal expansion rate.

[Resin (C)] The resin (C) is not particularly limited, and may be, for example, at least one selected from the group consisting of a cyanate compound (D), an epoxy compound (E), a maleimide compound (F), a phenol compound (G), an oxycyclobutane resin (H), a benzophenone compound (I), and a compound having a polymerizable unsaturated group (J). The resin (C) may be used alone or in combination of two or more.

Among them, the resin (C) preferably contains an epoxy compound (E), a phenol compound (G) and/or a cyanate compound (D). By using such a resin (C), the phenol compound (G) and/or the cyanate compound (D) act as a hardener for the epoxy compound (E), and the obtained rigid substrate tends to have better formability and lower thermal expansion rate. The following is a detailed description of each resin component.

(Cyanate compound (D)) The cyanate compound (D) may be any compound having two or more cyanate groups (cyano groups) directly bonded to an aromatic ring in one molecule, and any known compound may be used appropriately, and its type is not particularly limited.

The cyanate compound (D) is not particularly limited, and examples thereof include naphthol aralkyl cyanate compounds, novolac cyanate compounds, aromatic hydrocarbon formaldehyde cyanate compounds, and biphenyl aralkyl cyanate compounds. The cyanate compound (D) may be used alone or in combination of two or more.

Among them, from the viewpoint of moldability and low thermal expansion, naphthol aralkyl type cyanate ester compounds or novolac type cyanate ester compounds are preferred.

The naphthol aralkyl type cyanate compound is not particularly limited, and for example, the compound represented by the following formula (VI) is preferred. [Chemistry 6] In the above formula (VI), R ⁵ each independently represents a hydrogen atom or a methyl group, wherein a hydrogen atom is preferred. In the above formula (VI), n6 represents an integer greater than 1. The upper limit of n6 is preferably 10, and more preferably 6.

The novolac type cyanate compound is not particularly limited, and for example, the compound represented by the following formula (VII) is preferred. In the above formula (VII), R ⁶ each independently represents a hydrogen atom or a methyl group, wherein a hydrogen atom is preferred. In the above formula (VII), n7 represents an integer greater than 1. The upper limit of n7 is preferably 10, and more preferably 7.

The content of the cyanate compound (D) is preferably 30 to 70 parts by mass, more preferably 35 to 65 parts by mass, and even more preferably 40 to 60 parts by mass relative to 100 parts by mass of the resin (C). When the content of the cyanate compound (D) is within the above range, there is a tendency for better moldability and lower thermal expansion coefficient. In addition, when two or more cyanate compounds (D) are used in combination, the total content of the cyanate compounds (D) preferably meets the above value.

[Epoxy compound (E)] The epoxy compound (E) may be any compound having one or more epoxy groups in one molecule, and known compounds may be used. The type of epoxy compound (E) is not particularly limited. The number of epoxy groups per molecule of the epoxy compound (E) is 1 or more, preferably 2 or more.

The epoxy compound (E) is not particularly limited, and conventionally known epoxy resins may be used, for example, biphenyl aralkyl epoxy compounds, naphthalene epoxy compounds, bis-naphthalene epoxy compounds, polyfunctional phenol epoxy resins, naphthyl ether epoxy resins, phenol aralkyl epoxy resins, phenol novolac epoxy resins, cresol novolac epoxy resins, Xylene novolac type epoxy resin, naphthalene skeleton modified novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenyl novolac type epoxy resin, phenol aralkyl novolac type epoxy resin, naphthol aralkyl novolac type epoxy resin, aralkyl novolac type epoxy resin, aromatic hydrocarbon formaldehyde type epoxy compound, anthraquinone type Epoxy compounds, anthracene type epoxy resins, naphthol aralkyl type epoxy compounds, dicyclopentadiene type epoxy resins, XYLOK type epoxy compounds, bisphenol A type epoxy resins, bisphenol E type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol A novolac type epoxy resins, phenol type epoxy compounds, biphenyl type epoxy resins, Aralkylphenol novolac type epoxy resin, tris(II) skeleton epoxy compound, triglycidyl isocyanurate, aliphatic epoxy resin, polyol type epoxy resin, glycidylamine, glycidyl ester resin, compounds obtained by epoxidation of double bond of double bond-containing compounds such as butadiene, and compounds obtained by reaction of hydroxyl-containing polysilicone resins with epichlorohydrin, etc. The epoxy compound (E) may be used alone or in combination of two or more in any combination and ratio.

In addition, as exemplified above, in this specification, when a resin or compound is epoxidized to obtain an epoxide compound, the term "epoxide-type epoxide compound" may be added to the name of the resin or compound.

Among them, the epoxy compound (E) is preferably one or more selected from the group consisting of biphenyl aralkyl epoxy compounds, naphthalene aralkyl epoxy compounds, bis(naphthalene) aralkyl epoxy compounds, aromatic hydrocarbon formaldehyde aralkyl epoxy compounds, anthraquinone aralkyl epoxy compounds, and naphthol aralkyl epoxy compounds, from the viewpoint of improving the adhesion between the insulating layer and the conductive layer and the flame retardancy.

Furthermore, from the viewpoint of lowering the thermal expansion coefficient of the resin composition, the epoxy compound (E) is preferably one or more selected from the group consisting of biphenyl aralkyl epoxy compounds, naphthalene epoxy compounds, bis-naphthalene epoxy compounds and anthraquinone epoxy compounds, and biphenyl aralkyl epoxy compounds are more preferred.

The biphenyl aralkyl type epoxy compound is not particularly limited, and for example, the compound represented by the following formula (I) is preferred. By using such a biphenyl aralkyl type epoxy compound, in addition to the above, there is a tendency for better moldability and lower thermal expansion coefficient. [Chemistry 8] In formula (I), n1 represents an integer greater than 1. The upper limit of n1 is preferably 10, more preferably 7.

The content of the epoxy compound (E) is preferably 30 to 70 parts by mass, more preferably 35 to 65 parts by mass, and even more preferably 40 to 60 parts by mass relative to 100 parts by mass of the resin (C). When the content of the epoxy compound (E) is within the above range, there is a tendency for better moldability and lower thermal expansion coefficient. In addition, when two or more epoxy compounds (E) are used in combination, the total content of the epoxy compounds (E) should preferably meet the above value.

(Maleimide compound (F)) The maleimide compound (F) may be any compound having one or more maleimide groups in one molecule, and known compounds may be used appropriately, and the type is not particularly limited. The number of maleimide groups per molecule of the maleimide compound (F) is 1 or more, preferably 2 or more.

The maleimide compound (F) is not particularly limited, and examples thereof include N-phenylmaleimide, N-hydroxyphenylmaleimide, bis(4-maleimidephenyl)methane, 2,2-bis{4-(4-maleimidephenoxy)-phenyl}propane, bis(3,5-dimethyl-4-maleimidephenyl)methane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, bis(3,5-diethyl-4-maleimidephenyl)methane, a maleimide compound represented by the following formula (IV), a maleimide compound represented by the following formula (V), prepolymers of these maleimide compounds, and prepolymers of the above maleimide compounds and amine compounds. The maleimide compound (F) may be used alone or in combination of two or more in any combination and ratio.

Among them, it is preferred to contain at least one selected from the group consisting of bis(4-maleimidephenyl)methane, 2,2-bis{4-(4-maleimidephenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, a maleimide compound represented by the following formula (IV), and a maleimide compound represented by the following formula (V). [Chemistry 9] In formula (IV), R ³ each independently represents a hydrogen atom or a methyl group, and n4 represents an integer of 1 to 10. [Chemical 10] In formula (V), there are a plurality of R ^4's , each independently representing a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n5 is an average value, which represents 1＜n5≦5.

The content of the maleimide compound (F) is preferably 1 to 35 parts by mass, more preferably 10 to 30 parts by mass, and even more preferably 15 to 20 parts by mass relative to 100 parts by mass of the resin (C). When the content of the maleimide compound (F) is within the above range, there is a tendency for better moldability and lower thermal expansion coefficient. In addition, when two or more maleimide compounds (F) are used in combination, the total content of the maleimide compounds (F) preferably meets the above value.

(Phenol compound (G)) The phenol compound (G) may be any compound having two or more phenolic hydroxyl groups in one molecule, and any known compound may be used appropriately, and its type is not particularly limited.

The phenol compound (G) is not particularly limited, and examples thereof include cresol novolac type phenolic resins, biphenyl aralkyl type phenolic resins represented by the following formula (II), naphthol aralkyl type phenolic resins represented by the following formula (III), aminotriazine novolac type phenolic resins, naphthalene type phenolic resins, phenol novolac resins, alkylphenol novolac resins, bisphenol A type novolac resins, dicyclopentadiene type phenolic resins, XYLOK type phenolic resins, terpene-modified phenolic resins, and polyvinylphenols. The phenol compound (G) may be used alone or in combination of two or more.

Among them, cresol novolac type phenolic resin, biphenyl aralkyl type phenolic resin represented by the following formula (II), naphthol aralkyl type phenolic resin represented by the following formula (III), aminotriazine novolac type phenolic resin, and naphthalene type phenolic resin are more ideal from the viewpoint of moldability and low thermal expansion. Biphenyl aralkyl type phenolic resin represented by the following formula (II) and naphthol aralkyl type phenolic resin represented by the following formula (III) are more ideal. [Chemical 11] In formula (II), n2 represents an integer from 1 to 10. In formula (III), n3 represents an integer from 1 to 10.

The content of the phenol compound (G) is preferably 30 to 70 parts by mass, more preferably 35 to 65 parts by mass, and even more preferably 40 to 60 parts by mass relative to 100 parts by mass of the resin (C). When the content of the phenol compound (G) is within the above range, there is a tendency for better moldability and lower thermal expansion coefficient. In addition, when two or more phenol compounds (G) are used in combination, the total content of the phenol compounds (G) preferably meets the above value.

(Oxycyclobutane resin (H)) Oxycyclobutane resin (H) can be a generally known product, and its type is not particularly limited. Specific examples thereof include cyclohexane, 2-methylcyclohexane, 2,2-dimethylcyclohexane, 3-methylcyclohexane, 3,3-dimethylcyclohexane and other alkylcyclohexanes, 3-methyl-3-methoxymethylcyclohexane, 3,3-bis(trifluoromethyl)perfluorocyclohexane, 2-chloromethylcyclohexane, 3,3-bis(chloromethyl)cyclohexane, biphenyl-type cyclohexane, OXT-101 (trade name of Toagosei Co., Ltd.), OXT-121 (trade name of Toagosei Co., Ltd.), etc. These cyclohexane resins (H) may be used alone or in combination of two or more.

The content of the cyclohexane resin (H) is preferably 1 to 99 parts by mass, more preferably 3 to 90 parts by mass, and even more preferably 5 to 80 parts by mass relative to 100 parts by mass of the resin (C). When the content of the cyclohexane resin (H) is within the above range, heat resistance and the like tend to be better.

(Benzothiophene compound (I)) As for the benzothiophene compound (I), any compound having two or more dihydrobenzothiophene rings in one molecule may be used, and generally known products may be used, and the type thereof is not particularly limited. Specific examples thereof include bisphenol A type benzothiophene BA-BXZ (trade name of Konishi Chemicals), bisphenol F type benzothiophene BF-BXZ (trade name of Konishi Chemicals), bisphenol S type benzothiophene BS-BXZ (trade name of Konishi Chemicals), etc. These benzothiophene compounds (I) may be used alone or in combination of two or more.

The content of the benzophenone compound (I) is preferably 1 to 99 parts by mass, more preferably 3 to 90 parts by mass, and even more preferably 5 to 80 parts by mass relative to 100 parts by mass of the resin (C). When the content of the benzophenone compound (I) is within the above range, heat resistance and the like tend to be better.

(Compounds (J) with polymerizable unsaturated groups) Compounds (J) with polymerizable unsaturated groups can be generally known products, and there is no particular limitation on their types. Specific examples include vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, and divinylbiphenyl; methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, polypropylene glycol di(meth)acrylate, trihydroxymethylpropane di(meth)acrylate, trihydroxymethylpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, hexa(meth)acrylate; (Meth)acrylates of monohydric or polyhydric alcohols such as dipentatyritol ester; epoxy (meth)acrylates such as bisphenol A epoxy (meth)acrylate and bisphenol F epoxy (meth)acrylate; allyl compounds such as allyl chloride, allyl acetate, allyl ether, propylene, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl isophthalate, and diallyl maleate; benzocyclobutene resin. These compounds (J) having polymerizable unsaturated groups may be used alone or in combination of two or more.

The content of the compound (J) having a polymerizable unsaturated group is preferably 1 to 99 parts by mass, more preferably 3 to 90 parts by mass, and even more preferably 5 to 80 parts by mass relative to 100 parts by mass of the resin (C). When the content of the compound (J) having a polymerizable unsaturated group is within the above range, heat resistance, toughness, etc. tend to be better.

[Silane coupling agent and wetting dispersant] The resin composition of this embodiment may further contain a silane coupling agent and a wetting dispersant. By containing a silane coupling agent and a wetting dispersant, the dispersibility of the inorganic filler (B) and the bonding strength of the resin component, the inorganic filler (B), and the substrate described below tend to be better.

The silane coupling agent is not particularly limited as long as it is a silane coupling agent generally used for surface treatment of inorganic substances, for example: amino silane compounds such as γ-aminopropyl triethoxysilane and N-β-(aminoethyl)-γ-aminopropyl trimethoxysilane; epoxy silane compounds such as γ-glycidoxypropyl trimethoxysilane; acrylic silane compounds such as γ-acryloxypropyl trimethoxysilane; cationic silane compounds such as N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyl trimethoxysilane hydrochloride; phenyl silane compounds, etc. The silane coupling agent may be used alone or in combination of two or more.

Regarding the wetting dispersant, there is no particular limitation as long as it is a dispersing stabilizer used for coating purposes, for example: DISPERBYK (registered trademark)-110, 111, 118, 180, 161, BYK-W996, W9010, W903, etc. manufactured by BYK Chemie Japan Co., Ltd.

[Hardening accelerator] The resin composition of this embodiment may further contain a hardening accelerator. The hardening accelerator is not particularly limited, for example: imidazoles such as 2-ethyl-4-methylimidazole and 2,4,5-triphenylimidazole; organic peroxides such as benzoyl peroxide, lauryl peroxide, acetyl peroxide, p-chlorobenzoyl peroxide, di-tert-butyl diperoxyphthalate; azo compounds such as azobisnitrile; N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N-methylthiophene, triethanolamine, triethylenediamine , tetramethylbutylene diamine, N-methylpiperidine and other tertiary amines; phenols such as phenol, xylenol, cresol, resorcinol, catechol and other phenols; organic metal salts such as lead cycloalkanoate, lead stearate, zinc cycloalkanoate, zinc octanoate, manganese octanoate, tin oleate, dibutyltin apple acid, manganese cycloalkanoate, cobalt cycloalkanoate, iron acetylacetonate; solutions of these organic metal salts dissolved in phenol, bisphenol and other hydroxyl-containing compounds; inorganic metal salts such as tin chloride, zinc chloride, aluminum chloride; organic tin compounds such as dioctyltin oxide, other alkyl tins, alkyl tin oxides, etc.

[Solvent] The resin composition of this embodiment may further contain a solvent. By containing a solvent, the viscosity of the resin composition during preparation is reduced, the workability is improved, and there is a tendency for better impregnation of the substrate described later.

The solvent is not particularly limited as long as it is a solvent that can dissolve part or all of the resin components in the resin composition, for example: ketones such as acetone, methyl ethyl ketone, methyl cellulose; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide; propylene glycol monomethyl ether and its acetate, etc. The solvent may be used alone or in combination of two or more.

The resin composition of the present embodiment described above can be appropriately used as a material for constituting the metal foil-clad laminate described below. In particular, the resin composition constituting the metal foil-clad laminate contains black particles (A), an inorganic filler (B), and a resin (C), wherein the content of the black particles (A) is 15 to 100 parts by mass relative to 100 parts by mass of the aforementioned resin (C), and the content of the inorganic filler (B) is 20 to 110 parts by mass relative to 100 parts by mass of the aforementioned resin (C). The metal foil-clad laminate manufactured using the resin composition preferably meets the following requirements (1) and (2). Requirement (1): After the metal foil is removed from the aforementioned metal foil laminate, the transmittance of the substrate in the wavelength range of 400~2000nm is less than 0.1% Requirement (2): After the metal foil is removed from the aforementioned metal foil laminate, the thermal expansion rate in the surface direction at 60℃ to 120℃ is less than 10ppm/℃

With such a structure, a rigid substrate having excellent light-shielding properties and low thermal expansion properties can be obtained.

In the substrate after the metal foil is removed from the metal foil laminate, the transmittance of light in the wavelength range of 400 to 2000 nm is preferably 0.1% or less, and more preferably 0.01% or less. There is no particular restriction on the lower limit of the transmittance, and it is preferably below the detection limit. With a transmittance of 0.1% or less, it has sufficient light-shielding properties. The transmittance can be adjusted by the content of black particles (A), the content ratio of black particles (A) to inorganic filler (B), and the type of black particles (A). The transmittance can be measured according to the measurement method of the embodiment.

In addition, in this embodiment, "transmittance" refers to the value when the thickness of the substrate, that is, the insulating layer, is 0.1 mm without the metal foil. Even if the thickness of the substrate actually measured is not 0.1 mm, the transmittance in this embodiment can be obtained by calculating the transmittance of the thickness of the actually measured substrate and then converting the transmittance value to calculate the transmittance equivalent to the thickness of 0.1 mm.

In addition, in the substrate after the metal foil is removed from the metal foil laminate, the thermal expansion coefficient in the plane direction at 60°C to 120°C is preferably 10 ppm/°C or less. The lower the thermal expansion coefficient, the better, and there is no particular restriction on its lower limit, for example, 0.01 ppm/°C or more. The thermal expansion coefficient can be adjusted by the content of black particles (A), the content ratio of black particles (A) to inorganic filler (B), and the type of black particles (A). The thermal expansion coefficient can be measured using the measurement method of the embodiment.

In addition, in the present embodiment, "thermal expansion coefficient" refers to the thermal expansion coefficient in the plane direction unless otherwise specified.

[Manufacturing method of resin composition] The manufacturing method of the resin composition of this embodiment is not particularly limited, for example: a method of mixing black particles (A), inorganic filler (B), resin (C), and the other components mentioned above into a solvent in order and stirring them thoroughly. At this time, in order to make each component dissolve or disperse uniformly, known treatments such as stirring, mixing, and kneading can be implemented. Specifically, by using a stirring tank equipped with a stirrer with appropriate stirring capacity to implement stirring and dispersing treatment, the dispersibility of black particles (A) and inorganic filler (B) in the resin composition can be better. The above-mentioned stirring, mixing and kneading treatment can be appropriately performed using a known device for the purpose of mixing, such as a ball mill or a bead mill, or a revolving or rotating mixing device.

Furthermore, during the preparation of the resin composition, a solvent may be used as needed. There is no particular limitation on the type of solvent as long as it can dissolve the resin in the composition.

[Application] The resin composition of the present embodiment described above can be ideally used in prepregs, resin sheets with supports, laminates, metal-clad laminates, printed wiring boards, or build-up materials. The following is a description of each application.

[Prepreg] The prepreg of the present embodiment has a substrate, and the resin composition of the present embodiment impregnated in or coated on the substrate. The method for manufacturing the prepreg can be carried out according to the conventional method without special restrictions. For example, the prepreg of the present embodiment can be manufactured by impregnating or coating the resin composition of the present embodiment on the substrate, and then heating it in a dryer at 100~200℃ for 1~30 minutes to semi-harden it (B stage).

The content of the resin composition of the present embodiment in the prepreg is preferably 30-90% by mass, more preferably 35-85% by mass, and even more preferably 40-80% by mass, relative to the total amount of the prepreg. When the content of the resin composition is within the above range, the moldability tends to be better.

(Substrate) The substrate is not particularly limited, and any known material used for printed wiring boards can be appropriately selected according to the intended use and performance. Specific examples of the fiber constituting the substrate are not particularly limited, and include, for example, glass fibers such as E glass, D glass, S glass, Q glass, spherical glass, NE glass, L glass, and T glass; inorganic fibers other than glass such as quartz; wholly aromatic polyamides such as poly(p-phenylene terephthalate) (Kevlar (registered trademark), manufactured by DuPont), co-poly(p-phenylene terephthalate) and 3,4'-oxydiphenylene terephthalate (Technora (registered trademark), manufactured by Teijin Technoproducts Co., Ltd.); 2,6-hydroxynaphthoic acid (naphthoic acid) and p-hydroxybenzoic acid (vectran (registered trademark), manufactured by Kuraray Co., Ltd.), Zxion (registered trademark, KB SEIREN, LTD) and other polyesters; poly(p-phenylene benzobis(oxazole) (Zylon (registered trademark), manufactured by Toyobo Co., Ltd.), polyimide and other organic fibers. These base materials may be used alone or in combination of two or more.

Among them, at least one selected from the group consisting of E glass cloth, T glass cloth, S glass cloth, Q glass cloth, and organic fiber is preferred.

The shape of the substrate is not particularly limited, for example: woven fabric, non-woven fabric, coarse yarn, chopped strand felt, surface felt, etc. The weaving method of the woven fabric is not particularly limited, for example: plain weave, basket weave, twill weave, etc., and can be appropriately selected from these well-known ones according to the intended use or performance. In addition, glass woven fabrics obtained by opening the fibers or surface treating them with a silane coupling agent are suitable for use. The thickness or mass of the substrate is not particularly limited, and generally, about 0.01 to 0.3 mm is suitable for use. In particular, considering the strength and water absorption, the substrate is preferably a glass woven fabric with a thickness of less than 200 μm and a mass of less than 250 g/m ² , and more preferably a glass woven fabric composed of glass fibers of E glass, S glass and T glass.

[Resin sheet with support] The resin sheet with support of the present embodiment has a support and the resin composition of the present embodiment disposed on the support. The resin sheet with support can be produced by directly coating the resin composition on a support such as a metal foil or a resin film and drying it. The resin sheet with support can be thinned to form an insulating layer of a metal foil-clad laminate, a printed wiring board, etc.

The support is not particularly limited, and known materials used in various printed wiring board materials can be used. For example: organic film substrates such as polyimide film, polyamide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film, polyethylene (PE) film, polycarbonate film, ethylene tetrafluoroethylene copolymer film, and release films coated with release agents on the surface of these films, conductive foils such as metal foils, glass plates, SUS plates, plate-shaped inorganic films such as FPR. Among them, electrolytic copper foil and PET film are preferred.

The coating method includes, for example, dissolving the resin composition of the present embodiment in a solvent to form a solution, and then coating the solution on a support using a coating rod, a die coater, a scraper, a Baker applicator, or the like.

The resin sheet with support is preferably prepared by applying the resin composition to a support and semi-hardening it (B-stage). Specifically, for example, the resin composition is applied to a support such as a metal foil and then semi-hardened in a dryer at 100-200°C for 1-60 minutes to prepare the resin sheet with support. The amount of the resin composition attached to the support is preferably in the range of 1-300 μm based on the resin thickness of the resin sheet with support.

Other aspects of the support-attached resin sheet of this embodiment include a single-layer resin sheet. The single-layer resin sheet includes a resin composition. The single-layer resin sheet is formed into a sheet by forming the resin composition. The manufacturing method of the single-layer resin sheet can be carried out according to the conventional method without special restrictions. For example, it can be obtained by peeling off or etching the support from the above-mentioned resin sheet with a support. Alternatively, the resin composition of this embodiment can be dissolved in a solvent to form a solution, and then supplied to a mold having a sheet-shaped cavity and dried to form a sheet, so as to obtain a single-layer resin sheet without using a support.

[Laminated board] The laminated board of this embodiment is formed by laminating the above-mentioned prepregs. The laminated board can be any one or more prepregs without any particular limitation, and can also have any other layers. The manufacturing method of the laminated board can appropriately adopt a generally known method without any particular limitation. For example, the laminated board can be obtained by laminating the above-mentioned prepregs with each other, or the prepreg and other layers, and heating and pressing them to form. The heating temperature at this time is not particularly limited, and 65~300℃ is more ideal, and 120~270℃ is more ideal. In addition, the pressing pressure is not particularly limited, and 2~5MPa is more ideal, and 2.5~4MPa is more ideal. The laminated plate of this embodiment can be suitably used as a metal foil-clad laminated plate described later by further comprising a layer made of metal foil.

[Metal foil-clad laminate] The metal foil-clad laminate of this embodiment contains one or more selected from the group consisting of the above-mentioned prepreg and the above-mentioned resin sheet with a support, and has metal foil arranged on one side or both sides of the laminate. In the metal foil-clad laminate of this embodiment, the prepreg and the resin sheet form an insulating layer, and the insulating layer may be composed of one layer of the prepreg and the resin sheet, or may be composed of two or more layers of the above-mentioned prepreg and the resin sheet.

Copper, aluminum, etc. can also be used as metal foil. The metal foil used here is not particularly limited as long as it is a printed wiring board material. It is preferably a well-known copper foil such as a rolled copper foil and an electrolytic copper foil. In addition, the thickness of the metal foil (conductor layer) is not particularly limited, but 1 to 70 μm is ideal, and 1.5 to 35 μm is more preferred.

The forming method and forming conditions of the metal-clad laminate are not particularly limited, and the methods and conditions of general laminates and multi-layer laminates for printed wiring boards can be adopted. For example, a multi-stage press, a multi-stage vacuum press, a continuous forming machine, a high-pressure autoclave forming machine, etc. can be used for forming the metal-clad laminate. In addition, in the forming of the metal-clad laminate, generally speaking, the temperature is 100~300℃, the pressure is a surface pressure of 2~100kgf/ ^cm2 , and the heating time is in the range of 0.05~5 hours. Furthermore, post-hardening can be performed at a temperature of 150~300℃ as needed. In addition, a multi-layer board can be made by combining the above-mentioned prepreg and a wiring board for the inner layer produced separately and laminating them.

In particular, the metal foil-clad laminate of the present embodiment comprises a laminate formed of at least one selected from the group consisting of a prepreg and a resin sheet with a support, and metal foil disposed on one or both sides of the laminate, wherein the prepreg comprises a substrate and a resin composition impregnated or coated on the substrate, the resin sheet with a support comprises a support, and the aforementioned resin composition laminated on one or both sides of the support, wherein the resin composition comprises black particles (A), an inorganic filler (B), and a resin (C ), the content of the black particles (A) is 15-100 parts by mass relative to 100 parts by mass of the resin (C), the content of the inorganic filler (B) is 20-110 parts by mass relative to 100 parts by mass of the resin (C), the transmittance of the substrate after the metal foil is removed from the metal foil-clad laminate in the range of wavelength 400-2000nm is less than 0.1%, and the thermal expansion coefficient in the plane direction at 60°C to 120°C is preferably less than 10ppm/°C.

By having such a structure, a metal-clad laminate having excellent light-shielding properties and low thermal expansion properties and a printed wiring board using the same can be obtained.

The transmittance of the substrate after the metal foil is removed from the metal foil laminate is preferably 0.1% or less, more preferably 0.01% or less in the wavelength range of 400 to 2000 nm. There is no particular restriction on the lower limit of the transmittance, but it is preferably below the detection limit. The transmittance is below 0.1%, which has sufficient light-shielding properties. The transmittance can be adjusted by the content of black particles (A), the content ratio of black particles (A) to inorganic filler (B), and the type of black particles (A). The transmittance can be measured according to the measurement method of the embodiment.

In addition, the thermal expansion coefficient of the substrate after the metal foil is removed from the metal foil laminated plate in the surface direction at 60°C to 120°C is preferably 10 ppm/°C or less. The lower the thermal expansion coefficient, the better, and there is no special restriction on its lower limit, for example, it is 0.01 ppm/°C or more. The thermal expansion coefficient can be adjusted by the content of black particles (A), the content ratio of black particles (A) to inorganic filler (B), and the type of black particles (A). The thermal expansion coefficient can be measured according to the measurement method of the embodiment.

In the embodiment, the transmittance and thermal expansion coefficient were measured using a metal foil-clad laminate having the following E glass fabric composition from the viewpoint of specifying the measurement conditions. However, the glass fabric used to form the prepreg using the resin composition of the embodiment is not limited to the E glass fabric having the following composition, and the aforementioned various substrates can be used. In addition, the molding method and molding conditions of the metal foil-clad laminate are not particularly limited to the above conditions. Corresponding IPC item: 2116 Density (pieces/25mm) vertical: 62 Density (pieces/25mm) horizontal: 58 Thickness (mm): 0.100 Mass (g/m ² ): 108.5 There is no particular restriction on commercially available E-glass fabrics having the above-mentioned structure, for example: 1031NT-1270-S640 manufactured by Arisawa Manufacturing Co., Ltd.

[Printed wiring board] The printed wiring board of the present embodiment has an insulating layer including the resin composition of the present embodiment, and a conductive layer formed on the surface of the insulating layer. Such a printed wiring board can be manufactured by using the above-mentioned prepreg, the above-mentioned resin sheet with a support, and/or the above-mentioned metal-clad laminate as a build-up material. The above-mentioned metal-clad laminate can be ideally used as a printed wiring board by forming a predetermined wiring pattern. In addition, the above-mentioned metal-clad laminate has good light-shielding properties, low thermal expansion coefficient, and good formability, and can be effectively used in particular as a material for a printed wiring board for a semiconductor package that requires such performance.

The example of manufacturing a printed wiring board using a metal foil laminate is used for explanation. First, the metal foil laminate is prepared. Then, the surface of the metal foil laminate is etched to form an inner circuit to make an inner substrate. The inner circuit surface of the inner substrate is subjected to surface treatment to improve the bonding strength as needed, and then the required number of prepregs are stacked on the inner circuit surface, and then the metal foil for the outer circuit is stacked on the outer side, and the heat and pressure are applied to form an integral body. In this way, a multi-layer laminate is manufactured in which a base material and an insulating layer composed of a cured product of the resin composition of the present embodiment are formed between the metal foil for the inner layer circuit and the outer layer circuit. Then, after the multi-layer laminate is subjected to hole opening processing for through holes and vias, a desmearing treatment is performed to remove the resin residue, i.e., the resin residue from the resin component contained in the cured product. Thereafter, a metal film is formed on the wall surface of the hole to conduct the metal foil for the inner layer circuit and the outer layer circuit, and then the metal foil for the outer layer circuit is subjected to an etching treatment to form the outer layer circuit, thereby manufacturing a printed wiring board.

The printed wiring board obtained in the above manufacturing example has an insulating layer and a conductive layer formed on the surface of the insulating layer, and the insulating layer contains the resin composition of the above-mentioned embodiment, that is, the above-mentioned prepreg (substrate and the above-mentioned resin composition attached thereto) and the resin composition layer of the metal foil-clad laminate (a layer composed of the above-mentioned resin composition) constitute the insulating layer containing the above-mentioned resin composition.

Furthermore, when a metal-clad laminate is not used, a conductor layer forming a circuit may be formed on the prepreg, the support-attached resin sheet, or the resin composition to produce a printed wiring board. In this case, the conductor layer may be formed by electroless plating.

Furthermore, a step of applying a solder resist to the printed wiring board obtained as described above and forming an insulating film to protect the circuit pattern can also be performed. More specifically, a method having the following steps can be listed: preparing a printed wiring board as described above; forming a photosensitive component layer that is cured with light of a wavelength of 350 to 420 nm on both sides of the printed wiring board; and configuring a mask pattern on the surface of the photosensitive component layer, and exposing it to light of a wavelength of 350 to 420 nm through the mask pattern. After exposure, the uncured portion of the photosensitive component layer is developed to obtain a printed wiring board with a protected circuit pattern. In addition, the photosensitive component layer, for example, a solder resist layer.

In addition, a method for manufacturing a coreless printed wiring board, for example, does not carry out the step of preparing the printed wiring board as described above, but instead carries out the step of preparing a core substrate, and the step of obtaining a laminated body formed by laminating at least one insulating layer containing the resin composition of the present embodiment and a conductive layer disposed on the outermost surface of the insulating layer on the core substrate. That is, by laminating one or more insulating layers and one or more conductive layers on the core substrate, a laminated body with a build-up layer formed on the core substrate can be obtained. Thereafter, by removing (peeling off) the core substrate, a coreless printed wiring board (also referred to as a coreless substrate) is formed.

Furthermore, by performing a step of forming a photosensitive composition layer and a step of exposing the coreless substrate, a coreless printed wiring board having a circuit pattern formed thereon can be obtained.

[Build-up material] The resin composition of this embodiment can be used as a build-up material. Here, "build-up" means stacking prepregs, resin sheets with supports, and/or metal foil laminates, and repeating hole processing, wiring formation, etc. layer by layer to produce a printed wiring board with a multi-layer structure.

More specifically, a prepreg, a resin sheet with a support, or a metal-clad laminate using the resin composition of the present embodiment can be used as a build-up material for a printed wiring board. In a printed wiring board formed using the prepreg or the resin sheet with a support of the present embodiment, the prepreg or the resin sheet with a support constitutes an insulating layer. In addition, in a printed wiring board formed using a metal-clad laminate, the prepreg (base material and the resin composition attached thereto) constitutes an insulating layer.

Specifically, when the prepreg of this embodiment is used as a build-up material, the prepreg is first used to make a metal-clad laminate according to the above-mentioned method for making a metal-clad laminate, and then the printed wiring board of this embodiment can be obtained by the above-mentioned method. Or when it is used as a material for a multi-layer printed wiring board as described later, the prepreg can also be directly used as a build-up material.

When the resin sheet with a support of the present embodiment is used as a build-up material, the printed wiring board of the present embodiment can be obtained by performing surface treatment on the resin composition layer (insulating layer) of the resin sheet with a support according to a conventional method and forming a wiring pattern (conductor layer) on the surface of the insulating layer by plating.

Furthermore, when the metal foil-clad laminate of the present embodiment is used as a build-up material, the metal foil of the metal foil-clad laminate is etched according to the conventional method, the layer composed of the prepreg (insulating layer) is surface treated, and a wiring pattern (conductor layer) is formed on the surface of the insulating layer by plating, thereby obtaining the printed wiring board of the present embodiment.

In any case, other various steps may be added as needed (for example, hole opening processing to form through holes, vias, etc.). [Example]

The present invention is described in more detail below using examples and comparative examples. The present invention is not limited to the following examples.

[Synthesis Example 1] Synthesis of naphthol aralkyl cyanate compound (SNCN) 300 g (1.28 mol in terms of OH group) of α-naphthol aralkyl resin (SN495V, OH group equivalent: 236 g/eq., manufactured by Nippon Steel Chemical Co., Ltd.) and 194.6 g (1.92 mol) of triethylamine (1.5 mol per 1 mol of hydroxyl group) were dissolved in 1800 g of dichloromethane, and the mixture was named Solution 1.

125.9g (2.05mol) of cyanogen chloride (1.6mol per 1mol of hydroxyl), 293.8g of dichloromethane, 194.5g (1.92mol) of 36% hydrochloric acid (1.5mol per 1mol of hydroxyl), and 1205.9g of water were stirred, and solution 1 was added over 30 minutes while maintaining the liquid temperature at -2~-0.5℃. After the addition of solution 1 was completed, the mixture was stirred at the same temperature for 30 minutes, and then a solution (solution 2) prepared by dissolving 65g (0.64mol) of triethylamine (0.5mol per 1mol of hydroxyl) in 65g of dichloromethane was added over 10 minutes. After the addition of solution 2 was completed, the mixture was stirred at the same temperature for 30 minutes to complete the reaction.

The reaction solution was then allowed to stand to separate the organic phase and the aqueous phase. The obtained organic phase was washed 5 times with 1300 g of water. The electrical conductivity of the waste water from the 5th washing was 5 μS/cm, confirming that the ionic compounds had been fully removed by washing with water.

The organic phase after washing was concentrated under reduced pressure and finally concentrated and dried at 90°C for 1 hour to obtain 331 g of the target naphthol aralkyl type cyanate compound (SNCN) (orange viscous substance). The mass average molecular weight Mw of the obtained SNCN was 600. In addition, the infrared absorption spectrum of SNCN showed absorption at 2250 cm ^-1 (cyanate group) and no absorption of hydroxyl group.

[Example 1] 50 parts by mass of a biphenyl aralkyl epoxy compound (NC-3000-FH, manufactured by Nippon Kayaku Co., Ltd.), 50 parts by mass of a biphenyl aralkyl phenol resin (KAYAHARD GPH-103, hydroxyl equivalent: 231 g/eq., manufactured by Nippon Kayaku Co., Ltd.), 20 parts by mass of bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (BMI-70, manufactured by Yamato Kasei Kogyo Co., Ltd.), and a mixed oxide containing La and Mn (GY107, La content in terms of La ₂ O ₃ : 60% by mass, Mn content in terms of MnO ₂ : 35% by mass, volume resistivity: 1.0×10 ⁸ ) as black particles (A) were prepared. Ω・cm, average particle size 1.0μm, manufactured by Nakajima Sangyo Co., Ltd.), 50 parts by mass of silica (SC4500-SQ, manufactured by Admatechs Co., Ltd., average particle size 1.5μm), 70 parts by mass of talc coated with zinc molybdate (KEMGARD 911C, zinc molybdate loading: 10% by mass, Sherwin-Williams Chemicals), 10 parts by mass of a wetting dispersant (DISPERBYK (registered trademark)-161, manufactured by BYK Chemie Japan Co., Ltd.), and 0.3 parts by mass of a curing accelerator (2,4,5-triphenylimidazole, manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and diluted with methyl ethyl ketone to obtain a varnish.

This varnish was impregnated onto a 0.1mm thick E-glass fabric (manufactured by Arisawa Seisakusho, 1031NT-1270-S640), and dried at 165°C for 3 minutes to obtain a prepreg (0.1mm thick) containing 50% by mass of the resin composition. The properties of the E-glass fabric used are as follows. Corresponding IPC item: 2116 Density (roots/25mm) vertical: 62 Density (roots/25mm) horizontal: 58 Thickness (mm): 0.100 Mass (g/m ² ): 108.5

The black particles (A) (GY107) have a calcium titanite phase having a diffraction peak with a maximum intensity in a diffraction angle 2θ range of 31° to 34° in X-ray diffraction measurement using CuKα rays as an X-ray source, and contain Mn ₃ O ₄ having a spinel structure as Mn oxide.

[Example 2] The same method as Example 1 was used except that the amount of black particles (A) (GY107) was set to 20 parts by mass and the amount of silicon dioxide (SC4500-SQ) was set to 120 parts by mass to obtain a prepreg.

[Example 3] The same method as Example 1 was followed except that the amount of black particles (A) (GY107) used was 30 parts by mass and the amount of silicon dioxide (SC4500-SQ) used was 90 parts by mass to obtain a prepreg.

[Example 4] The same method as Example 1 was followed except that the amount of black particles (A) (GY107) used was 120 parts by mass and the amount of silicon dioxide (SC4500-SQ) used was 20 parts by mass to obtain a prepreg.

[Example 5] A prepreg was obtained in the same manner as in Example 1 except that 50 parts by weight of SNCN was used instead of biphenyl aralkyl phenolic resin (GPH-103).

[Example 6] A prepreg was obtained in the same manner as in Example 1 except that 50 parts by weight of SNCN was used instead of biphenyl aralkyl phenolic resin (GPH-103) and bis(3-ethyl-5-methyl-4-maleimidephenyl)methane was not used.

[Comparative Example 1] A prepreg was obtained in the same manner as in Example 2 except that the black particles (A) (GY107) were not used.

[Comparative Example 2] The same method as Example 2 was followed except that the amount of black particles (A) (GY107) used was 15 parts by mass to obtain a prepreg.

[Comparative Example 3] The same method as Example 1 was followed except that the amount of black particles (A) (GY107) was 130 parts by mass and the amount of silicon dioxide (SC4500-SQ) was 10 parts by mass to obtain a prepreg.

[Comparative Example 4] The same method as Example 1 was followed except that the amount of black particles (A) (GY107) used was 20 parts by mass and the amount of silicon dioxide (SC4500-SQ) used was 130 parts by mass to obtain a prepreg.

[Comparative Example 5] Instead of using black particles (A) (GY107), 10 parts by mass of insulating coated carbon black (product name #B503, manufactured by Mikoku Color Co., Ltd., average particle size 0.1 μm) was used. The same procedure as in Example 2 was followed to obtain a prepreg.

[Comparative Example 6] A prepreg was obtained in the same manner as in Comparative Example 5 except that ¹⁰ parts by mass of non-insulating carbon black (product name: MHI Black #273, manufactured by Mikoku Color Co., Ltd.) was used instead of using insulating coated carbon black (product name: #B503, volume resistivity: 1.0×10 3 Ω·cm or less, manufactured by Mikoku Color Co., Ltd., average particle size: 0.1 μm).

[Formability] Electrolytic copper foils (3EC-LPIII, manufactured by Mitsui Metal & Mining Co., Ltd.) with a thickness of 12 μm were placed above and below the prepreg obtained in the embodiment or the comparative example, and laminate forming was performed for 120 minutes at a pressure of 30 kgf/ ^cm2 and a temperature of 220°C to obtain a copper-clad laminate with an insulating layer thickness of 0.1 mm as a metal foil-clad laminate. After the copper foil of the copper-clad laminate was removed by etching, the surface was observed to confirm whether there were pores, and the formability was evaluated according to the following evaluation criteria. 0: Pores were considered to be absent ×: Pores were considered to be present

[Light-shielding property] Electrolytic copper foils (3EC-LPIII, manufactured by Mitsui Metal & Mining Co., Ltd.) with a thickness of 12 μm were placed above and below the prepreg obtained in the embodiment or the comparative example, and laminated for 120 minutes at a pressure of 30 kgf/cm ² and a temperature of 220°C to obtain a copper-clad laminate with an insulating layer thickness of 0.1 mm as a metal-clad laminate. The substrate obtained by etching away the copper foil of the copper-clad laminate was used as a sample, and the transmittance of light with a wavelength of 400 to 2000 nm was measured. The measurement was performed using a spectrophotometer U-4100 manufactured by Hitachi Advanced Technologies. The light-shielding property was evaluated based on the obtained transmittance according to the following evaluation criteria. ◎: The transmittance of light in the wavelength range of 400-2000nm is 0.01% or less ○: The transmittance of light in the wavelength range of 400-2000nm exceeds 0.01% and is 0.1% or less ×: The transmittance of light in the wavelength range of 400-2000nm exceeds 0.1%

[Thermal expansion coefficient] The copper foil of the copper-clad laminate with an insulating layer thickness of 0.1 mm obtained as described above was removed by etching. According to JIS C 6481, the linear thermal expansion coefficient (ppm/℃) in the plane direction was measured as the thermal expansion rate from 60℃ to 120℃ by heating from 40℃ to 340℃ at a rate of 10℃ per minute using a thermomechanical analysis device (manufactured by TA INSTRUMENT) according to the TMA method (Thermo-mechanical analysis).

[Insulation resistance] Eight prepregs obtained in the embodiments or comparative examples were stacked, and electrolytic copper foils (3EC-LPIII, manufactured by Mitsui Metal & Mining Co., Ltd.) with a thickness of 12 μm were placed on the top and bottom. Lamination molding was performed at a pressure of 30 kgf/cm ² and a temperature of 220°C for 120 minutes to obtain a copper-clad laminate with an insulation layer thickness of 0.8 mm as a metal foil-clad laminate. After removing the copper foil of the copper-clad laminate by etching, the samples were cut into 20×40mm samples and treated for 24 hours at 121℃ and 2 atmospheres in a pressure cooker tester (manufactured by Hirayama Seisakusho, PC-3 model) under the conditions of humidity and heat resistance. After that, 500V DC was applied and the insulation resistance between the terminals was measured after 60 seconds.

[Table 1] Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Formability ○ ○ ○ ○ ○ ○ Light blocking test ◎ ○ ◎ ◎ ◎ ◎ Thermal expansion rate [ppm] 9 9 9 9 9 9 Insulation resistance(Ω) Normal 2.0×10 ¹⁵ - - - 2.0×10 ¹⁵ 2.0×10 ¹⁵ PCT 24h after treatment 2.0×10 ¹⁴ - - - 2.0×10 ¹⁴ 2.0×10 ¹⁴ Comparison Example 1 Comparison Example 2 Comparison Example 3 Comparison Example 4 Comparison Example 5 Comparison Example 6 Formability ○ ○ × × ○ × Light blocking test × × ◎ ○ ◎ ◎ Thermal expansion rate [ppm] 9 9 ＊ ＊ 11 ＊ Insulation resistance(Ω) Normal 2.0×10 ¹⁵ - ＊ ＊ 2.0×10 ¹⁵ ＜1.0×10 ⁸ PCT 24h after treatment 2.0×10 ¹⁴ - ＊ ＊ 2.0×10 ¹⁴ ＜1.0×10 ⁸ ※-: Not measured ※＊: Unable to measure due to pores [Industrial applicability]

The resin composition of the present invention is industrially applicable as a material used in the manufacture of a rigid substrate.

Claims (16)

A resin composition comprises black particles (A), an inorganic filler (B), and a resin (C), wherein the black particles (A) comprise a mixed oxide containing La and Mn, the inorganic filler (B) comprises one or more selected from the group consisting of silica, aluminum hydroxide, aluminum oxide, alumina, magnesium oxide, molybdenum oxide, zinc molybdate, and magnesium hydroxide, and the resin ( C) contains at least one selected from the group consisting of a cyanate compound (D), an epoxy compound (E), and a maleimide compound (F), the content of the black particles (A) is 15 to 100 parts by mass relative to 100 parts by mass of the resin (C), and the content of the inorganic filler (B) is 20 to 110 parts by mass relative to 100 parts by mass of the resin (C). The resin composition of claim 1, wherein the mixed oxide has a calcium-titanium phase, the calcium-titanium phase has a diffraction peak with maximum intensity in the range of 31° to 34° of the diffraction angle 2θ in X-ray diffraction measurement using CuKα rays as the X-ray source, and the mixed oxide contains Mn ₃ O ₄ with a spinel structure as the Mn oxide. The resin composition of claim 1 or 2, wherein the content of La in the mixed oxide is 35-70 mass % relative to 100 mass % of the total amount of the mixed oxide when converted _{as La2O3} , and the content of Mn in the mixed oxide is 25-60 mass % relative to 100 mass % of the total amount of the mixed oxide when converted as _MnO2 . The resin composition of claim 1 or 2, wherein the volume resistivity of the black particles (A) is greater than 1.0×10 ⁷ Ω‧cm. The resin composition of claim 1 or 2, wherein the black particles (A) are not coated with insulating material. The resin composition of claim 1 or 2, wherein the epoxy compound (E) comprises a compound represented by the following formula (I);

In formula (I), n1 represents an integer from 1 to 10. The resin composition of claim 1 or 2, wherein the maleimide compound (F) comprises at least one selected from the group consisting of bis(4-maleimidephenyl)methane, 2,2-bis{4-(4-maleimidephenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, a maleimide compound represented by the following formula (IV), and a maleimide compound represented by the following formula (V);

In formula (IV), R ³ each independently represents a hydrogen atom or a methyl group, and n4 represents an integer of 1 to 10;

In formula (V), there are a plurality of R ^4's , each independently representing a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n5 is an average value, which represents 1<n5≦5. A prepreg having: a substrate; and a resin composition as described in any one of claims 1 to 7 impregnated in or coated on the substrate. A resin sheet with a support, comprising: a support; and a resin composition as described in any one of claims 1 to 7 laminated on one or both sides of the support. A laminated board is formed by laminating layers of prepreg as claimed in claim 8. A metal foil-clad laminate comprises one or more laminates selected from a group consisting of a prepreg as in claim 8 and a resin sheet with a support as in claim 9, and has metal foil disposed on one or both sides of the laminate. A metal-clad laminate as claimed in claim 11, wherein, in a substrate after the metal foil is removed from the metal-clad laminate, the transmittance of light in the wavelength range of 400 to 2000 nm is less than 0.1%, and the thermal expansion coefficient in the plane direction at 60°C to 120°C is less than 10 ppm/°C. A printed wiring board is made using the prepreg as claimed in claim 8 as a build-up material. A printed wiring board is made using a resin sheet with a support as claimed in claim 9 as a build-up material. A printed wiring board made using the metal-clad laminate of claim 11 or 12 as a build-up material. A printed wiring board comprises: an insulating layer containing the resin composition as described in any one of claims 1 to 7, and a conductive layer formed on the surface of the insulating layer.